1. DEVELOPMENT OF HIGH DENSITY POLYETHYLENE/RICE HUSK COMPOSITES Hieu Nguyen, Thanh Tran and Loan Doan a, Thai Nguyen and Long Truong b, Son Do and Thao Vo c and Thoi Ho d a Da Nang University of Technology - The University of Danang - Vietnam b Plastics and Rubber Technology Center - Vietnam c HCM City University of Technology - Vietnam d International Polymer Consultant - USA Houston, 2011 International Polyolefins Conference 2011

2. Outline Introduction Review of natural fibers/polyolefin composite technologies Preliminary results of rice husk/HDPE composite Conclusions/ Path Forward

3. Green composites Competitive price /performance Environmentally safe (Recycling or incineration at end-of-life with energy recovery) Renewable resource Natural fibres Specific mechanical properties (high strength/low density) Widely applicable Low machine wear Safe working condition (vs. Glass fibre) Low density Green composites: Composites of the future

4. Global Production of WPC Plastic Information Europe Global production of WPC: 3.3 Billion lb

5. Source: Freedonia Inc Market in US in 2010 about $2 Billion. Annual growth rate of about 20%

7. Natural fibers as fillers for green composites Availability of major biomass sources in Vietnam in 2006 Natural fibers RICE HUSK

8. Rice’s Statistics Rice feeds 50% of world population World rice production in 2007 :1430 B lb Rice contains 20wt% of rice husk Rice husk available in 2007 is 286 B lb About one pound of rice husk available for each pound of polyolefin produced world wide!

9. W (B lb)China (B lb)India (B lb)VN (B lb)US (B lb) 2868262164 Estimated Rice Husk Available in 2007 Cost rice husk: -Get it free from rice mill -Cost of rice husk -Cost of transportation -Plus cost of grinding

10. How the rice husk is used in Vietnam? Dumping on the river Burning openly  Mainly using for daily cooking Using for daily cooking (Cookstoves)  Polluting the air, water, land…  Disposal cost Dumping in rivers

11. Our Vision of Using Rice Husk in Future +

12. Review of Natural Fibers/Polyolefin Composite Technology

13. Which polymers should be used as matrices for rice husk composites? Bio-Polymers Polyolefins PET PU, PS ABS, PC PVC “Green Peace” Triangle Polyolefins continue to substitute these polymers Environmental Friendliness

14. ComponentsChemicalWt % Base resinsPP, HDPE50-80 Natural fibersWood (100-200 micron20-50 CompatibilizerMAH -HDPE/MAH -PP2-4 Processing aidFatty acid esters, waxes1-4 Other additivesAO, UV, FR, Fungicide, Neutralizer0.1-0.3 Summary of WPC Technologies Optimat Ltd and MERL Ltd D Gardener http://www.umaine.edu/adhesion/gardner/5502002/wpc ext over 3-11-02.pdf

15. Key Mechanical Properties of WPC Reinforcing effectiveness: Glass>Talc>Wood>CaCO 3 English et al

16. FiberCellulose (%) Lignin (%)Silica (%) Rice straw28-3612-169-14 Rice Husk38-4515-2219 Soft wood40-4526-34<1 Hard wood38-4823-30<1 Composition of Some Selected Natural Fibers Rice husk has much higher silica and lower lignin content than woods

17. Potential Advantages of Rice Husk Abundant resource of rice husk (286 Blb /year world wide) Rice husk is agricultural waste product (low cost / help the environment/reduce dependence on oil ) Rice husk is “greener” than wood High silica content: – High mildew and fungi resistance – Better fire retardant than wood/polyolefin composite – Lower water absorption than wood /polyolefin composite

18. SampleComposition (%) Flexural Strength (MPa) Flexural Modulus (MPa) Impact Strength (KJ/m2) APP/RH (70/30)2616004 BPP/RH (60/40)2318002.5 CPP/RH/MAPP (56/40/4)3517003.5 DPP/RH/POE/MAPP (56/30/10/4) 2813005.0 EPP/RH/POE/MAPP (46/30/20/4) 1780015.0 PPProfax SM240013006.5 PP/TalcSM2400/10% Talc1800*3* Reported Key Mechanical Properties of PP/Rice Husk Composites PP= Profax SM 240 (d=0.9g/cc, MFR=25g/10min, POE=Engage 8150, MAPP=Licomont AR504 A, B, C, D, E: Data from M. Mustapa et al (Simposium Polymer Kebangsaan Ke-V) (2005) * Estimated value Samples B and D have comparable key mechanical properties with PP+10% Talc

19. Development of Rice Husk /HDPE Composite

20. Experimental IngredientsWeight (%) Rice husk38 - 58 HDPE38 - 58 MAPE4 Rice husks (RH): Long An province, Vietnam (particle size???). High density polyethylene (HDPE): Sabic Asia Pacific PTE. LTD, Philippin. Maleic anhydride-grafted polyethylene Fusabond E226 (MAPE): DuPont. Songnox 417 (0.15 wt%): Songwon, Korea. Calcium stearate (0.1 wt%).  Materials:

21. Experimental (HDPE +MAPE) Melt-blending (Brabender) compression molding Rice husks GrindingDrying Processing Composite samples T = 160 o C  = 10 min = 54 rpm Tensile test: ASTM D638 Bending test: ASTM D790 Notched impact test: ASTM D256 Water absorption

22. Results: Tensile strength and modulus RH content  polar RH/ apolar HDPE interfacial area   tensile strength . RH fillers have higher stiffness than the polymer matrices  tensile modulus of the composites  with rice husk content.

23. RH content  bending strength  and then . Bending modulus of the composites  with rice husk content. Results: Bending strength and modulus

24. Results: notched impact toughness RH fillers is more brittle than HDPE matrix  impact toughness of the composites decreased as rice husk content increased.

25. Results: Water absorption RH content   water absorption  Water absorption of 38 wt.% RH composite is lower to that of commercial composite sample for decking application.

26. Conclusions RH can improve significantly modulus of pure HDPE and composites. Impact toughness, tensile and bending strength of the composites decrease much at high amount of rice husk. RH/ HDPE composite have comparable key properties with commercial WPC Successful development of rice husk/polyolefin composites: Production of low cost composite for construction materials Generate economic development for the rural areas Reduction of environmental pollution

27. Path Forward Identify target applications for RH/HDPE Optimize composite composition/additives to meet the performances for the applications – Mechanical properties – Processability – Processing stability: discoloration/Mw degradation /Bubble formation – Durability (water absorption/fire retardant, mildew resistance, UV stability, etc)

28. Acknowledgements 2010 International Polyolefin Conference/PMAD for warding a scholarship to Thanh Tran The following companies for providing resins and additives -The Dow Chemical Company -Dupont Company -Chemtura -BASF -Songwon

29. for your attention Merci Danke Thank you Arigato Cám ơn