Active and Intelligent Packaging www.actinpak.eu
Paper as a Substrate for (Active and) Intelligent Packaging
Martti Toivakka Laboratory of Paper Coating and Converting Center for Functional Materials Åbo Akademi University
Martti Toivakka 2017
AIPIA - Active & Intelligent Packaging Intelligent Packaging Industry Association (www.aipia.info)
Active Solutions Intelligent Solutions • Bio-Chemical active films •Sensors and Tags • Antimicrobial packaging • NFC Technology in packaging
•Oxygen, CO2, Gas-scavenging • Printed Electronics • Moisture control • RFID Technology • Anti-Oxidation • Track, Trace and Control Systems • Temperature Controlled Packaging • Telecommunications • Active labels • IT solutions, software • Nano-technology enabled packaging • Time- and temperature indicators • Hardware (logistical) • Supply chain order,- control- and information systems • Anti-theft devices • Tamper proofing and Anti Counterfeit Systems • Mobile Commerce • Transport & Logistics Martti Toivakka 2017 Modified from www.attophotonics.com Martti Toivakka 2017
1 Fortune-magazine: ”McDonalds Unveils ’McBike’ Bicycle-Friendly Bic Mac Packaging”
Fulton Innovation Martti Toivakka 2017 Martti Toivakka 2017
Hype and Unreasonable Expectations… Communicative Packaging – Bar- and QR(Quick Response)-codes http://www.abo.fi/lpcc
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2 Fordom odlade man vindruvsranka Fordom odlade man vindruvsranka avCommunicative vars frukt man gjorde Packaging ädelt vin. – avCommunicative vars frukt man gjorde Packaging ädelt vin. – Nu man pressar saften ur en planka, Nu man pressar saften ur en planka, doftandeBar- and av äkta QR(Quick terpentin. Response)-codes doftandeBar- and av äkta QR(Quick terpentin. Response)-codes Höj nu bägaren o broder, syster. Höj nu bägaren o broder, syster. Låt den finska skogen rinna kall. Låt den finska skogen rinna kall. Ner i strupenhttp://www.abo.fi/lpcc Ner i strupenhttp://www.abo.fi/lpcc och om du är dyster, och om du är dyster, låt oss dricka upp en liten tall. låt oss dricka upp en liten tall.
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www.huhtamaki.com/adtone www.huhtamaki.com/adtone
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3 Electronically Readable Communicative Communicative Packaging for Medicine Packaging
RFID (Radio Frequency Identification)
NFC (near field communication)
Stora Enso Pharma DDSi Wireless
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Paper Electronics = Disposable Printed Communicative Packaging for Medicine Electronics on/in Paper with Commercial Potential
Incontinence detection, Sensible Solutions Sweden AB
Electro-magnetic blocking, Patient adherence tracking De Barros et al. Pharma DDSi, StoraEnso
Self-cooking soup packaging Stora Enso Pharma DDSi Wireless Fulton Innovation
Martti Toivakka 2017 Martti Toivakka 2017
4 Hybrid Products Product Concepts Based on Electrochemistry Confidex •Combine, e.g. silicon-based Li-ion paper-batteries, “Zero-Cost Diagnostics” Jabbour et al. G.M. Whitesides RFID-chips with printed antenna: › Contactless smartcards and tickets › Product tracing and copy protection Walki® Pantenna
Powercoat® Alive
Ultra thin chips
NDSU Printable LEDs
Gas sensor on paper, Printed bio-sensing platform, Acreo Peltonen et al., FunMat/FlexSens Laser-enabled advanced packaging (LEAP) Martti Toivakka 2017 Martti Toivakka 2017
Functional Printing on Paper
Inkjetted Particulate Silver Ink
Embedding Intelligence R. Bollström et al., 2013. Inkjetted PEDOT:PSS-SWCNT Ink in Paper-based Products
Martti Toivakka 200 µm Laboratory of Paper Coating and Converting Center for Functional Materials • Poor performance due to: Åbo Akademi University › high surface roughness › uncontrolled spreading › uncontrolled absorption P. Angelo et al. NPPRJ 27(2):486, 2012 Martti Toivakka 2017
5 Challenges of Using Paper as Substrate for Printed Electronics
•High surface roughness and porosity, large pore size •Hygroscopicity and poor dimensional stability •Poor long time heat resistance •Complex surface chemistry •Poor barrier properties •Dusty material not allowed in clean room environment used by printed electronics manufacturers
