By Dong Wang Huntsman Advanced Materialsfeiplar.com.br/materiais/palestras/aeroespacial/Huntsman.pdf · By Dong Wang Huntsman Advanced Materials ... Araldite® MT 35700 (BPF)

By Dong Wang

Huntsman Advanced Materials

Benzoxazine Resin for Aerospace Interior Applications

Advanced Materials Advanced Materials

Outline

Background and challenges

Huntsman ADMAT product-line and benzoxazine technology overview

Benzoxazine resin for transportation interior application

− Resin chemistry comparison to traditional phenolic resin

− XU 35710 FST neat resin properties

− XU 35710 FST composite laminate properties

− XU 35710 FST resin for pre-pregging process

Summary

Disclaimer


Background and Challenges

Examples of Aerospace interior applications

− Liners

− Ceilings

− Floor panels

− Overhead bins

− Bulkheads

Phenolic resin laminate for aerospace interior applications

− Low cost

− Excellent FST performance



Main issues of using traditional phenolic resin

Volatile release

during curing

EHS concerns

Long manufacturing

cycle time

Low mechanical

performances

Laminate quality

control difficulty

Other issues of using traditional phenolic resin

− Poor storage stability

− Typically solvent based



Ideal target of next generation resin for interior application

Performance:

− Comparable FST performance

− Improved laminate mechanical performance

− Improved storage stability

Processing:

− Low volatile release curing

− Short manufacturing cycle time

− Easy laminate quality control

− Processible by liquid molding (RTM, VARTM, RFI, etc)

Others:

− Comparable cost


Base Resins Specialty Components Formulations

Curing Agents Multifunctionals

Matting agents Crosslinkers

Reactive Diluents

BisF/EPN/ECN

Waterbornes Reactive PAA

Adhesives Encapsulation

Tooling Insulation

Composites Protection

Liquid epoxy resins

Solid epoxy resins

Epoxy solutions

Laminates

Huntsman Advanced Materials ― Our Products


High-Performance Building Blocks for Advanced Composites

￭ Liquid & Solid Bis-A Epoxies

￭ Bis-F Epoxies

￭ EPNs

￭ ECNs

￭ Reactive Epoxy Diluents

￭ Brominated Bis-A Epoxy

￭ Toughened Epoxies

￭ Cycloaliphatic Epoxies

￭ Specialty Multifunctional Epoxies –

Liquids & Solids

￭ Bismaleimides / Polyimides

￭ Polyamide-Imide

￭ Cyanate Esters

￭ Aliphatic Amine

￭ Cycloaliphatic Amine

￭ Polyamides

￭ Phenalkamines

￭ Aromatic Amines

￭ Anhydride

￭ Accelerators

￭ Specialty Latent Hardeners

Curing Agents

Chemistry Offered by Huntsman Advanced Material


High-Performance Building Blocks for Advanced Composites

Product Families Features

Multifunctionals Araldite® MY 720 Family Liquid, easy processing, high Tg

Araldite® MY 0500 Family Low-viscosity liquid, high Tg

Araldite® MY 0600 Family Liquid, high modulus, high Tg

Other / Misc Araldite® MY 0816 Low-viscosity liquid, high toughness

Tactix® 742 High Tg, high thermal stability

Tactix® 556 / 756 High moisture resistance, high Tg

Novolac Resins Araldite® Epoxy Phenol Novolacs (EPNs) Chemical & heat resistance

Araldite® Epoxy Cresol Novolacs (ECNs) Chemical & heat resistance

Bismaleimides Matrimid® 5292 A/B Very high temperature resistance (above

300ºC), good water & chemical resistance

Curing Agents Aradur® 9664-1 / 976-1 High Tg, high modulus, good chemical and

thermal resistance

Aradur® 9719-1 High modulus, high toughness

Typical Product Offered by Huntsman Advanced Material


S

N

O O

N

CH3

CH3

O O

NN

CH

2

O O

NN

N

O

N

O

O

O N

O O

N

Thiodiphenol-based

Benzoxazine

Bisphenol A-based

Benzoxazine

Bisphenol F-based

Benzoxazine

Dicyclopentadiene-based

Benzoxazine

Phenolphthalein-based

Benzoxazine

NO

R

Mono-phenol-based

Benzoxazine

Huntsman Benzoxazine Technology

Advanced Materials

Product Advantages/Benefits Potential Application

XU35610 (BPA)

• Good solvent solubility • Volatile/void free during curing • High Tg/modulus

• Aerospace structural • High temp tooling

Araldite® MT 35700 (BPF)

• High-Tg/modulus • Good chemical resistance • Good flammability properties

• Aerospace structural • Transportation interior • High temp tooling

XU35710 FST

• Good FST • Low viscosity • Low temperature (350F) curing • Low cost • High Modulus/tough-ness

