P. Pereira, C. N. Barbosa, J. C. Viana. University of Minho, Portugal

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P. Pereira, C. N. Barbosa, J. C. Viana University of Minho, Portugal

» University of Minho Guimarães, Portugal 26 October 211

» Aims INTERREG EUROPEANPROJECT PROJECT : TECNA» To promote the uses of polymer (ternary) nanocomposites in the fields of automotive and mechanics industry» To contribute to the understanding of the relation between chemical structure, morphology, mechanical and electrical properties» Develop methodologies for transfer scientific knowledge from universities and technology institutes to industries in the SUDOE Region 11 26 October 2

» Industrial Needs SURVEY RESULTS Portugal Number of companies: 288 Industrial area: automotive (26 %) Number of views: 77 construction (22 %) Number of answers: 16 Plastic manufacturer (23 %) Injection moulding (38 %) 26 October 2 11 Company characterisation: < 5 workers (75 %) < 1M (euros) (75 %) National market (48 %) International market (48 %) Relevant material properties: Cost (26 %) Mechanical resistance (22 %)

» Industrial Needs SURVEY RESULTS Spain Number of companies: 131 Industrial area: Automotive (3 %) Number of views: 7 Vertical transport (3 %) Number of answers: 15 Plastic manufacturer (29 %) Injection moulding (29 %) 26 October 2 11 Company characterisation: < 25 workers (8 %) < 5M (euros) (73 %) National market (43 %) International market (48 %) Relevant material properties: Weight (11 %) Cost (1 %) Mechanical resistance (17 %)

» Industrial Needs SURVEY RESULTS France Number of companies: 76 Industrial area: Aerospace (25 %) Number of views: 32 Automotive (17 %) Number of answers: 9 Reinforced Plastic (27 %) Thermoforming (23 %) 26 October 2 11 Company characterisation: < 25 workers (66 %) < 5M (euros) (75 %) Local market (31 %) International market (46 %) Relevant material properties: Weight (12 %) Cost (9 %) Energy abortion (9 %)

» Industrial Needs SURVEY RESULTS SUDOE REGION 26 October 211

» Industrial Needs SURVEY RESULTS SUDOE REGION Does the company have knowledge of Is there motivation to work with Does the company know these materials as nanocomposites and/ or nanotechnology nanomaterials ( SUDOE )? fillers or as coatings can enhance several (SUDOE )? polymers properties ( SUDOE )? 11 26 October 2 Does the company think there is a need of new material properties ( SUDOE )? Is the company interested in participating an European nanotechnology -based project (SUDOE )? Is there interest to participate in meetings, seminars, workshops, etc., related with advanced materials ( SUDOE )?

» Masterbatch preparation by co rotating twin screw extruder ARNITE D4 3 (unreinforced PET) and. PYROGRAPH III TM CNF were dried in a dry air dehumidifier at 12 ºC for 6hbefore compounding by melt processing (extrusion). The blend were processed in a co rotating twin screw extruder using two material feeders, a barrel temperature profile from 27 ºC (at the feeder) to 265 ºC (at the die) and a screw speed of 1 rpm. At the die exit both masterbatch were immediately cooled down with water and afterwards milled in conventional milling equipment. 26 October 2 11 (1) PET + CNF Air dehumidifier (6h @ 12 ºC) Co-rotating twin screw extruder Tb (ºC) = 27 (feeder) to 265 (die) N = 1 rpm Milling equipment (pellets of d = 1.3 mm and l = 3. mm) MB 2A PET + 1 % CNF MB 2B PET + 2 % CNF MASTERBATCH

» Mixtures preparation by injection moulding Masterbatch produced were added to the neat PET materials in order to get all blends. All materials pellets were dried in a dry air dehumidifier at 12 ºC for 6hbefore injection process. Mix 3 = [PET+2%GF+3.%CNF] Mix 4 = [PET+2%GF+4.%CNF] %CNF] Mix 6 = [PET+2%GF+6.%CNF] 26 October 2 11 (2) MB2A/B+ PET2 Tumble mixer (3 min.) Vi = 3 mm/s Ph = 2 bar Air dehumidifier (6h @ 12 ºC) Injection moulding Mix 1 = [PET+2%GF+1.%CNF] TERNARY NANOCOMPOSITES Ti [MB+PET2] = 29 ºC Tw [MB+PET2] = 13 ºC (MB 2B only used Mix 1 )