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Example Substrate Concept Printed Electronics Requires Surface for Paper Electronics Smoothness •A combination of: › sufficient smoothness (~50nm RMS), Calandered topcoating Omya › solvent barrier/sealing properties (Kaolin) (DCB, acids, bases etc.), RMS 55 nm › adjustable printability for given Barrier layer functional ink through control of (Latex) surface energy and surface porosity, RMS 260 nm › thermal performance allowing for IR Smoothing layer (Kaolin) sintering Basepaper: 80 g/m2 woodfree Mylar® 250 A µm •Roll-to-roll processable, recyclable RMS 300 nm RMS 30 nm Precoating and compostable (GCC) RMS 580 nm Bollström, R., A. Määttänen, D. Tobjörk, P. Ihalainen, N. Kaihovirta, R. Österbacka, J. Peltonen, and M. Toivakka. "A multilayer coated fiber-based substrate suitable for printed functionality." Organic Electronics 10:1020–1023. J. Järnström, P. Ihalainen, K. Backfolk, J. Peltonen: Applied Surface Science 2542 (2008) 5741 Bollström et al. "Method for creating a substrate for printed or coated functionality, substrate, functional device and its use“, R. Bollström, A. Määttänen, P. Ihalainen, M. Toivakka, J. Peltonen: Chinese patent (ZL 201080006446.5), European patent (2392197) EPO Patent EP2392197, Chinese Patent ZL 201080006446.5 Martti Toivakka 2017 R. Bollstrom, D. Tobjörk, A. Määttänen, P. Ihalainen, R. Österbacka, J. Peltonen, M. Toivakka,: Org. Electronics, 10, 1020 (2009) Martti Toivakka 2017
6 Roughness vs. Conductivity Printing of Functional Materials by Inkjet
Ag comb structure: Silver - Line width 185 µm Barrier layer Topcoat - Gap 595 µm
Precoat Smoothing layer
Base paper
Silver ink for inkjet: Silver content 20 wt% Viscosity 10-13 cps @ 25 °C Surface tension 27-31 dynes/cm
Määttänen, et al., Colloid Surfaces A 367 (2010) 76-84 Martti Toivakka 2017 Martti Toivakka 2017
Improved Inkjet Printability Through Flexography as a Fabrication Process Control of Wettability Ink: 0.5 wt.% P3HT in o-dichlorobenzene (o-DCB), V = 10 pl
P3HT
PET
Määttänen, A., Ihalainen, P., Bollström, R., Toivakka, M., & Peltonen, J. (2010). Colloids and Surfaces A: Physicochemical and Engineering Aspects, 367(1-3), 76–84. Martti Toivakka 2017 Martti Toivakka 2017
7 Surface Porosity Minimizes Commercial Papers for Printed Characteristic “Squeeze” Electronics in Flexography Arjowiggins Felix Schoeller
Ilford Printed Electronics Ltd
Low surface porosity High surface porosity Martti Toivakka 2017 Martti Toivakka 2017
Intelligent Packaging: from Components to Devices and Products Low-voltage Printed Transistor on Paper Sensor component – e.g., chemiresistor, piezoelectrics, HIFET (Hygroscopic Insulator FET): accelerometer, touch sensor Input/Output – e.g., •Source and drain electrochromic inks, color indicators, Power Supply – e.g., › AgNP-ink: Inkjet printed external interface printed battery, and IR-sintered (10 s) supercapacitor, solar Device cell, fuel cell •Organic semiconductor Smart label, Package, › Sensor, Diagnostic P3HT: Inkjet printed FUJIFILM Dimatix, Inc system… •Dielectric (hygroscopic insulator) Memory - e.g., › PVP: Reverse gravure coated WORM, combinations Logic component – of transistors transistor, e.g., Ion •Gate contact modulating FET › PEDOT:PSS: Inkjet printed or drop cast Connectors, Resistors Mini‐Labo, Yasui Seiki Co. Martti Toivakka 2017 Martti Toivakka 2017
8 “FunPrinter” - Custom-built Hybrid R2R-printed Transistors Printer for Functional Materials on Paper
Martti Toivakka 2017 Martti Toivakka 2017
Towards Logic Circuits on Paper Electronically Readable, Printed
CSorb transistor pH Sensor on Paper characteristics
Inverter Ring- oscillator
NOR-gate SR-latch
Electronics, Pettersson, F., Paper- and Membrane-Based Ion-Modulated 2015, PhD thesis, Åbo Akademi Martti Toivakka 2017 Martti Toivakka 2017
9 Electrochromic Pixels Simple Hydrogen Sulfide Sensor
10 ppm H2S at 40% RH
-1.5 V 0 V +1.5 V • Flexography/Inkjet-printed interdigitated electrodes P. Andersson, D. Nilsson, P. O. Svensson, M. X. Chen, A. Malmstrom, T. Remonen, T. Kugler, M. Berggren, “Active matrix displays based on all- • Spray-/reverse gravure coated, or organic electrochemical smart pixels printed on paper”, Advanced Materials inkjet-printed 2002, 14, 1460 › Copper chloride P. Andersson, R. Forchheimer, P. Tehrani, M. Berggren, Printable all-organic › Copper acetate J. Sarfraz, A. Määttänen, P. Ihalainen, M. Keppeler, M. Lindén, J. Peltonen. Printed copper acetate electrochromic active-matrix displays, Adv. Funct. Mater. 17 (2007) 3074– based H2S sensor on paper substrate, Sensors and Actuators B 173:868-873. 3082.
