Final Event Materials- Research and Results Zaragoza, 24 February 2016
INSTM-UNIPI Key activities INSTM Consortium of Italian Universities for the Science and Technology of Materials, groups 45 Italian Universities where research on Materials is carried out. The group of Prof. Lazzeri, INSTM- Research unit of Pisa University, is active in the chemical and physical characterisation of nanomaterials, polymers, and ceramics as well as in processing, composite, production, microwave processing, green polymeric materials from renewable and sustainable matters, development of new tough and stiff nanocomposite materials. Key figures The Research Unit from INSTM-Pisa University consist of 2 full Professor, 2 researcher, 2 technicians, several PhD and Master Degree students Localisation(s) INSTM administrative offices of INSTM are located at Florence (http://www.instm.it) UNIPI Research Unit is located in Pisa (http://materials.diccism.unipi.it) 2
INSTRUMENTS MiniLab II Haake Rheomex CTW 5 conical twin-screw extruder, Haake MiniJet II mini injection molder COMAC co-rotating twin screw extruder EBC 25HT Thermal Properties (Differential Scanning Calorimetry, Dynamic Mechanical Thermal Analysis GABO) Mechanical Tests: Instron, Impact Charpy FTIR, GS,... etc 3
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Preparation, characterization and optimization of bio-plastic based nanocomposites: the matrix characterization FT-IR %T FT-IR spectra of PLA2002D (black) and PLA2003D (blue) cast film: the spectra 175 of the 4,52 two PLA batches are fully comparable. 4000,0 3000 2000 1500 1000 450,0 x1e4 cm-1 SEC Sample Mn (mol/g) Mw (mol/g) PDI PLA2002D (pellets) 125000 213200 1.7 PLA2002D_180 110500 192300 1.7 PLA2003D (pellets) 115200 200000 1.7 PLA2003D_180 129700 207300 1.6 Torque (Nm) 14 12 10 8 6 4 2 Torque Brabender Mixer 0 0 60 120 180 240 300 360 420 480 540 600 100 80 TG % 60 40 20 0 NITROGEN Time (s) PLA2002D_180 PLA2003D_180 0 100 200 300 400 500 600 700 Temperature ( C) PLA 2002D PELLET PLA 2003D PELLET Temperature: 180 C; Rate: 50 rpm Time: 10 min TGA100 80 60 TG % PLA2003D_180 is a little bit more stable than PLA2002D_180 PLA2002D and PLA2003D have a different thermal behaviour: the second heating scan of PLA2002D (pellets) does not show cold crystallization neither melting 40 20 0 0 100 200 300 400 500 600 700 Temperature ( C) PLA 2002D_180 PLA 2003D_180 5
Preparation, characterization and optimization of bioplastic based nanocomposites: the nanofillers selection Eventually modified with interactive or reactive functional groups..fully characterized 6
Preparation, characterization and optimization of bioplastic based nanocomposites: the plasticizers O HO O R n n= 3-15 R= high MW linear alcohols GLYPLAST OLAs HO O adipic acid + O OH HO propylene glycol OH GLYPLAST 206/X GLYPLAST OLA8 GLYPLAST OLA9 GLYPLAST OLA8 DIACID GLYPLAST OLA8 DIACID SALT GLYPLAST OLA8-MAL GLYPLAST OLA-0,5AN-1100FW GLYPLAST OLA-2,5AN-1500FW GLYPLAST OLA-2,5AN-3000FW GLYPLAST 206-3NL 7