» Thermal Characterization TGA Tests Extrusion Samples 12 MB2 PET2 Mix3_ext_cGF Mix4_ext_cGF Mix6_ext_cGF 1 Weigh ht (%) 8 6 4 2 Injection Samples 12 1 2 4 6 8 Temperature (ºC) MB2 PET2 Mix3_injinj Mix4_injinj Mix6_injinj Mix1_injinj Weight (% %) 8 6 4 2 2 4 6 8 Temperature (ºC)

» Mechanical characterisation Tensile tests performed @ 23 ºCC 26 October 2 11 Tensile Tests Conditions 7 Young s Modulus (MPa) 6 5 4 3 2 1 v= 1mm/min. L = 22mm T(room) = 23±2ºC Tensile to the Rupture 5 4 PET PET2 PET35 6 Strain at Break (%) 3 2 1 PET PET2 PET35 Raw Materials 18 Stressto to Yield (MPa) 16 14 12 1 8 6 4 2 PET PET2 PET35

» Mechanical characterisation Tensile tests performed @ 23ºC 26 October 2 11 Tensile Tests Conditions 5 4 3 2 1 v= 1mm/min. L = 22mm T(room) = 23±2ºC Tensile to the Rupture Young s Modulus (MPa) Composites Materials PET2 Mix3 Mix4 Mix6 Mix1 1 2 3 4 5 6 7 8 9 11112 8 6 4 2 15 1 5 Strain at Break (%) Stress to Yield (MPa) PET2 Mix3 Mix4 Mix6 Mix1 1 2 3 4 5 6 7 8 9 11112 PET2 Mix3 Mix4 Mix6 Mix1 1 2 3 4 5 6 7 8 9 1 11 12

» Mechanical characterisation 4 35 Composites Materials 26 October 2 11 Elastic Mo odulus (M MPa) 3 25 2 15 1 5 8% 14% 1% PET PET2 PET2_3%C15A PET2_3%CNF PP1 PP1 PP1 PP2

» Mechanical characterisation 12 Composites Materials to Yield (MPa) Stress 1 8 6 4 9% 6% 11% 26 October 2 11 2 PET PET2 PET2_3%C15A PET2_3%CNF PP1 PP1 PP1 PP2

» Mechanical characterisation Composites Materials Strain to Break (%) 6 5 4 3 2 Str rain to Break (% %) 7 6 5 4 3 2 1 PET2_3%C15A PET2_3%CNF 4% 26 October 2 11 1 PET PET2 PET2_3%C15A PET2_3%CNF PP1 PP1 PP1 PP2

» Electrical characterisation Tensile tests performed @ 23ºC Multifunctional CNF Nanocomposites Systems Electrical Properties 1,E+15 Extrusion Injection 26 October 2 11 Resistivity) (Ω Ω.m) log(volumic 1,E+12 1,E+9 1,E+6 1,E+3 1,E+ 1 2 3 4 5 6 7 8 9 1 11 CNF (% wt)

» Conclusive remarks Survey main conclusions: Less of 1% of companies contacted for the survey answered. The cost and mechanical resistance of material was the most important specification laid down by companies. The motivation to work with nanomaterials is high, although knowledge on their properties being low The use of nanomaterials in various industries requires a new paradigm of production of new materials. 26 October 2 11

» Conclusive remarks Ternary Nanocomposite main conclusions: The main mechanical properties increase with addition of CNF to PET: 26 October 2 11 The mechanical properties increase with addition of Glass Fibre. In Nanocomposites materials, the Young s Modulus and Stress to Yield increase with increasing of CNF weight % although Strain to Break keep stable. For materials with the addition of 3% of CNF there is an decrease the Elastic Modulus compare with the same amount of C15A materials. However all over properties increase with addiction of CNF.

» Conclusive remarks Ternary Nanocomposite main conclusions: 26 October 2 11 The electrical properties seem to be entirely dependent of method processing. For samples processed by extrusion (less orientation of the conductor nanoreinforcement) electrical percolation is achieved with much less load while driving i the injection process (high orientation of the conductor nanoreinforcement ) for this behaviour is much later.

» Acknowledgments 26 October 211

» Acknowledgments and THANK YOU!... and THANK YOU! 26 October 211