Benzoxazine Resin for Aerospace Interior Applications. By Dong Wang Huntsman Advanced Materials

Transcription

1 Benzoxazine Resin for Aerospace Interior Applications By Dong Wang Huntsman

2 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 FST neat resin properties XU FST composite laminate properties XU FST resin for pre-pregging process Summary Disclaimer

3 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

4 Background and Challenges Main issues of using traditional phenolic resin EHS concerns Laminate quality control difficulty Volatile release during curing Low mechanical performances Long manufacturing cycle time Other issues of using traditional phenolic resin Poor storage stability Typically solvent based

5 Background and Challenges 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

6 Huntsman Our Products Base Resins Specialty Components Formulations Liquid epoxy resins Curing Agents Multifunctionals Adhesives Encapsulation Solid epoxy resins Matting agents Crosslinkers Tooling Insulation Epoxy solutions Reactive Diluents BisF/EPN/ECN Composites Protection Waterbornes Reactive PAA Laminates

7 High-Performance Building Blocks for Advanced Composites Chemistry Offered by Huntsman Advanced Material 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 Curing Agents Aliphatic Amine Aromatic Amines Cycloaliphatic Amine Anhydride Polyamides Accelerators Phenalkamines Specialty Latent Hardeners

8 High-Performance Building Blocks for Advanced Composites Typical Product Offered by Huntsman Advanced Material 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 / High Tg, high modulus, good chemical and thermal resistance Aradur High modulus, high toughness

9 Huntsman Benzoxazine Technology O CH 3 O O C H 2 O N CH 3 N N N Bisphenol A-based Benzoxazine Bisphenol F-based Benzoxazine O N O Thiodiphenol-based Benzoxazine S N O O N Mono-phenol-based Benzoxazine O R O N O N N Dicyclopentadiene-based Benzoxazine N Phenolphthalein-based Benzoxazine O O

10 Benzoxazine Products for Composites Application Product Advantages/Benefits Potential Application XU35610 (BPA) Araldite MT (BPF) Good solvent solubility Volatile/void free during curing High Tg/modulus High-Tg/modulus Good chemical resistance Good flammability properties Aerospace structural High temp tooling Aerospace structural Transportation interior High temp tooling XU35710 FST Good FST Low viscosity Low temperature (350F) curing Low cost High Modulus/tough-ness XU (Thiodiphenol) Low viscosity Low temperature (350F) curing High Tg/ modulus Aerospace and other transportation interior Industrial composite (auto, down-hole, etc.) FST tooling Aerospace structural Industrial composite (auto, down-hole, etc.) High temp tooling XU (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

11 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!

12 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

13 Resin Chemistry Comparison Traditional Resole Curing OH OH CH 2 O CH 2 + H 2 O 2 R OH CH 2 OH CH 2 OH R CH 2 OH OH CH 2 OH R CH 2 OH + H 2 O + CH 2 O R CH 2 OH R CH 2 OH Water and formaldehyde released Gardziella, A.; Pilato, L. A.; Knop, A., Phenolic Resins: Chemistry, Application, Standardization, Safety and Ecology, Springe, 1999

14 Resin Chemistry Comparison Benzoxazine Synthesis Amine is used beside phenol and formaldehyde as raw material Water removed before curing Ring structure instead of reactive methylol group, better storage stability Lower viscosity due to monomeric ring structure

15 Resin Chemistry Comparison Benzoxazine Curing O N R 2 OH OH n N R 2 n R 1 R 1 R 1 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

16 Neat Resin Properties XU FST Product Characteristics XU FST Physical Form Amber viscous liquid Total Solid* >99% Viscosity at 100 o C (cps) cps Gelling time at 200 o C (sec)

17 Neat Resin Properties XU FST Processing Characteristics The product has a low viscosity compared to typical BPA or BPF benzoxazines, and provides better processability and easier resin handling

18 Neat Resin Properties XU FST Processing Characteristics Long pot-life for liquid molding application

19 Neat Resin Properties XU FST Reactivity

20 Neat Resin Properties XU FST Curing Characteristics Volatile/void free during curing Dish casting results with no pre-degassing

21 Neat Resin Properties Physical Properties of XU FST Neat Resin Properties XU 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 K 1C, Mpa m G 1C, J/m Cured resin shows high modulus, high strength, and high toughness

22 Laminate Properties by RTM FST Properties of 2 ply XU FST/7781 Glass Laminate by RTM Test Method Specification XU Benzoxazine Flammability 60 second vertical burn Extinguish Time Burn Length Drip Extinguish Time - FAR (a) < 15 seconds < 6 inches < 3 seconds Smoke Density Specific Optical Density - FAR (d) < 200 (Ds) 11 Heat release Total Heat Release Peak Heat Release- FAR (d) < 65 kw.min /m 2 < 65 kw/m Toxicity BSS 7239 HCN <150. CO Ref. NOx <100. SO2 <100. HF <200. HCL <500. *: 50% fiber volume *: curing condition: 2h@150 o C +2h@180 o C

23 Laminate Properties by RTM Mechanical Properties of XU FST/7781 Glass Laminate Properties Method XU FST Typical Aero Phenolic Flexural modulus (warp), Gpa ISO Flexural strength (warp), MPa Tensile modulus (warp), GPa ISO527 Tensile strength (warp), MPa ILSS (warp), MPa ISO Compression modulus (warp), GPa ISO14126 Compression strength (warp), MPa *: 50% fiber volume *: curing condition: o C +2h@180 o C

24 XU FST for Prepregging Process Increase XU FST Reactivity for Low Temperature Cure XU FST Novolac SD-1702* 0 20 DSC onset/peak temperature, o C 215/ /202 Curing profile 300 o F/1h +350 o F/ 90min 320 o F/1h Tg, o C 137 / 142 (re-run) 127/143(re-run) *: From Momentive Specialty Chemical

25 XU FST for Prepregging Process XU FST Based Formulation for Solvent Prepregging Process Formulation System # #1 #2 #3 DSC reactivity onset/peak, C 150/ / /183 Solvent prepregging condition: 130 C (265 o F) /3min Drape Good Good OK Press curing condition: 130 C (265 o F) /90min at 20psi Tg by DSC, C Tg by DMA (E ), C Press curing condition: 145 C (293 o F) /60min at 20psi Tg by DSC, C Tg by DMA (E ), C Post cured at 160 C/1h Tg by DSC, C Tg by DMA (E ), C Resin formulations based on XU FST show good Tg build-up and are curable with temperature as low as 130 o C (266 o F)

26 XU FST for Prepregging Process Rheology Profile of XU FST Based Formulation for Prepregging Process

27 XU FST for Prepregging Process Formulation Test Method Specification Formulation #1 Formulation #2 Formulation #3 Curing condition 145 o C (293 o F) /1h Fibre volume content, % Flammability 60 second vertical burn Extinguish Time Burn Length Drip Extinguish Time - Smoke Density Specific Optical Density - Heat release Total Heat Release Peak Heat Release- FAR (a) FAR (d) FAR (d) < 15 seconds < 6 inches < 3 seconds < 200 (Ds) < 65 kw.min /m 2 < 65 kw/m 2 Toxicity BSS 7239 HCN <150. CO Ref. NOx <100. SO2 <100. HF <200. HCL < < <5 <5 < < <5 <5 < < <5 <5 <5

28 Summary New cost-effective benzoxazine building block XU 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.

29 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