Fakultet kemijskog inženjerstva i tehnologije

1. Fakultet kemijskog inženjerstva i tehnologije Modifikacija i stabilnost višefaznih polimernih sustava Voditelj projekta: dr. sc. Vesna Rek, red. prof.

2. Modification and stability of multiphases polymer systems Investigators: Prof. dr. sc. Vesna Rek – principal investigator Prof. dr. sc. Emi Govorčin Bajsić Dr. sc. Tamara Holjevac Grgurić Nina Vranješ, dipl. ing. Vesna Ocelić, dipl. ing. Dr. sc. Želimir Jelčić Mr. sc. Andrea Strineka Foreign researchers: Prof. dr. sc. Ivan Fortelny – Institute of Macromolecular Chemistry, Prague Prof. dr. sc. Dorota Pietkiewicz – University of North Texas, Denton, USA

3. Hypothesis Mixing plastomers (P) with various degrees of crystallinity and polarity and P with thermoplastic elastomers (TPE) and bitumen enable the achievement of new polymer blends (PMB) and polymer bitumen (PmB) engineering properties. The aim • Design properties for applications • Development new multiphases systems, PMB and PmB • Commodity plastics • Engineering plastic • Correlations between the composition of multiphase polymer systems, PMB and PmB • Morphological structure; phase interaction • Rheological properties in processing and use • Mechanical properties; tensile and impact properties • Wear resistance

4. Application • Construction and building, road technology • Medical purpose • Thermoforming • Packing • Mixed plastic waste recycling • Economical and ecological important Education:knowledge about the structure/properties relationship in PMB and PmB

5. Systems Blends • PS/HDPE compatibilizer: SEBS • PP/PS compatibilizer: SEBS and SEBS- g- MA • PS/PB compatibilizer: SB, SBS, SBSBS • PP/HDPE compatibilizer: EPDM • TPU/PP modifier: PP • PC/TPU modifier:TPU • Polymer bitumen modifier: SBS Methodology • Processing characteristics; TQ, Output, app • Morphology; SEM, IA, TEM, SAXS,OM,WAXD, PM • Rheological properties in use; DMA, DSR • Mechanical properties; tensile and impact properties • PMB – prepared in a twin-screw extruder • Samples preparation by compression and injection molding • PmB – prepared by mixing bitumen+SBS with Silverson mixer

6. PS/HDPE/SEBS – processing parameters a) b) c) • Processing parameters: (a) TQ, (b) TQ/Q, (c) p/Q. • Decrease with HDPE content • SEBS did not significantly influence

7. Morphology a) • Coarse morphology • Two phases structure • Improvement interfacial adhesion • Homogeneous structure • Localization of SEBS at interphase d) b) e) f) c) Microphotographs: PS/HDPE 80/20 (a), PS/HDPE/SEBS 80/20/5 (b), PS/HDPE/SEBS 80/20/7 (c), PS/HDPE40/60(d), PS/HDPE/SEBS 40/60/5 (e) and PS/HDPE/SEBS 40/60/7 (f)

8. Mechanical properties Mechanical propertiesof examinedsystems • Izod impact strength and elongation at • break increased with SEBS • It is more expressed in HDPE rich blend • Tensile strength did not change • significantly

9. DMA measurements a) b) c) d) • Master curves at Tref 25 °C for a) PS/HDPE/SEBS 80/20/5, b) PS/HDPE/SEBS 40/60/5, c) PS/HDPE/SEBS80/20/7, d) PS/HDPE/SEBS 40/60/7. • With HDPE and SEBS contents creep modulus decreased; the creep values increased.

10. Morphology a) d) • Coarse morphology • Two phases structure • Co-continuous morphology • Reduction of the particle size • Homogeneous structure b) e) c) f) Microphotographs: PP/PS 90/10; 2000x (a), PP/PS/SEBS90/10/5; 2000x (b), PP/PS/SEBS 90/10/7; 2000x (c), PP/PS 20/80; 500x (d), PP/PS/SEBS 20/80//7; 500x (e) and PP/PS/SEBS 20/80/7; 2000 x(f)

11. Scratch resistance Singlescratching • Higher penetration depth with higher force and with scratch number Multiplescratching SEM microphotographs after single scratch at 20 N PP/PS/SEBS 90/10/7 PP/PS 90/10 Adhesive wear mechanism Ploughing wear mechanism

12. The blends of PS/PB/SBS and PS/PB/SB+SBS have the highest tensile impact strength and ductility index. Tensile impact strength of PS/PB blends. Ductility index of PS/PB blends obtained by Charpy impact test (load deflection curves). AP – propagation energy AT – total fracture energy

13. TPU/PP blends DMA measurements • Tg’s maxima of the TPU and PP phases slightly broaden and shift towards to each other • E’ increases with increasing PP content • Partial compatibility of the TPU and PP chains

14. Mechanical properties • Stepwise decrease of the elongation at break and increase of Young modulus occur between the TPU/PP 80/20 and 60/40 blends • Ductile – brittle transition occurred in this concentration region

15. Polarization microscopy Wide-Angle X-Ray Diffraction • Stable monoclinic -phase of semicrystalline isotactic PP; low degree of crystallinity of TPU • Stepwise change of reflections intensity between the TPU/PP 80/20 and 60/40 blends (a) neat PP, (b) TPU/PP 40/60, (c) TPU/PP 60/40, and (d) TPU/PP 80/20 blend • Stepwise decrease of spherulite size from TPU/PP 60/40 to TPU/PP 80/20 blends • Matrix → dispersed phase inversion in this concentration region