Preparation, characterization and optimization of bio-plastic based nanocomposites: the plasticizers selection 1200 GLYPLAST OLA8 2H GLYPLAST 206-3NL 2H 1000 Wg -1 800 600 400 200 0 Sample Mn (mol/g) Mw (mol/g) PDI PLA 180 110500 192300 1.7 68900 133800 1.9 PLA 15 OLA8 1380 1560 PLA 15 206-3NL PLA 20 OLA8 PLA 20 206-3NL PLA 15 OLA9 89600 2200 58200 1100 79100 2300 75900 1100 152200 3000 111100 1460 130300 3200 148500 1600 1.7 1.9 1.7 1.9 DTG mg/min 1.400 1.200 1.000 0.800 0.600 0.400 0.200 0.000-0.200-0.400 DTA uv -140-120 -100-80 -60-40 -20 0 20 40 T ( C) 100.0 200.0 257.6Cel 95.0% 259.3Cel 95.0% 300.0 400.0 Temp Cel 380.3Cel 1.258mg/min 381.9Cel 1.016mg/min GLYPLAST 206-3NL lime:in azoto blu:in aria 500.0 689.9Cel 1.2% 600.0 690.0Cel 0.2% 125.0 120.0 115.0 110.0 105.0 100.0 95.0 90.0 85.0 80.0 75.0 70.0 65.0 60.0 55.0 50.0 45.0 40.0 35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0-5.0-10.0-15.0-20.0 TG % 8
Preparation, characterization and optimization of bioplastic based nanocomposites: the methodology Plasticizer PLA + Inorganic nanostructured material Masterbatch ❶ Nanocomposite ❷ Aim: the use of plasticizers as coupling agent able to disperse the nanofiller and favor the intercalation of PLA chains 9
Preparation, characterization and optimization of bioplastic based nanocomposites: the characterizations 40000 35000 30000 PLA Andib 20 1 % PLA 15 OLA Andib 20 1% PLA 206 3NL Andib 20 1% endo 32 30 28 26 PLA PLA 1% Mg(OH) 2 AO PLA 15% OLA8 PLA 15% OLA8 1% Mg(OH) 2 AO PLA 15% OLA8 3% Mg(OH) 2 AO intensity a.u. 25000 20000 15000 Heat Flow 24 22 20 18 16 14 10000 12 5000 10 8 torque (Nm) 14 12 10 8 6 4 2 0 5 10 15 20 25 30 2θ angle 0 60 120 180 240 300 360 420 480 540 600 tempo (s) PLA (4,13) PLA 15 OLA8 (1,10) PLA 15 206-3NL (2,11) Torque evolution and SEC analysis at different time 3.5, 5 and 10 min for OLA8 3.5, 8 and 10 min for 206-3 NL Mn=105800 D Mw=182800 D Mn=75000 D Mw=140000 D Mn=73000 D Mw=146600 D Mn=90700 D Mw=156700 D Mn=110500 D Mw=192300 D Mn=89600 D Mw=152200 D Mn=68900 D Mw=133800 D DTG mg/min 6 40 60 80 100 120 140 160 180 T ( C) DTA uv 100.0 259.7Cel 95.2% 242.0Cel 95.1% 200.0 275.4Cel 95.2% 300.0 316.5Cel 94.9% 400.0 Temp Cel Nitrogen black: PLA blue: PLA 1 Mg(OH)2 2,5 AO purple: PLA 1 Mg(OH)2 fuchsia: PLA 1 Zn(OH)2 500.0 600.0 115.0 110.0 105.0 100.0 95.0 90.0 85.0 80.0 75.0 70.0 65.0 60.0 55.0 50.0 45.0 40.0 35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0-5.0-10.0-15.0 TG % 10
Preparation, characterization and optimization of bio-plastic based nanocomposites: selection by properties correlation EXAMPLE: PLA2002D/15 206-3NL/1 clay composites Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 Mn Mw 4 3 2 1 Young modulus (GPa) Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 Mn Mw 300 250 200 150 100 50 Elongation (%) 0 0,0 PLA180 PLA 15 206-3NL PLA 15 206-3NL 1 ANDIB19 PLA 15 206-3NL 1 ANDIB20 0 0,0 PLA180 PLA 15 206-3NL PLA 15 206-3NL 1 ANDIB19 PLA 15 206-3NL 1 ANDIB20 Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 0,0 PLA180 PLA 15 206-3NL PLA 15 206-3NL 1 ANDIB19 Mn Mw PLA 15 206-3NL 1 ANDIB20 350 300 250 200 150 100 Tonset ( C) Conclusions: The addition of 1 wt% nano clay from AVANZARE allows improving the elongation at break of the 206-3NL plasticised PLA and to reach the highest Young's Modulus of the series. At the same time, T onset of PLA2002D/15 206-3NL/1 nano clay is very close to that of pure PLA 11
