Final Event. Materials- Research and Results. Zaragoza, 24 February 2016

Transcription

1 Final Event Materials- Research and Results Zaragoza, 24 February 2016

2 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 ( UNIPI Research Unit is located in Pisa ( 2

3 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

4 4

5 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 x1e4 cm-1 SEC Sample Mn (mol/g) Mw (mol/g) PDI PLA2002D (pellets) PLA2002D_ PLA2003D (pellets) PLA2003D_ Torque (Nm) Torque Brabender Mixer TG % NITROGEN Time (s) PLA2002D_180 PLA2003D_ Temperature ( C) PLA 2002D PELLET PLA 2003D PELLET Temperature: 180 C; Rate: 50 rpm Time: 10 min TGA 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 Temperature ( C) PLA 2002D_180 PLA 2003D_180 5

6 Preparation, characterization and optimization of bioplastic based nanocomposites: the nanofillers selection Eventually modified with interactive or reactive functional groups..fully characterized 6

7 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

8 Preparation, characterization and optimization of bio-plastic based nanocomposites: the plasticizers selection 1200 GLYPLAST OLA8 2H GLYPLAST 206-3NL 2H 1000 Wg Sample Mn (mol/g) Mw (mol/g) PDI PLA PLA 15 OLA PLA NL PLA 20 OLA8 PLA NL PLA 15 OLA DTG mg/min DTA uv T ( C) Cel 95.0% 259.3Cel 95.0% Temp Cel 380.3Cel 1.258mg/min 381.9Cel 1.016mg/min GLYPLAST 206-3NL lime:in azoto blu:in aria Cel 1.2% Cel 0.2% TG % 8

9 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

10 Preparation, characterization and optimization of bioplastic based nanocomposites: the characterizations PLA Andib 20 1 % PLA 15 OLA Andib 20 1% PLA 206 3NL Andib 20 1% endo 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 Heat Flow torque (Nm) θ angle tempo (s) PLA (4,13) PLA 15 OLA8 (1,10) PLA NL (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 NL Mn= D Mw= D Mn=75000 D Mw= D Mn=73000 D Mw= D Mn=90700 D Mw= D Mn= D Mw= D Mn=89600 D Mw= D Mn=68900 D Mw= D DTG mg/min T ( C) DTA uv Cel 95.2% 242.0Cel 95.1% Cel 95.2% Cel 94.9% 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) TG % 10

11 Preparation, characterization and optimization of bio-plastic based nanocomposites: selection by properties correlation EXAMPLE: PLA2002D/ NL/1 clay composites Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 Mn Mw Young modulus (GPa) Molecular weight (mol/g) 2,0x10 5 1,6x10 5 1,2x10 5 8,0x10 4 4,0x10 4 Mn Mw Elongation (%) 0 0,0 PLA180 PLA NL PLA NL 1 ANDIB19 PLA NL 1 ANDIB20 0 0,0 PLA180 PLA NL PLA NL 1 ANDIB19 PLA NL 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 NL PLA NL 1 ANDIB19 Mn Mw PLA NL 1 ANDIB 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/ NL/1 nano clay is very close to that of pure PLA 11

12 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 NL PLA NL EXAMPLE: PLA2002D/ NL/1 fibrecomposites Mn Mw PLA NL 1NFT Mn Mw PLA NL 1NFT PLA NL 1NFT5 PLA NL 1NFT5 PLA NL 1NFT10 PLA NL 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, 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 NL PLA NL 1NFT PLA NL 1NFT5 PLA NL 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 elongation % 12

13 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 > Fehri MK, Mugoni C, Cinelli P, Anguillesi I, Coltelli MB, Fiori S, Montorsi M, Lazzeri A. express Polymer Letter 2016; 10(4): 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

14 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

15 Samples properties and Industrial requirements Sample Mechanical properties E (Mpa) σ y (MPa) e y (%) σ b (MPa) e b (%) PLA2003D NL 1 Mg(OH)AO PLA2003D NL 3 Mg(OH)AO PLA2002D NL 1 Nanoclay PLA2002D NL 3 Nanoclay PLA2002D NL 1 NANOFIBER PLA2002D NL 3 NANOFIBER Films Jars standard Premium Bottle >100%

16 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

17 Nano composites by extrusion Mechanical properties E(Gpa) σy(mpa) εy(%) σb(mpa) εb(%) PLA2002D 206-3NL 1 NF T a PLA2003D 206-3NL 1 NF T b PLA2002D 206-3NL 3 NF T a PLA2003D 206-3NL 3 NF T b a produced by melt blending in Brabender, b produced with extrusion in the mini lab. y= Yield, b= Break (PLA2003D+ 15% 206-3NL)1%NANOFIBER T E=1,4 GPa σ y =22 MPa ε y =2,2 % σ b =29 MPa (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) Def.(%) Def.(%) 17

18 Sample Nano composites by extrusion E (Gpa) σ y (MPa) Mechanical properties e y (%) σ b (MPa) PLA2002D NL 1 Mg(OH)AO a PLA2003D NL 1 Mg(OH)AO b PLA2002D NL 3 Mg(OH)AO a PLA2003D NL 3 Mg(OH)AO b PLA2002D NL 1 Clay a e b (%) PLA2002D NL 1 Clay b PLA2002D NL 3 Clay a PLA2002D NL 3 Clay b a produced by melt blending in Brabender, b produced with extrusion in the mini lab., y= Yield, b= Break 18

19 Nano composites with Mg(OH)2 [PLA90/2063NL10] 97% Mg(OH)2 x 2,5AO 3% 19

20 Nano Composites with Nano Fibres [PLA/2063NL] NanoFiberT Sepiolite 20

21 Nano coomposites with Nano Clays [PLA/2063NL] Nanoclay Bentonite 21

22 Mechanical Properties Sample PLA Mg(OH) 2 2,5AO PLA Nano FibreT PLA Nano clay σy εy εb σb E (MPa) (%) (%) (MPa) (GPa)

23 FLAT DIE 23

24 Processing on Industrial scale Sheets with 0.35 mm thickness 24

25 SHEETS MECHANICAL PROPERTIES

26 PLA/206-3NL OLA2 Same concentration E (GPa) 1 σb (MPa) 32.6 εb (%) 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

27 Possible Exploitation Products Modulus Sforzo Elongation Film - Sheets MPa MPa >100 % Rigid packaging (jars) MPa MPa 2% Flexible packaging MPa MPa >100 % PLA/OLA2/ 206/3NL PLA/BST 206/3NL 27

28 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

29 THANKS FOR YOUR ATTENTION CONTACTS INSTM Prof. Andrea Lazzeri Dr. Patrizia Cinelli CNR-ICCOM Dr. Elisa Passaglia elisa Dr. Francesca Cicogna Nanobarrier-Dibbiopack Workshop Frankfurt, 1st of October