Fakultet kemijskog inenjerstva i tehnologije

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Fakultet kemijskog inenjerstva i tehnologije

• Modifikacija i stabilnost viefaznih polimernih
  sustava
• Voditelj projekta dr. sc. Vesna Rek, red. prof.

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Modification and stability of multiphases polymer
systems

• Investigators
• Prof. dr. sc. Vesna Rek principal investigator
• Prof. dr. sc. Emi Govorcin Bajsic
• Dr. sc. Tamara Holjevac Grguric
• Nina Vranje, dipl. ing.
• Vesna Ocelic, dipl. ing.
• Dr. sc. elimir Jelcic
• 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

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• 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

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

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• 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

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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

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Morphology
a)
d)

• Coarse morphology
• Two phases structure
• Improvement interfacial adhesion
• Homogeneous structure
• Localization of SEBS at interphase

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/HDPE
40/60(d), PS/HDPE/SEBS 40/60/5 (e) and
PS/HDPE/SEBS 40/60/7 (f)
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Mechanical properties of examined systems
Mechanical properties

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

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DMA measurements
a)
b)
d)
c)

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

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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/SEBS 90/10/5 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)
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Scratch resistance
Single scratching

• Higher penetration depth
• with higher force and with
• scratch number

Multiple scratching
SEM microphotographs after single scratch at 20 N
PP/PS/SEBS 90/10/7
PP/PS 90/10
Ploughing wear mechanism
Adhesive wear mechanism
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• The blends of PS/PB/SBS and PS/PB/SBSBS 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
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DMA measurements
TPU/PP blends

• Tgs 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

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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

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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

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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
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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
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DSR measurements

• BIT
• Sharp test 58 ºC

b) PmB Sharp test 64 ºC
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• 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

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• Chapters in books
• Rek, Vesna Vranje, Nina Barjaktarovic, Zrinka
  M., Evaluation of ageing properties of polymer
  modified bitumen, Natural and Artifical Ageing of
  Polymers, 2005, 369-379.
• Rek, Vesna Barjaktarovic, Zrinka, Holjevac
  Grguric Tamara, The rheological properties of
  aged polymer bitumen, Natural and Artifical
  Ageing of Polymers, 2004, 151-162.
• Articles in Impact factor journals
• Rek, Vesna Vranje, Nina louf, Miroslav
  Fortelny, Ivan Jelcic, elimir, Morphology and
  properties of SEBS block copolymer compatibilized
  PS/HDPE blends, J Elast Plast, 40 (2008) , 3
  237-251.
• Brostow, W., Holjevac Grguric, T., Olea-Mejia,
  O., Rek, V., Unni, Y., PPPS Blends with
• compatibilizer 1. Morphology and
  Thermophysical Properties, e-polymers, (2008),
  033
• Brostow, W., Holjevac Grguric, T., Olea-Mejia,
  O., Pietkiewicz, D., Rek, V., PPPS
• Blends with a compatibilizer 2. Mechanical
  and Tribological Properties, e-polymers,
• (2008), 034
• Vranje, Nina Lednicky, Frantiek 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.
• Agic, Ante Govorcin Bajsic, Emi, Strategy for
  kinetic parameter estimation thermal
  degradation of polyurethane elastomers, J Appl
  Polym Sci, 103 (2007) 764-772 .
• Govorcin Bajsic, Emi mit, Ivan Leskovac,
  Mirela, Blends of thermoplastic polyurethane and
  polypropylene. I. Mechanical and phase behavior,
  J Appl Polym Sci, 104 (2007) 3980-3985.

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• Vranje, Nina Rek, Vesna, Effect of EPDM on
  morphology, mechanical
• properties, crystallization behavior
  and viscoelastic properties of iPPHDPE blends,
  Macromolecular Symposia, 258 (2007) 90-100.
• Agic, Ante Govorcin Bajsic, Emi Rek, Vesna,
  Kinetic parameters estimation for
• thermaldegradation of polyurethane
  elastomers, J Elast Plast, 38 (2006) 105.
• Jelcic, elimir, Holjevac Grguric, 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 Vranje, Nina Barjaktarovic, Zrinka
  M., Evaluation of ageing properties of polymer
  modified bitumen, Mat Res Innov, 9 (2005)
  670-691.
• Govorcin Bajsic, Emi Rek, Vesna, Dynamic
  mechanical study of thermoplastic
  polyurethane/polypropylene blends, e-polymers
  (2004), 073 1-10.
• Rek, Vesna Holjevac Grguric, Tamara Jelcic,
  elimir 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.
• Govorcin Bajsic, Emi Rek, Vesna Agic, Ante,
  Thermal Degradation of polyurethane Elastomers
  Determination of kinetics parameters, J Elast
  Plast, 35 (2003) 311-323.
• Rek, Vesna Holjevac Grguric, Tamara Jelcic,
  elimir, Creep relaxation and stress relaxation
  of PS-HI/SEBS blends, Macromolecular Symposia,
  202 (2003) 127-141.
• Rek, Vesna Holjevac Grguric, Tamara Jelcic,
  elimir, Processing and dynamic mechanical
  properties of PS-HI/SEBS, Macromolecular
  Symposia, 202 (2003) 143-150.
• Rek, Vesna Barjaktarovic, Zrinka, Dynamic
  mechanical behaviour of polymer modified bitumen,
  Mat Res Innov, 6 (2002) 39-43.