SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 www.life-sirena.com SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 International Conference on Structural Nano-composites, NANOSTRUC 2014. Madrid, 21/05/2014 www.life-sirena.com 2 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 A2: Materials: A2.1. Nano-composites / Nano-materials selection from each of the industrial sectors under evaluation (Aerospace, Automotive, Construction): A decision framework will be developed in order to carry out the prioritization. If necessary (because there are multiple competing criteria, for example) and if there is enough data available a prioritization matrix will be designed. A2.2. Nano-composites Manufacturing: For each sector of interest three different samples will be produced (one reference samples plus two nano-composite samples with two different selected fillers) A2.3. Verification of the improved performance of nano-reinforced materials versus non-reinforced / traditionally reinforced ones (mechanical, electrical properties…) A test plan will be designed and implemented in order to ensure that all necessary aspects, required to reach a definite conclusion with respect to the potentially improved properties of the non and traditionally reinforced composites versus manufactured nano-composites are evaluated. www.life-sirena.com 3 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 Material Selection from A2.1 Market Matrix Nanoreinforcement Property to be improved Aeronautical Epoxy Carbon nanotubes (CNT) Electrical conductivity Carbon nanofibres (CNFs) Energy Polyester SiO2 NPs Al2 O3 NPs Automotive Polypropilene (PP) Wollastonite (WO) Montmorillonite (MMT) www.life-sirena.com Mechanical properties (Tensile, Flexural and Impact behaviour) Mechanical properties (Tensile, Flexural and Impact behaviour) 4 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 Formulation prepared from A2.1 selection Market Reference Material Nanoreinforcements Formulation to be prepared/studied Aeronautical Epoxy Carbon nanotubes (CNT) Neat Epoxy Carbon nanofibres (CNFs) Epoxy + 2% CNTs SiO2 NPs Neat Polyester Al2 O3 NPs Polyester + 5% SiO2 Energy Polyester Epoxy + 2% CNFs Polyester + 5% Al2 O3 Automotive Polypropilene 20% Talcum Wollastonite (WO) PP + 20% Talcum Montmorillonite (MMT) PP + 5% WO PP+ 5% MMT www.life-sirena.com 5 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 A2.2. Nanomaterials, Nanocomposites Manufacturing www.life-sirena.com 6 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 Material Selection for testing specimens Matrices: •Epoxy Resin: •Polyester Resin: •Polypropylene 20% Talc: •Polypropylene: •Coupling Agent (MAPP): Bi-component resin system MVR444R from CYTEK Unsaturated orthophtalic polyester from RESICHIM HOSTACOM XM2416 from BASELL MOPLEN HP 648T from BASELL POLYBOND 3200 from ADDIVANT Nano-reinforcements: •Carbon Nanotubes (CNT): •Carbon Nanofibres (CNF): •Si O2: •Al203 •Wollastonita (WO): •Montmorillonita (MMT): Multi-walled Graphistrength C100 from ARKEMA PR24-XT-LHT from PYROGRAF SiO2 type 1 from TORRECID Al2 O3 type 1 from TORRECID Harwoll 7ST6, from NORDKALK NANOMER I30T from NANOCOR www.life-sirena.com 7 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AERONAUTICAL Objective: To improve electrical conductivity performance Testing specimens Manufacturing Procedure: CALANDERING (a) Schematic diagram showing the general configuration of a threeroll mill. (b) Region of high shear mixing between the feed and center rolls. EXAKT 80E three roll mill www.life-sirena.com 8 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AERONAUTICAL Testing specimens Manufacturing Procedure: 1. 2. First the nanofillers (carbon nanotubes or carbon nanofibres) and the epoxy component were hand mixed during 3 minutes. Then this mixture was fed in the three-roll mill and it was processed according to the parameters shown in Table 1. Gap between the feed roll and the center roll (µm) 40 20 15 5 3. 