Preparation, characterization and optimization of bio-plastic based nanocomposites: selection by properties correlation Molecular weight (mol/g) Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 0,0 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 0,0 PLA_180 PLA_180 PLA 15 206-3NL PLA 15 206-3NL EXAMPLE: PLA2002D/15 206-3NL/1 fibrecomposites Mn Mw PLA 15 206-3NL 1NFT Mn Mw PLA 15 206-3NL 1NFT PLA 15 206-3NL 1NFT5 PLA 15 206-3NL 1NFT5 PLA 15 206-3NL 1NFT10 PLA 15 206-3NL 1NFT10 3,2 3,0 2,8 2,6 2,4 2,2 2,0 1,8 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 350 300 250 200 150 Modulus GPa Tonset ( C) Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 0,0 Conclusions: PLA_180 Mn Mw PLA 15 206-3NL PLA 15 206-3NL 1NFT PLA 15 206-3NL 1NFT5 PLA 15 206-3NL 1NFT10 The Young's Modulus of the composites prepared by adding 1 wt% of fibers T5 and T10 to the 15 wt% 206-3NL plasticized PLA is higher than that of their matrix sample and the elongation and break is substantially unchanged and compatible with a plasticized system T onset is also elevated confirming the very good effect of these fillers in improving the thermal stability of PLA and plasticized PLA samples Notably the degradation of the plasticized PLA is also avoided 250 200 150 100 50 0 elongation % 12
Nucleating agents LAK (%) PDLA (%) Crystallization half time t ½ (sec) Crystallinity (%) Tensile Strength Yield (GPa) E (GPa) Tensile Strength at Break (MPa) Elongation at Break (%) 0 0 >1800-27 1.5 19 293 5 0 61 4.2 28 2.0 18 247 5 5 48 6.5 11 1.0 20 278 3 5 46 7.3 18 2.0 23 285 0 2 151 4.3 33 1.1 28 640 Fehri MK, Mugoni C, Cinelli P, Anguillesi I, Coltelli MB, Fiori S, Montorsi M, Lazzeri A. express Polymer Letter 2016; 10(4): 274-288 Composition dependence of the synergistic effect of nucleating agent and plasticizer in poly(lactic acid): A Mixture Design study Nanobarrier-Dibbiopack Workshop Frankfurt, 1st of October 2014 13
Preparation, characterization and optimization of bioplastic based nanocomposites: results Fiber T, T5 (1-3%) Glyplast 206-3NL (15-20%) PLA LAK, PDLA Nanoclay (1-3%) 14
Samples properties and Industrial requirements Sample Mechanical properties E (Mpa) σ y (MPa) e y (%) σ b (MPa) e b (%) PLA2003D 15 206-3NL 1 Mg(OH)AO 1500 17 2.4 27 173 PLA2003D 15 206-3NL 3 Mg(OH)AO 1500 30 2.0 29 210 PLA2002D 15 206-3NL 1 Nanoclay 1400 21 1.7 30 200 PLA2002D 15 206-3NL 3 Nanoclay 1500 21 1.8 28 200 PLA2002D 15206-3NL 1 NANOFIBER 1400 22 2.2 29 175 PLA2002D 15206-3NL 3 NANOFIBER 2200 23 2.6 31 206 Films Jars standard Premium Bottle 250-350 25-30 1000-2000 3000 20-30 50 2000 30-40 >100% 200 2 2-100 15
Preparation, characterization and optimization of bioplastic based nanocomposites: the scale-up 206/X series prepared by esterification of adipic acid with propylenglycol PLA 2003D with 5%, 10% and 15% by weight of plasticizer 16
