Enhancement of PLA properties by nanoparticles
17.9.2012
Enhancement of PLA properties by nanoparticles
Prof. Dr. Clemens Holzer Trends in Bioplastics, Ljubljana, September 17th 2012
Otto Gloeckel-Straße 2, A-8700 Leoben, Tel.: +43 3842 402 3501
[email protected] www.kunststofftechnik.at
Chair of Polymer Processing, Department of Polymer Engineering and Science, Montanuniversitaet Leoben
LEOBEN
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www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Montanuniversitaet Leoben Numbers and facts About 3´500 students (women 23 %) About 450 beginners Foreign students ~ 13 % ca. 300 graduates / year ca. 1000 employees: 40 Professors and 700 scientific workers (ca. 300 of them financed by projects) Global budget 38 Mio €, in addition 23 Mio € from projects Montanuniversitaet educates for important industry sectors exclusively www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Polymer Engineering and Science at Leoben More than 40 years of success >650 graduates -> highly responsible for the success of companies in the fields of Polymer engineering Currently +30 graduates per year More than 200 employees (university and PCCL) Science and applied R&D in tight cooperation with companies Hundreds of big (e.g. EC-projects) and small projects More than 600 publications within the last 5 years International activities: conferences and co-operations with companies and institutes www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
4 Pillar-Model From molecule
to material
via processing
to components / products / systems
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Department of Polymer Engineering and Science Leoben Chairs Chemistry of Polymeric Materials Prof. Wolfgang Kern Designing Polymeric and Composite Materials Prof. Rudolf Wörndle Injection Moulding of Polymers Prof. Walter Friesenbichler Materials Science and Testing of Polymers Prof. Gerald Pinter Polymer Processing Prof. Clemens Holzer Processing of Composites Prof. Ralf Schledjewski www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
New Polymer Center Leoben Home of the Department since April 2010, 6600 m2
Investments: Building ~17 Mio. € Interior ~2 Mio. € 4,4 Mio € for new R&D-equipment: - 1´200´000 € Injection Moulding-Compounder - 800´000 € Component testing device - 1´000´000 € R&D-Center for polymer micro- and nanotechnology - 1´200´000 € New extruders and injection moulding machines - 150´000 € Laboratory equipment www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Polymer Competence Center Leoben GmbH PCCL COMET K1-Center 2010 - 2017 „Center of Excellence“ for application-oriented research in the field of polymeric materials
Key Figures CEO
Martin Payer
CSO
Wolfgang Kern
R&D-projects
35
Patents
12
Headquarters of PCCL (Leoben, Austria) www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Polymer Engineering and Science Leoben Facts and Figures
Department Turnover (third party funds) Employees
> 5 Mio € (3 Mio €) 107
Scientific staff Non scientific staff
PCCL > 6 Mio € 90
52 34 21
Students
Office and laboratory space
6´600 m2
1´200 m2
Equipment (new)
10 Mio €
2 Mio €
Σ : 11 Mio € and 200 people www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Content
Polymer nanocomposites Processing of nanocomposites Results Conclusion
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Basics for successful products
Processing
Product Design Construction
Material
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Impact strength and stiffness 60 Unfilled Polypropylene
55
Nanocomposites
Izod Impact, J/m
50
Projected Performance
45 40 35
40% Calcium Carbonate
30
40% Mica
40% Talc
25 20 0
2
4 6 Tensile Modulus, GPa
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Dow, “Nanostructures and Transportation Applications” U.S. Department of Transportation Volpe Center, Boston June 24-5, 1999
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Polymer nanocomposites Modification of material properties Rheological properties • viscosity, melt strength, melt elasticity Mechanical properties • volume properties: Young modulus, tensile strength, toughness, etc. • surface properties: hardness, abrasion, crack grow, etc. Functional properties • barrier, optical (transparency) and thermal properties, flammability, dimensional stability, easy- or self-cleaning surface etc.
0,1 – 5 wt.%
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Prof.Dr. Clemens Holzer
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Types of nanoparticles Fullerene
Nanotubes
[2]
[1]
0,4-100 nm L/D > 10.000
1-6 nm Me, Me-Oxide
HeiQ
Layered Silicates
[3]
1-6 nm L/D ~ 500
10-50 nm www.kunststofftechnik.at
SiO2
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
[4]
10-500 nm 14
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Enhancement of PLA properties by nanoparticles
17.9.2012
Structure of montmorillonite
Source: Süd Chemie, Inc.
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Prof.Dr. Clemens Holzer
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Properties of montmorillonite • High Young modulus (270 GPa, Monte Carlo Simulation) • Large specific surface (400 - 600 m2/g) • High aspect ratio (100 - 500) • Fire resistance • Possibility of surface modification
Cloisite Na+ www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
Cloisite 30B 16
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Enhancement of PLA properties by nanoparticles
17.9.2012
Structures of layered silicates in polymer
conventional
intercalated
exfoliated
Source: Kaempfer D. „Nanocomposites aus technischen Thermoplasten und organophilen Schichtsilikaten“, PhD Thesis, 2005
Available – effortable – technological controllable
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Functionalisation of layered silicates Substances for intercalation Ammonium salts, mostly ammoniumbromide z.B.: hexadecyltrimethylammoniumbromid
Substances for coating Fatty acids e.g.: Oleic acid
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Possible application of nanocomposites Reduction in gas permeability and flammability with layered silicate
without layered silicate
Source: Süd Chemie, Inc.