• Aerospace and other transportation interior • Industrial composite (auto, down-hole, etc.) • FST tooling

XU 35910 (Thiodiphenol)

• Low viscosity • Low temperature (350F) curing • High Tg/ modulus

• Aerospace structural • Industrial composite (auto, down-hole, etc.) • High temp tooling

XU 35500 (Cardanol)

• Liquid • Green chemistry

• Viscosity diluent for Box formulation in various applications • Industrial composite building-block (auto, down-hole, etc)

DT 300 / DT 310 • White crystals • Catalysts used to lower cure temperature or shorten cure cycle. Suitable for Benzoxazines or BOX/Epoxy blends

Benzoxazine Products for Composites Application


Benzoxazine for Interior Application

Main advantages of benzoxazine resins (for interior application)

− High modulus

− Low water absorption / moisture pick-up

− High Tg/thermal performance

− Good flame retardant properties

− Low curing shrinkage

− Good electrical properties

− No volatile release during cure

− Storage stable at room temperature

− Cost-effective

Promising candidate to replace phenolic resin for interior application !


Resin Chemistry Comparison

Traditional Resole Synthesis

− Poor storage stability due to high reactivity of methylol groups,

Gardziella, A.; Pilato, L. A.; Knop, A., “Phenolic Resins: Chemistry, Application, Standardization, Safety and Ecology”, Springe, 1999


OH

R

CH2OH

CH2OH2

OH

CH2 O CH2

R

CH2OH

OH

R

CH2OH

OH

CH2

R

CH2OH

OH

CH2OH

R

+ H2O

+ H2O + CH2O


Traditional Resole Curing

− Water and formaldehyde released

Gardziella, A.; Pilato, L. A.; Knop, A., “Phenolic Resins: Chemistry, Application, Standardization, Safety and Ecology”, Springe, 1999


Benzoxazine Synthesis

− Water removed before curing

− Ring structure instead of reactive methylol group, better storage stability

− Lower viscosity due to monomeric ring structure

− Amine is used beside phenol and formaldehyde as raw material



Benzoxazine Curing

− Ring opening mechanism

− No extra volatile release due to water pre-removal

− Low void content in resin/laminate

− Higher aromatic content retained , comparable FST

− Nitrogen element could further contribute to FST properties

NO

R1

R2OH

N

R1

OH

R1

R2nn



XU 35710 FST

Physical Form Amber viscous liquid

Total Solid* >99%

Viscosity at 100 oC (cps) 30-100 cps

Gelling time at 200 oC (sec) 300-450

XU 35710 FST Product Characteristics

Neat Resin Properties


XU 35710 FST Processing Characteristics

− The product has a low viscosity compared to typical BPA or BPF

benzoxazines, and provides better processability and easier resin handling



XU 35710 FST Processing Characteristics

− Long pot-life for liquid molding application



XU 35710 FST Reactivity



XU 35710 FST Curing Characteristics

− Volatile/void free during curing

Dish casting results with no pre-degassing



Properties

XU 35710 FST

Flexural strength, Mpa 121

Flexural modulus, Gpa 5.2

Flexural ultimate elongation, % 2.3

Tensile strength, Mpa 60

Tensile modulus, Gpa 4.9

Tensile ultimate elongation, % 1.3

K1C, Mpa ·m0.5 0.92

G 1C, J/m2 200

Physical Properties of XU 35710 FST Neat Resin

− Cured resin shows high modulus, high strength, and high toughness



Laminate Properties by RTM

Test Method Specification XU 35710 Benzoxazine

Flammability – 60 second vertical

burn

Extinguish Time –

Burn Length –

Drip Extinguish Time -

FAR 25.853(a)

< 15 seconds

< 6 inches

< 3 seconds

0.0

3.7

0.0

Smoke Density

Specific Optical Density -

FAR 25.853(d)

< 200 (Ds)

11

Heat release

Total Heat Release –

Peak Heat Release-

FAR 25.853(d)

< 65 kW.min /m2

< 65 kW/m2.

18

29

Toxicity BSS 7239 HCN – <150.

CO – Ref.

NOx – <100.

SO2 – <100.

HF – <200.

HCL – <500.

