development of injection and blow extrusion molded ... · plasticizers gas barrier properties ......
TRANSCRIPT
OBJECTIVES
V. Peinado1, P. Castell1, A. Fernández1 , E. Passaglia2, R. Spiniello2, C. De Monte2, F. Cicogna2, S. Coiai2,A.Lazzeri3, P. Cinelli3, S.Fiori4, J.Pérez5, J.Hewitt6, C.Konkel6 , B.Gonzalvo1
1 AITIIP Technological Centre, Pol Ind Empresarium. Calle Romero 12, Zaragoza, Spain; 2 National Research Council - Institute of Chemistry of OrganoMetallic Compounds (ICCOM) UOS Pisa; 3 Inter University Consortium Materials Science and Technology (INSTM) 4 Condensia
Quimica, S.A. ; 5 Avanzare Innovación Tecnológica S.L.; 6 Innovia Films Ltd.,
Development of injection and blow extrusion molded biodegradable and multifunctional packages by
nanotechnology: improvement of structural and barrier properties, smart features and sustainability
Grant agreement no: 280676
Product
WaterCO2
Plants
Starch
LactideAcid
PolyLactidAcid
Environmental
Circulation of
PLA *
Photosynthesis
Biodegradation / Incineration
Lactic FermentationPurification
Processing
Polymerization
• Renewable source of materials• Sustainability• Energy consumption and material use
reduction• Eco design
Environment
• Barrier properties• Thermal resistance• Processability
Performances
• Safety• O2 sensor• Intelligent Antimicrobial device• Traceability
Functionalities
SOLUTIONS
* PHA/PHB and cellulose as contingency plan of the project
Improvable processability Plasticizers
Gas Barrier propertiesMechanical properties Thermal behaviour
Biopolymer, biodegradable CompostableHigh TransparencyWater solubility resistance
CONSORTIUM: 19 Partners, 10 Countries
PLA - Advantages & Disadvantages
Processes & Techniques
Injection MouldingBlow Extrusion Moulding
Biaxial Oriented
Film Extrusion
Supercritical Fluids / Foaming
Plasma treatment
Smart DevicesIntelligent Release
Antimicrobial O2 Sensor RFID Tag
NANOADDITIVES
(Bio) Materials & Nanomaterials
•Processand technologies
•Smart
Devices
•Materials&
Nanom
aterialsAPPLICATIONS
Food
Cosmetic
Pharmaceutical
PREL
IMIN
ARY
RES
ULTS
PLA/PlasticizersOrgano-Bentonites
● O-Bentonite long alkyl chain organo-modifier● D43B alkyl and aromatic chain organo-modifier
● NT non modified● NT5 highly long chain hydrophobic
organo-modifier● NT10 hydrophilic organo-modifier
Mg(OH)2
Layered HydroxidesNanofibrous SilicatesSample Mn (mol/g) Mw (mol/g) PDI
PLA 180 110500 192300 1.7PLA 15 OLA8 68900 133800 1.9PLA 20 OLA8 58200 111100 1.9PLA 15 206-3NL 89600 152200 1.7PLA 20 206-3NL 79100 130300 1.7
The use of GLYPLAST® 206-3NL as PLA plasticizer allows a betterpreservation of the polymer Mn and Mw at both the investigatedconcentrations.
Plasticized PLA based nanocomposites
0 50 100 150 200 250 3000
10
20
30
40
50
σ (M
Pa)
ε %
PLA 15 206NL 1Nanofiber T PLA 15 206NL
Nanofibrous silicate composites
● The thermal stability is improvedby the addition of the silicatenanofibers.
● Good mechanical performanceis achieved with a low fillercontent (1% wt).
Nanofibrous silicates are promisingfillers for the preparation of PLA-basednanocomposites for flexiblepackaging applications.
Mg(OH) 2AO
Zn(OH)2
200 250 300 350 400 450 5000
20
40
60
80
100
PLA PLA 1% NANOFIBER T PLA 1% NANOFIBER T5 PLA 1% NANOFIBER T10
weig
ht lo
ss %
T (°C)
GLYPLAST® OLA8
HO
O
O Rnn = 3-15
GLYPLAST® 206/3 NL O
O
O
HO OH
n
Acid number 0.5; Mn (mol/g) =2200; Mw (mol/g)= 2700
Acid number 1.7; Mn (mol/g) =879; Mw (mol/g)= 1226
Sample % weight
1 PLA2 PLA 90/ OLA8 103 PLA 78.2-OLA8 20 - PDLA 1.84 PLA 72.2 – OLA8 20 – LAK 2.8 - PDLA 55 PLA 70 - OLA8 20 - LAK 5 - PDLA 56 PLA 75 - OLA8 20 - LAK 5
A mixture design was used to study the effect of OLA8,and nucleating agents such as PDLA or LAK301 fromTakemoto, on the crystallization time of PLA. Onincreasing the amount of plasticizer (OLA8), it wasobserved a parallel decrease in crystallinity, that can beexplained by the increased mobility of the PLAmolecules in presence of OLA8. The presence ofnucleating agents (LAK and PDLA) also lead to anincrease in crystallinity, and elastic modulus whiledecreasing the elongation at break. However the mostimportant result is a drastic reduction of thecrystallization time. The results of the mixture designevidenced a stronger effect of LAK than of PDLA inreducing the time of crystallization.
Composite compositions :PLA/plasticizer/nanofillera) 84/15/1 (by weight )b) 82/15/3 (by weight)
Figure 1: Parameters of crystallization
Figure 2: Mechanical properties variation
Figure 3: Stress-strain curve ofplasticized PLA and nanocompositecontaining nanofiber T (1 %wt) andplasticizer GLYPLAST® 206/3 NL
Figure 4: TGA analysis of PLA/Nanofiber (1% wt)composites without plasticizer
Scheme 1: Preparation of PLA nanocomposites by a two-step procedureTable 1: Mn,MW , and PDI values calculated by SEC analysis
37,5
3 2,320,46 0,48 1,01
05
10152025303540
1 2 3 4 5 6
ΔH J/g % cryst. t 1/2
6 5.6
310285 278
247
0
50
100
150
200
250
300
350
0
10
20
30
40
50
60
70
1 2 3 4 5 6
E'(GPa) σy(MPa) Ts(MPa) %EL
ACKNOWLEDGEMENTS:The authors want to thank the European Commission for the funds received from the grant agreement number 280676,related to the DIBBIOPACK project and funded under the call “NMP.2011.1.1-1 - Smart and multifunctional packagingconcepts utilizing nanotechnology”, without which this research and development would not be carried out.
Inside Outside
Lidding Film
Polimer Matrix
Superb Barrier Coating
Barrier Coating
INJECTED TRAY
IML Label
O2 SensorRFID
Superb Barrier Coating
Antimicrobial Coating
Inside Outside
Lidding Film
Label Matrix
INJECTED JAR
Traceability and customer relation device
Superb Barrier Coating
Antimicrobial Coating Superb barrier
coating
Foamed PLA
Inside Outside
Lidding Cap
Label Matrix
BLOW-EXTRUDED BOTTLESuperb Barrier Coating
Superb barrier coating
PLA foamed + nanoadditivated
Solutions Proposed
Project Progress
March 2012
Feb. 2016
M12 M24 M36