Nano composites by extrusion Mechanical properties E(Gpa) σy(mpa) εy(%) σb(mpa) εb(%) PLA2002D 206-3NL 1 NF T a 1.1 32 4.0 48 222 PLA2003D 206-3NL 1 NF T b 1.4 22 2.2 29 175 PLA2002D 206-3NL 3 NF T a 1.6 32 3.4 41 13.7 PLA2003D 206-3NL 3 NF T b 2.2 23 2.6 31 206 a produced by melt blending in Brabender, b produced with extrusion in the mini lab. y= Yield, b= Break 40 30 (PLA2003D+ 15% 206-3NL)1%NANOFIBER T E=1,4 GPa σ y =22 MPa ε y =2,2 % σ b =29 MPa 40 30 (PLA2003D+ 15% 206-3NL) 3%NANOFIBER T E=2,2 GPa σ y =23,4 MPa ε y =2,6 % σ b =31 MPa ε b =175 % ε b =206 % Stress (MPa) 20 Stress (MPa) 20 10 10 0 0 50 100 150 200 250 Def.(%) 0 0 50 100 150 200 250 Def.(%) 17
Sample Nano composites by extrusion E (Gpa) σ y (MPa) Mechanical properties e y (%) σ b (MPa) PLA2002D 15 206-3NL 1 Mg(OH)AO a 1.6 14 3.3 25 267 PLA2003D 15 206-3NL 1 Mg(OH)AO b 1.5 17 2.4 27 173 PLA2002D 15 206-3NL 3 Mg(OH)AO a 1.0 13 3.4 22 262 PLA2003D 15 206-3NL 3 Mg(OH)AO b 1.5 30 2.0 29 210 PLA2002D 15 206-3NL 1 Clay a 1.0 13 3.8 21 250 e b (%) PLA2002D 15 206-3NL 1 Clay b 1.4 21 1.7 30 200 PLA2002D 15 206-3NL 3 Clay a 1.7 24 3.2 25 268 PLA2002D 15 206-3NL 3 Clay b 1.5 21 1.8 28 200 a produced by melt blending in Brabender, b produced with extrusion in the mini lab., y= Yield, b= Break 18
Nano composites with Mg(OH)2 [PLA90/2063NL10] 97% Mg(OH)2 x 2,5AO 3% 19
Nano Composites with Nano Fibres [PLA/2063NL] NanoFiberT Sepiolite 20
Nano coomposites with Nano Clays [PLA/2063NL] Nanoclay Bentonite 21
Mechanical Properties Sample PLA Mg(OH) 2 2,5AO PLA Nano FibreT PLA Nano clay σy εy εb σb E (MPa) (%) (%) (MPa) (GPa) 24.5 1.5 182.3 24.3 1.8 23.0 6.3 202.3 30.2 2.2 15.3 2.0 182.2 28.5 1.9 22
FLAT DIE 23
Processing on Industrial scale Sheets with 0.35 mm thickness 24
SHEETS MECHANICAL PROPERTIES
PLA/206-3NL OLA2 Same concentration E (GPa) 1 σb (MPa) 32.6 εb (%) 169.2 σy (MPa) 38.3 εy (%) 1.2 Same PLA/206-3NL BST concentration E (GPa) 3 σb (MPa) 41.2 εb (%) 5.3 σy (MPa) 53 εy (%) 2.3
Possible Exploitation Products Modulus Sforzo Elongation Film - Sheets 250-350 MPa 25-30 MPa >100 % Rigid packaging (jars) 1000-3000 MPa 20-30 MPa 2% Flexible packaging 250-350 MPa 25-30 MPa >100 % PLA/OLA2/ 206/3NL PLA/BST 206/3NL 27
CONCLUSIONS Extensive screening of plasticizers and nano additives allowed selecting promising formulation for scale up production. Polymeric matrix based on PLA 2003D and 5-15% by weight of plasticizer, and <5% of nano additves. Nano clays are suitable, and Nano sepiolite based fibres most performing. Several batches of PLA based formulation were prepared on pilot scale and delivered to the industrial partners for processing tests and prototypes production. Melt Strength Enhancer, OLA2, and Nucleating agents (LAK, PDLA) improves processing and performances. 28
THANKS FOR YOUR ATTENTION CONTACTS INSTM Prof. Andrea Lazzeri andrea.lazzeri@unipi.it Dr. Patrizia Cinelli patrizia.cinelli@diccism.unipi.it CNR-ICCOM Dr. Elisa Passaglia elisa passaglia@pi.iccom.cnr.it Dr. Francesca Cicogna francesca.cicogna@pi.iccom.cnr.it Nanobarrier-Dibbiopack Workshop Frankfurt, 1st of October 2014 29