4. 5. CALANDERING Gap between the center roll and the apron roll (µm) 120 60 45 15 Speed of the feed roll ω1 (rpm) 28 28 28 28 Speed of the center roll ω2 (rpm) 83 83 83 83 Speed of the apron roll ω3 (rpm) 250 250 250 250 Number of passes 1 1 1 2 The epoxy/nanofiller dispersion obtained after calendering was mixed with the hardener for 15 min by mechanical stirring at 20 rpm under vacuum. Then the mixture was cast in a metallic mould, it was degassed during 20 min Curing in an oven according to a curing cycle of 75min at 160 ºC + 2h at 180 ºC. www.life-sirena.com 9 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AERONAUTICAL Produced Specimens Epoxy CNF Epoxy CNT Epoxy DRILLING (to be divided): • 3 plate of neat Epoxy: 1D-E-1, 1D-E-2, 1D-E-3 • 3 plate of Epoxy + 5% CNT : 1D-E-CNT-1, 1D-ECNT-2, 1D-E-CNT-3 • 3 plate of Epoxy + 5% CNF: 1D-E-CNF-1, 1D-ECNT-2, 1D-E-CNT-3 CRASH: • 3 plate of neat Epoxy: 1C-E-1, 1C-E-2, 1C-E-3 • 3 plate of Epoxy + 5% CNT: 1C-E-CNT-1, 1C-ECNT-2, 1C-E-CNT-3 • 3 plate of Epoxy + 5% CNF: 1C-E-CNF-1, 1C-ECNT-2, 1C-E-CNT-3 18 Specimens 90*130*5 mm 10 www.life-sirena.com SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 ENERGY/CONSTRUCTION Objective: To improve mechanical performance Testing specimens Manufacturing Procedure: 1. 2. 3. 4. 5. DISPERMAT Addition of 5% of nano-reinforcement to Part A of polyester resin Dispermat (high speed mixer) 10 min at 1500rpm Degasing of the mixture in a vacuum chamber during 30 min. Addition 3% of catalyst (Part B) and mixing manually avoiding air entrapment Casting into the mold www.life-sirena.com 11 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 ENERGY/CONSTRUCTION Produced Specimens 5% Doped Polyester Polyester SiO2 Polyester Al2O3 Polyester DRILLING (to be divided): • 3 plate of neat Polyester: 1D-P-1, 1D-P-2, 1D-P-3 • 3 plate of Polyester + 5% SiO2: 1D-P-SIO2-1, 1D-PSIO2-2, 1D-P-SIO2-3 • 3 plate of Polyster + 5% Al2O3: 1D-P-AI2O3-1, 1DP-AI2O3-2, 1D-P-AI2O3-3 CRASH: • 3 plate of neat Polyester: 1C-P-1, 1C-P-2, 1C-P-3 • 3 plate of Polyester + 5% SiO2: 1C-P-SIO2-1, 1C-PSIO2-2, 1C-P-SIO2-3 • 3 plate of Polyster + 5% Al2O3: 1C-P-Al2O3-1, 1CP-Al2O3-2, 1C-P-Al2O3-3 18 Specimens 90*130*5 mm 12 www.life-sirena.com SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE Objective: To obtain a material formulation based on PP doped with montmorillonite (MMT) and/or wollastonite (WO) able to achieve the same mechanical properties than a PP filled with a 20% of Talc with a density decrease of a 10%. • • • • • Polypropylene 20% Talc: Polypropylene (PP): Coupling Agent (MAPP): Wollastonita (WO): Montmorillonita (MMT): HOSTACOM XM2416 from BASELL MOPLEN HP 648T from BASELL (93%) POLYBOND 3200 from ADDIVANT (2%) Harwoll 7ST5, from NORDKALK (5%) NANOMER I30T from NANOCOR (5%) The no polar nature of PP and the high polarity of both silicates (MMT and WO) require the addition of a coupling agent (MAPP, anhydrid maleic polypropylene) in order to assure the right adhesion between nano-fillers and PP thermoplastics matrix. www.life-sirena.com 13 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE Testing specimens Manufacturing Procedure: COPERION ZSK 26 MEGA Compounder Twin Screw Extruder to be used for the preparation of PP EXTRUSION/INJECTION Injection machine ARBURG ALL ROUNDER 270C-300-100 www.life-sirena.com 14 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE Testing specimens Manufacturing Procedure: a) b) c) d) EXTRUSION/INJECTION (a) Extrusion Parameters: (b) Screw Speed: 800 rpm (c) Feeding: Lateral (d) Temperatures: PP 20% Talc PP PP (93%) MAPP(2%) MMT (5%) PP (93%) MAPP(2%) WO (5%) T1 T2 T3 T4 T5 T6 0 190 190 195 195 200 T7 T8 T9 T10 TDie 200 205 210 210 210 20 Specimens “bone” sized 15 www.life-sirena.com SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE Testing specimens Manufacturing Procedure: EXTRUSION/INJECTION DRILLING: • D-PP1; D-PP2; D-PP3, D-PP4, D-PP5. • D-PP-TALC1; D-PP-TALC2; D-PP-TALC3, D-PP-TALC4, D-PP-TALC5 • D-PP-WO1; D-PP-WO2; D-PP-WO3, D-PP-WO4; D-PP-WO5 • D-PP-MMT1; D-PP-MMT2; D-PP-MMT3, D-PP-MMT4; D-PP-MMT5 40 Plate Specimens 140*100*1,6 mm CRASH: • C-PP1; C-PP2; C-PP3; C-PP4; C-PP5 • C-PP-TALC1; C-PP-TALC2; C-PP-TALC3; C-PP-TALC4; C-PP-TALC5 • C-PP-WO1; C-PP-WO2; C-PP-WO3; C-PP-WO4; C-PP-WO5 • C-PP-MMT1; C-PP-MMT2; C-PP-MMT3; C-PP-MMT4; C-PP-MMT5 www.life-sirena.com 16 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 A2.3. Verification of the improved performance of nano-reinforced materials vs non reinforced ones www.life-sirena.com 17 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AERONAUTICAL Objective: To improve electrical conductivity performance Electrical Conductivity Test Description: • Direct Current (DC) conductivity measurements • Sourcemeter Keithley 2410 and a resistivity chamber Keithley 8009 • Chamber is specially designed to perform the test according to the ASTM D-257 standard, for insulating materials, and ASTM D-4496 standard, for moderately conductive materials • Dimensions of the specimens 90 x 70 mm x 2 mm. www.life-sirena.com 18 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AERONAUTICAL Objective: To improve electrical conductivity performance High increase of Electrical Conductivity www.life-sirena.com 19 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 ENERGY/CONSTRUCTION Objective: To improve mechanical performance Performed Mechanical Test: Impact resistance (DIN 53453)  6J Pendulum Flexural resistance (ISO 178) Sting rate 2mm/min Hardness (Shore D) Specimens dimensions for Performed Mechanical Test: Impact resistance (DIN 53453)  120*15*4mm Flexural resistance (ISO 178) 100*80*4mm Hardness (Shore C)  100*80*4mm www.life-sirena.com 20 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 ENERGY/CONSTRUCTION Objective: To improve mechanical performance www.life-sirena.com 21 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 ENERGY/CONSTRUCTION Objective: To improve mechanical performance Material Neat Polyester Polyester +5 wt.% SiO2 Polyester+ 5 wt.% Al2O3 Shore C 75 75 75 The ceramic nanoparticles addition on the polyester matrix, increase flexural resistance, maintain the hardness but they affect in the impact resistance. www.life-sirena.com 22 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE Objective: To obtain a material formulation based on PP doped with montmorillonite (MMT) and/or wollastonite (WO) able to achieve the same mechanical properties than a PP filled with a 20% of Talc with a density decrease of a 10%. Performed Mechanical Test: -Tensile Modulus (ISO 527) -Tensile Strength (ISO 527) -“Bone” sized specimens www.life-sirena.com 23 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE www.life-sirena.com 24 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 AUTOMOTIVE A 5% of Wollastonite can achieve the same tensile properties that a PP 20%Talc with a 10% of density decrease. MATERIAL PP 20% Talc PP 93% MAPP 2% WO 5% PP 93% MAPP 2% MMT 5% DENSITY (gr/cm3) 1,035 0,935 0,942 % of Density Reduction --10,0000 9,3000 We can manufacture a part a 10% lighter with the same mechanical performance www.life-sirena.com 25 SIMULATION OF THE RELEASE OF NANOMATERIALS FROM CONSUMER PRODUCTS FOR ENVIRONMENTAL EXPOSURE ASSESSMENT LIFE11 ENV/ES/596 CONCLUSIONS • AERONAUTICAL: High increase of Electrical Conductivity on epoxy resin when doped with CNT and CNF. Best performace with CNT • ENERGY/ CONSTRUCTION: The ceramic nanoparticles addition on the polyester matrix, increase flexural resistance, maintain the hardness but they affect in the impact resistance. (Pending 2% doped formulations) • AUTOMOTIVE: A 5% of Wollastonite can achieve the same tensile properties that a PP 20%Talc with a 10% of density decrease. We can manufacture a part a 10% lighter with the same mechanical performance www.life-sirena.com 26