development of injection and blow extrusion molded ... · plasticizers gas barrier properties ......

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