• Barrier for CO2, O2, N2
• Transport bands (Metallurgy)
• Beer bottles
• Cable insulation
• Soft drink packages
• Fire protective clothing
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Content
Polymer nanocomposites Processing of nanocomposites Results Conclusion
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Production of nanocomposites – scheme Polymer
Polymer
Modificated nanoparticles
Compounding
Polymer processing Processparameters
Processparameters
www.kunststofftechnik.at
Testing
Nanocomposites
Simulation
Prof.Dr. Clemens Holzer
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Production of nanocomposites Co-rotating twin-screw extruder Werner&Pfleiderer ZSK-25 (Coperion GmbH, Stuttgart, Germany) Feeding by gravimetrical dosage units Hopper feeding: Polymer matrix Side feeding: Clay
Materials: PLA: Ingeo 2003D Clays: different surface treatment Cloisite: Na+ based MMT Nanofil: Ca2+ based MMT Garamite www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Screw geometry
Kracalik M., Laske S., Gschweitl M., Friesenbichler W., Langecker G.R. (2009) J Appl Polym Sci 113(3): 1422-1428
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Prof.Dr. Clemens Holzer
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Characterization of nanocomposites Rheometry and tensile testing Physica MCR 501, Anton Paar, Graz, Austria - Cone-plate geometry - Strain-sweep test (linear viscoelastic region of γ = 0.001 – 0.3 %) - Frequency-sweep test (T = 210 / 270 ̊C, ω = 0.1 – 100 rad/s, γ = 0.01 %) Z010, Zwick Ltd & Co. KG, Ulm, Germany - Measurement set-up according to ISO 527-1 - Specimens prepared by compression molding (150 mm x 20 mm x 4 mm) - Experimental conditions (23 ± 2 °C / 50 ± 5% r.H.)
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Content
Polymer nanocomposites Processing of nanocomposites Results Conclusion
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Characterization of PLA nanocomposites Rheometry - viscosity 4
Complex viscosity (Pa.s)
10
3
10
PLA N 116 C 20A N 3010 C 10A C 30B Garamite
2
10
1
10
100
Angular frequency (rad/s) www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Characterization of PLA nanocomposites Tensile testing - extensibility 7
6
Extensibility (%)
5
4
3
2
1
0 PLA
N 116
C 20A
N 3010
C 10A
C 30B
Garamite
Sample www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Characterization of PLA nanocomposites Tensile testing – tensile strength 70
Tensile strength (MPa)
60
50
40
30
20
10
0 PLA
N 116
C 20A
N 3010
C 10A
C 30B
Garamite
Sample www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Characterization of PLA nanocomposites Tensile testing – Young´ ´s modulus 4
Young modulus (GPa)
3
2
1
0 PLA
N 116
C 20A
N 3010
C 10A
C 30B
Garamite
Sample www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
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Characterization of PLA nanocomposites Oxygen permeability 60
100
80
60
40 20
Difference (%)
SSD (cc/m²/day)
40
20
0
0 PLA
C 15A
C 20A
N 3010
N 116
C 10A
C 30B Garamite
Sample www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Conclusion PLA and nanoparticles: strong influence of filler on processing and utility properties Increased melt elasticity due to clay admixture, formation of 3D network Increased stiffness as well as toughness in some nanocomposites Significant reduction in oxygen permeability
Biopolymers can be enhanced significantly via nanoparticles
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Prof.Dr. Clemens Holzer
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Acknowledgement I would like to thank Martin Hirschenauer for the precious work he and his supervisors did: Dr. Michael Washüttl from OFI, Vienna and Dr. Milan Kracalik from the chair of Polymer Processing Special thanks to the head of Center of Compounding, Prof.Dr. Stephan Laske. The project N901•NAN PlaComp1 was founded by Austrian Nanoinitiative
Thank you for your attention! www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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Enhancement of PLA properties by nanoparticles
17.9.2012
Literatur [1] http://commons.wikimedia.org/wiki/File:Fullerene-C60.png (22.12.2010) [2] http://www.tech-faq.com/what-are-carbon-nanotubes-used-for.html (22.12.2010) [3] Meister, Einfluss des Verarbeitungsprozesses auf physikalische Eigenschaften von Nanocomposites, Masterarbeit 2010 IKV Leoben [4] http://www.whitehousescientific.com/images/news/silica.jpg (22.12.2010) [5] Biatain Ag.: Superior extrudate management and continuous release of silver, URL: www.biatain.coloplast.com, (Abgerufen am: 20.11.2011). [6] Zhifei Li, Guohua Luo *, Fei Wei, Yi Huang: Microstructure of carbon nanotubes/PET conductive composites fibers and their properties, Composites Science and Technology 66 (2006) 1022–1029 [7] HeiQ: Aus der Zusammenarbeit mit der Fa. HeiQ, Schweiz, www.heiq.com [8] Fritzsche, J.: Einsatz von innovativen Nanowerkstoffen in Gummimischungen zur Verbesserung der Funktionalitäten von reifen und technischen Elastomerprodukten im Automobilbereich, Vortrag WING Statusseminar zur Leitinnovation „Nanomobil“ – Verbundvorhaben Nano-Elastomer. [9] http://www.wasser-shop24.de/Aqua-Tower, 24.11.2011 [10] R. G. Egres Jr., M. J. Decker, C. J. Halbach, Y. S. Lee, J. E. Kirkwood, K. M. Kirkwood, N. J. Wagner: STAB RESISTANCE OF SHEAR THICKENING FLUID (STF)–KEVLAR COMPOSITES FOR BODY ARMOR APPLICATIONS, 24th Army Science Conference, Orlando, FL, 2 December 2004
www.kunststofftechnik.at
Prof.Dr. Clemens Holzer
Kunststoffverarbeitung an der Montanuniversität Leoben
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