16. Polymer bitumen modifier: SBS • Modification of rheological properties • Better viscoelastic properties – viscoelastic plateau • Broader temperature range of use DMA spectra's of a) bitumen, b) PmB- BIT/SBS 90/10 and c) PmB- BIT/SBS 87/13

17. Creep and recovery at constant stress for bitumen and PmB - BIT/SBS at different temperatures • Physical network in PmB– swollen PS and PB phases in BIT • Higher creep and recovery values of PmB • Better resistance to permanent deformation Micrograph of PmB - BIT/SBS 90/10

18. DSR measurements • BIT • Sharp test – 58 ºC b) PmB Sharp test – 64 ºC

19. Equipment: • Dynamical Mechanical Analyser, DMA, TA 983 • Modulated Differential Scanning Calorimeter, MDSC 822, Mettler Toledo • Instrument for mechanical testing, Zwick 1145 • Rondol extruder • RTFOT – Civil Engineering Institute of Croatia • Fluorescence microscope, Olympus BX51M - Civil Engineering Institute of Croatia • Scanning Electron Microscope, Jeol J. S. M. 5800 – Pliva • Brookfield viscosimeter • FTIR Perkin Elmer 297 • Contact angle • Dynamic Shear Rheometer, DSR - Civil Engineering Institute of Croatia

20. Chapters in books: • Rek, Vesna; Vranješ, Nina; Barjaktarović, Zrinka M., Evaluation of ageing properties of polymer modified bitumen, Natural and Artifical Ageing of Polymers, 2005, 369-379. • Rek, Vesna; Barjaktarović, Zrinka, Holjevac Grgurić Tamara, The rheological properties of aged polymer bitumen, Natural and Artifical Ageing of Polymers, 2004, 151-162. • Articles in Impact factor journals: • Rek, Vesna; Vranješ, Nina; Šlouf, Miroslav; Fortelny, Ivan; Jelčić, Želimir, Morphology and properties of SEBS block copolymer compatibilized PS/HDPE blends, J Elast Plast, 40 (2008) , 3; 237-251. • Brostow, W., Holjevac Grgurić, T., Olea-Mejia, O., Rek, V., Unni, Y., PP+PS Blends with • compatibilizer 1. Morphology and Thermophysical Properties, e-polymers, (2008),033 • Brostow, W., Holjevac Grgurić, T., Olea-Mejia, O., Pietkiewicz, D., Rek, V., PP+PS • Blends with a compatibilizer 2. Mechanical and Tribological Properties, e-polymers, • (2008),034 • Vranješ, Nina; Lednicky, František; Kotek, Jiri; Baldrian, Josef, Rek, Vesna; Fortelny, Ivan; Horak, Zdenek, Compatibilization efficiency of styrene-butadiene block copolymers as a function of their block number, J Appl Polym Sci, 108 (2008) 466-472. • Agić, Ante; Govorčin Bajsić, Emi, Strategy for kinetic parameter estimation – thermal degradation of polyurethane elastomers, J Appl Polym Sci, 103 (2007) 764-772 . • Govorčin Bajsić, Emi; Šmit, Ivan; Leskovac, Mirela, Blends of thermoplastic polyurethane and polypropylene. I. Mechanical and phase behavior, J Appl Polym Sci, 104 (2007) 3980-3985.

21. Vranješ, Nina; Rek, Vesna, Effect of EPDM on morphology, mechanical properties, crystallization behavior and viscoelastic properties of iPP+HDPE blends, Macromolecular Symposia, 258 (2007) 90-100. • Agić, Ante; Govorčin Bajsić, Emi; Rek, Vesna, Kinetic parameters estimation for thermaldegradation of polyurethane elastomers, J Elast Plast, 38 (2006) 105. • Jelčić, Želimir, Holjevac Grgurić, Tamara; Rek, Vesna, Mechanical properties and fractal morphology of high-impact polystyrene/poly(styrene-b-butadiene-b-styrene) blends, Polym Deg Stab, 90 (2005) 295-302. • Rek, Vesna; Vranješ, Nina; Barjaktarović, Zrinka M., Evaluation of ageing properties of polymer modified bitumen, Mat Res Innov, 9 (2005) 670-691. • Govorčin Bajsić, Emi; Rek, Vesna, Dynamic mechanical study of thermoplastic polyurethane/polypropylene blends, e-polymers (2004), 073; 1-10. • Rek, Vesna; Holjevac Grgurić, Tamara; Jelčić, Želimir; Hace, Drago.Effect of styrene/ethylene/buthylene/styrene block copolymer on dynamic mechanical behaviour and processability of high impact polystyrene, e-polymers (2004), 034; 1-13. • Govorčin Bajsić, Emi; Rek, Vesna; Agić, Ante, Thermal Degradation of polyurethane Elastomers: Determination of kinetics parameters, J Elast Plast, 35 (2003) 311-323. • Rek, Vesna; Holjevac Grgurić, Tamara; Jelčić, Želimir, Creep relaxation and stress relaxation of PS-HI/SEBS blends, Macromolecular Symposia, 202 (2003) 127-141. • Rek, Vesna; Holjevac Grgurić, Tamara; Jelčić, Želimir, Processing and dynamic mechanical properties of PS-HI/SEBS, Macromolecular Symposia, 202 (2003) 143-150. • Rek, Vesna; Barjaktarović, Zrinka, Dynamic mechanical behaviour of polymer modified bitumen, Mat Res Innov, 6 (2002) 39-43.