Thermoset Resins and Their Composites

Size: px

Start display at page:

Download "Thermoset Resins and Their Composites"

Elisabeth Welch
5 years ago
Views:

1 ACCE 22, September 13-14, 14, 22 Bio-based Thermoset Resins and Their Composites M. Misra,, L. T. Drzal, A. K. Mohanty,, L. Belchler, G. Mehta,, J-P. J Latere Dwan sisa Michigan State University 21 Engineering Building, East Lansing, MI, 48824

2 Presentation ut-line Introduction and motivation Bio-based resins, Bio-fibers and Bio-Composites Biobased Epoxies and Their Composites Biobased Polyurethanes and Their Composites Biobased Unsaturated Polyesters and Their Composites Conclusions Acknowledgements

3 Motivation TECHNLGY: To Improve Toughness ECNMY: Economically Viable HW? Example: Epoxy Resin Costs 126 cents/lb. Whereas Epoxidized ils Costs ~ 6 Cents/lb BLEND of Functionalized il WITH Thermoset Resins? (Thermoset Resins: Brittle & Expensive) ECLGICAL BENEFIT: Incorporation f Bio-resources To the Maximum Permissible Extent To achieve Required Properties

4 NATURAL FIBERS FLAX HEMP KENAF JUTE HENEQUEN Woven JUTE Cloth CIR WD CRN GRASS

5 Natural/Bio-Fiber Composites (Bio-Composites) Thermoplastic based Thermoset based Biofiber- Thermoplastic ( Polypropylene/PVC/PS) Green: PLA, Cellulose esters etc. Biofiber-Thermosets (Epoxy, Polyesters, Polyurethanes) Bio-based: Blend with functionalized Vegetable oil HYBRID BI-CMPSITES (Fiber blending/matrix blending)

6 Thermoset vs. thermoplastic composites 15% Reinforced thermoplastics 7% Reinforced unsaturated polyester Matrix pattern in Polymer Composites 15% other thermosets Use of reinforced thermoset composites: ~doubled in the last decade Expected to increase 47% during next 5 years through 24 ~ 65% of all composites use glass fiber - polyester composites. Natural fiber polyester composites: target is to replace glass-polyester composites

7 Bio-based Epoxies and their Composites

8 Reagents DGEBA (Diglycidylether of bisphenol A) CH 3 H CH 3 CH 2 CH C C CH 2 CH CH 2 CH 2 CH CH 2 CH 3 m =, 1, 2 m CH 3 J-T43 (Jeffamine T43) MPDA (m-phenylene diamine) CH 2 CH 2 CH CH 3 NH X 2 NH 2 CH 3 CH 2 C CH 2 CH 2 CH CH 3 NH 2 Y CH 2 CH 2 CH CH 3 NH Z 2 NH 2

9 Reagents: Epoxidized Soy(ES)/Linseed ils(el) CH 2 C CH 2 7 CH CH CH 2 CH CH CH 2 4 CH 3 CH 2 C CH 2 4 CH CH CH 2 CH CH CH 2 CH CH CH 2 4 CH 3 CH 2 C CH 2 7 CH CH CH 2 7 CH 3 Epoxy equivalent wt. of ES: CH 2 C CH 2 7 CH CH CH 2 CH CH CH 2 CH CH CH 2 CH 3 CH 2 C CH 2 4 CH CH CH 2 CH CH CH 2 CH CH CH 2 CH 3 CH 2 C CH 2 7 CH CH CH 2 7 CH 3 Epoxy equivalent wt. of EL:

10 Epoxy-Primary Amine Curing Reaction CH 3 H CH 3 CH 2 CH C C CH 2 CH CH 2 CH 2 CH CH 2 CH 3 m CH 3 C C + RNH 2 H C C NHR R C C + H C C NHR H C C N C C H

11 Modulus (GPa) Dynamic Mechanical Analysis of Bio-based Epoxy Resin with Jeffamine T43 at 3 C ES(1) ES(2) *ES(3) EL(1) EL(2) EL(3) Samples * taken from Tensile Measurements

12 Impact Strength and Glass Transition Temp. of Bio-based Epoxy Resin with T Impact Str. (J/m) IS Tg Tg ( C) ES(1%) ES(2%) ES(3%) EL(1%) EL(2%) EL(3%) Samples

13 Modulus of Elasticity (GPa) Modulus of Elasticity & Bending Strength of Epoxy Samples containing EL and MPDA ME Bending Str. % EL 3% EL 4% EL 5% EL Bending Strength (MPa) Samples

14 Impact Strength of Epoxy Samples containing MPDA and EL 12 Impact Strength (J/m) % EL 3% EL 4% EL 5% EL Samples

15 ESEMs of Impact Fractured Epoxy Resin containing MPDA and EL Scale: 5µm 1 µm 1 µm 3%EL X 6 4%EL X 6 5% EL X 5 Phase separation between epoxy-rich phase and EL-rich phase

16 Thermogravimetric Analysis of Surface Modified Henequen (HQ) Weight % Water-Washed (WW) 5%Alkali 2%Silane (Z-64)*** Plasma* UV** Water-Washed (WW) 5%Alkali 2%Silane (Z-64)*** Plasma* UV** Derivative Weight (%/ C) *55 W with 2 for 1 min. Temperature ( C) **12 sec. of UV at 6 C ***Epoxy compatible silane