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Printable Demonstrator Circuit for Gas Adjustable Packaging Line for the Future Sensors on Paper •Sensors and indicators for modified atmosphere packaging › E.g. for oxygen and hydrogen sulfide
FunMat/Flexsens/Peltonen et al. Martti Toivakka 2017 Martti Toivakka 2017
10 Oxygen Indicator Proof-of-concept Devices on Paper Methyleneblue+ TiO nanoparticles 2 •Transistors UV-activated Exposure to oxygen indicator •Ring oscillators •1-bit memory •Electrochromic pixels Exposure to oxygen •Light-emitting electrochemical cell •Ion-selective electrodes •Hydrogen sulfide sensors UV-activation •Oxygen sensors •Printable circuit for gas sensors •Reaction arrays •Digital microfluidics Saarinen J.J., Remonen T., Tobjörk D., Aarnio H., Bollström R., Österbacka R. and Toivakka M. (2017) Large-scale roll-to-roll patterned oxygen indicators for modified atmosphere packages. Packaging Technology and Science , 30, 219–227. Martti Toivakka 2017 Martti Toivakka 2017
Fabrication of Solution Processable Advantages of Using Paper as Substrate Devices on Paper for Printed Intelligence/Electronics •Success of fabrication (printability) is determined by •Low cost and large existing product base compatibility of ink – printing method – substrate: •Biodegradability, compostability, ease of disposal › Inks (solution processable functional materials): one-time use, “throw-away electronics”* • Conductive particulate inks, e.g. nanoparticle/micron-size silver, •Controllable mechanical properties: stiffness, flexibility, carbon, gold, copper… • Conductive polymer inks, e.g. PEDOT:PSS, PANI… foldability • Semiconducting inks, e.g. P3HT, PQT… •Adjustable printability of functional materials • Insulators, e.g. PVP, PMMA… •High temperature tolerance inexpensive infrared › Printing / coating method: sintering of functional inks • Inkjet, flexography, rotogravure, screen printing… • Reverse gravure, spray, slot, curtain… •Transparency by using nanopaper (=nanocellulosic films)
› Substrate: Paper/paperboard/nanocellulose film with adjustable •Biocompatibility beneficial for biological applications physico-chemical surface properties * Aliaga et al., The influence of printed electronics on the recyclability of paper: a case study for smart envelopes in courier and postal services. Waste Management 38:41-48, 2015
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11 Paper as a Substrate for Printed Electronics Conclusions and Outlook and Intelligent Packaging . Printed transistors, simple circuits and numerous other •Devices often need to be adapted for paper devices as well as sensors can be fabricated on specialty papers/paperboards •Device(s) to be fabricated, i.e. end-use . However, fabrication of complex devices directly in/onto application, determine which paper properties paper challenging in existing large volume converting and must to be measured and controlled: printing processes: › Barrier properties, surface roughness, surface energy, → Separate production of devices/components (on paper/ surface porosity, dimensional stability, thermal plastic/ silicon) resistance… → Integration in/onto products, e.g., as stickers/labels › …while maintaining the low cost and recyclability •No universal “Paper for printed electronics” exists . Active packaging solutions relatively easy to implement on (excluding perhaps plastic coated paper absorptive & porous paper: emitters, scavengers, absorbers, plastic) antioxidation agents, functional coatings etc.
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http://www.funmat.fi/
electronics
Toivakka M., Peltonen J. and Österbacka R. (2017) Paper electronics. In Irimia- Vladu, M., E.D. Glowacki, N.S. Sariciftci and S. Bauer, eds. Green materials for . Wiley.
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