2

19

3

0

1

0

FST Properties of 2 ply XU 35710 FST/7781 Glass Laminate by RTM

*: 50% fiber volume

*: curing condition: 2h@150 oC +2h@180 oC


Properties Method XU 35710 FST Typical Aero

Phenolic

Flexural modulus (warp), Gpa ISO178

27 20-24

Flexural strength (warp), MPa 663 470-550

Tensile modulus (warp), GPa

ISO527

28 19-24

Tensile strength (warp), MPa 457 380-400

ILSS (warp), MPa ISO14130 50 24-50

Compression modulus (warp), GPa

ISO14126

29 20-24

Compression strength (warp), MPa 555 350-380

Laminate Properties by RTM

Mechanical Properties of XU 35710 FST/7781 Glass Laminate

*: 50% fiber volume

*: curing condition: 2h@150 oC +2h@180 oC


Increase XU 35710 FST Reactivity for Low Temperature Cure

XU 35710 FST 100 100

Novolac SD-1702* 0 20

DSC onset/peak temperature, oC 215/227 174/202

Curing profile 300 oF/1h +350 oF/ 90min 320 oF/1h

Tg, oC 137 / 142 (re-run) 127/143(re-run)

*: From Momentive Specialty Chemical

XU 35710 FST for Prepregging Process



Formulation System # #1 #2 #3

DSC reactivity onset/peak, °C 150/188 117/183 127/183

Solvent prepregging condition: 130 °C (265 oF) /3min

Drape Good Good OK

Press curing condition: 130°C (265 oF) /90min at 20psi

Tg by DSC, °C 102 109 117

Tg by DMA (E’), °C 115 123 129

Press curing condition: 145°C (293 oF) /60min at 20psi

Tg by DSC, °C 121 134 127

Tg by DMA (E’), °C 129 134 139

Post cured at 160 °C/1h

Tg by DSC, °C 137 147 138

Tg by DMA (E’), °C 138 138 144

− Resin formulations based on XU 35710 FST show good Tg build-up and are curable

with temperature as low as 130 oC (266 oF)

XU 35710 FST Based Formulation for Solvent Prepregging Process



Rheology Profile of XU 35710 FST Based Formulation for Prepregging Process



Formulation Test Method Specification Formulation #1 Formulation #2 Formulation #3

Curing condition 145 oC (293 oF) /1h

Fibre volume content, % 55 52 50

Flammability – 60 second vertical burn

Extinguish Time –

Burn Length –

Drip Extinguish Time -

FAR 25.853(a)

< 15 seconds

< 6 inches

< 3 seconds

0.0

4.3

0.0

0.0

5.5

0.0

0.0

5.2

0.0

Smoke Density

Specific Optical Density -

FAR 25.853(d)

< 200 (Ds)

9.2

8.3

14.5

Heat release

Total Heat Release –

Peak Heat Release-

FAR 25.853(d)

< 65 kW.min /m2

< 65 kW/m2

22

46

38

51

30

41

Toxicity BSS 7239 HCN – <150. CO – Ref. NOx – <100. SO2 – <100. HF – <200. HCL – <500.

<5 45 8

<5 <5 <5

<5 101 11 <5 <5 <5

<5 56 7

<5 <5 <5


Summary

New cost-effective benzoxazine building block XU 35710 FST has been developed and evaluated for aerospace and other transportation interior applications.

The new resin demonstrates a series of advantages over traditional phenolic resin with comparable FST performances

− Volatile/void free during cure

− Improved resin modulus, strength and toughness

− Improved laminate mechanical performances

− Shorter manufacturing cycle time

− Better storage stability

− Easy to process by RTM or other liquid molding techniques with its low viscosity and long pot-life

The new resin also fits traditional solvent or hot-melt prepreg process with three formulation demonstrated. The formulated systems demonstrate good rheology control and low temperature cure characteristics, while still keep good FST performances.

With its performance and processing advantages, the resin could also be used by itself or with further formulation for other aerospace and industrial composite applications.


Disclaimer

The slides following hereafter contain information that is confidential and proprietary to Huntsman Corporation, and/or its appropriate affiliate(s) (“Huntsman”) Recipients of this presentation and the information contained herein shall not copy or replicate the same by any means whatsoever and shall not share or show such information to third patties..

While the information contained herein is, to the best of Huntsman’s knowledge, accurate as of the date of its presentation, it is the responsibility of recipients to determine the applicability and/or suitability of such information for their own particular purpose Huntsman accepts no responsibility for any damages of any kind incurred by recipient and/or third patties resulting from the use of, reliance upon, or the misuse of such information for any purpose.

All information contained herein is provided “as is” without any warranties, express or implied, and under no circumstances shall the authors or Huntsman be liable for any damages of any nature whatsoever resulting from the use or reliance upon such information. Nothing contained in this publication should be construed as a license under any intellectual property right of any entity, or as a suggestion, recommendation, or authorization to take any action that would infringe any patent. The term “Huntsman” is used herein for convenience only, and refers to Huntsman Corporation, its direct and indirect affiliates, and their employees, officers, and directors

Documents

By Dong Wang Huntsman Advanced Materialsfeiplar.com.br/materiais/palestras/aeroespacial/Huntsman.pdf · By Dong Wang Huntsman Advanced Materials ... Araldite® MT 35700 (BPF)