17 Modulus of Elasticity (ME) & Bending Strength of - Epoxy Composites containing 3% EL and 3V% HQ ME Bending Str ME (GPa) Bending Strength (MPa).5 2 No EL or HQ EL 3V%WW 3V%5%Alkali 3V%Plasma* 3V%2%Silane 3V%UV** HQ HQ HQ HQ HQ Samples

18 Conclusion The impact strength was directly proportional to the concentration of the epoxidized oils when using J-T43. The modulus, bending strength, and Tg were inversely proportional to the concentration of the epoxidized oils when using J-T43. The impact strength was directly proportional to the concentration of the EL when using 3 or 4% EL and MPDA.

19 Bio-based Polyurethanes & their Composites

20 Polyurethanes: Synthesis and Uses PLYL DIISCYANATE H H + CN NC + H H CN NC CN NC H H H H Fast reaction, no by-product PLYURETHANE Wide range of polyols and isocyanates numerous uses

21 Distinguishing Characteristics of Polyols Characteristics Molecular weight Functionality Hydroxyl number Elastomers, Coatings, Flexible foams 1, to 6,5 2. to to 16 Rigid coatings, Rigid foams 15 1, 3. to to 1, (SZYCHER S HANDBK F PURs), CRC Press (1999).

22 Soy phosphate ester polyol H H H H H P H H H H H H H H P Mw = 234 g/mol Functionality = mg KH/g H H H H H H H H H H H

23 Properties of Biobased Polyurethane's Entry Polyol H ratio (JEFFL / SPEP) Tg ( C) (DMA) G (3 C) (MPa) Density (g/cm 3 ) 1 1 / / / / / / Isocyanate / H ratio = 1.1. Jeffol 495 polyol: polyether polyol (495 mg KH /g) and SPEP (154 mg KH /g). Isocyanate: polymeric diphenylmethane diisocyanate (MDI).

24 Polyol Hybridization Biobased PURs with acceptable properties (thermal, mechanical performances) and effective cost Effect of the (Jeffol / SPEP) H molar ratio on flexural properties 8 Flexural stength (MPa) /1 25/75 5/5 75/25 9/1 1/ Modulus (MPa) Impact strength (J/m) /1 25/75 5/5 75/25 9/1 1/ H molar ratio (Jeffol/SPEP) Flexural Strength (MPa) Modulus (MPa)

25 Glass reinforced Polyurethanes from soy phosphate ester polyol: DMA Study Effect of glass fiber on G' of soy phosphate ester PU G' (MPa) Temperature (C) No fiber 15 wt % 3 wt % 5 wt %

26 Modulus of Elasticity (ME),Bending Strength and Impact Strength of Glass reinforced Polyurethanes 6 Flexural strength (MPa) No fiber 15 wt % 3 wt % 5 wt % Flexural strength (MPa) Modulus (MPa) Flexural modulus (MPa) Impact strength (J/m) Partial break No fiber 15 wt % 3 wt % 5 wt % Improvement of mechanical properties (dynamic, flexural and impact)

27 Impact Fractured surfaces of Glass reinforced Polyurethanes No fiber 1 wt % 1X 3 wt % 5 wt %

28 Conclusions Preparation of PURs from soy phosphate ester combined with petroleum-based polyol (tuning of properties). Commercially available plant-based polyols: low H content for preparation of RIGID polyurethanes Glass reinforced PURs from SPEP.

29 Unsaturated Polyester Resins and their Composites Exterior (Natural Fiber-Polyester): Under- floor panels, engine & transmission covers Ref.: DaimlerChrysler High Tech Report 1999

30 Classification Unsaturated Polyester Resins rtho resins Isoresins Bisphenol-A fumarates Chlorendics Vinyl ester resins General purpose polyester resins (Cheapest resin)

31 Nonwoven Hemp Unsaturated Polyester Composites Tensile Strength (MPa) Tensile Modulus (GPa) Impact Strength(J/m) A B C A B C A: Neat polyester, B: Raw Hemp (3 vol.%)-polyester, C: Surface treated Hemp-polyester

32 CNCLUSINS Thermoset resins can be effectively blended with functionalized vegetable oil (Stiffness-toughness toughness balance) Different Bio-based polyurethanes can be designed and engineered - - Reinforment with bio-fiber/glass fiber result superior physico-mechanical properties. Bio-Composites can Replace/Substitute Glass Fiber Composites Energy benefit Renewability,, biodegradability, C 2 sequestration Independent of dwindling petro-sources Value-Added pportunity for Agriculture Industry

33 Acknowledgements NSF-PATH (21 Award No ) Project GREEEN (GR1 37) Bayer AG, Huntsman, Johnson & Manville ATFINA Chemicals Flaxcraft & Hempline Kemlite Composite Materials & Structures Center - MSU

Material Characterization of Natural Fiber Acrylic Thermoset Composites

Material Characterization of Natural Fiber Acrylic Thermoset Composites Andre Bendo Jeremy Funk, John Norton, Dr. Gero Nordmann & Dr. Michael Kalbe BASF Corporation 08/01/2011 1 Presentation verview Key