Development of an Innovative Oxygen Scavenging Label: A journey from the Idea to the Product
Prof. Dr. Selcuk Yildirim Zürich University of Applied Sciences Institute of Food and Beverage Innovation
1 Zurich University of Applied Sciences
• Institute of Biotechnology
• Institute of Chemistry and Biological Chemistry
• Institute of Food and Beverage Innovation
• Institute of Natural Resource Sciences
• Institute of Applied Simulation
Zurich University of Applied Sciences
2 Department of Life Sciences and Facility Management Center for Food Processing and Packaging
Innovative and sustainable processes and packaging development for optimal food quality and safety
Prof. Dr. Selcuk Yildirim
Dr. Nadina Dr. Jürg Beatrice Stella Dr. Janice Dr. Claudia Dr. Mathias Philippe Ramona Patrick Näf Müller Buchli Baumer Cook Sych Müller Kinner Geiger Rüegg
Prof. Dr. Nadine Susanna Bettina Annica Barbara Pius Meier
Selcuk Yildirim Rüegg Miescher Röcker Jucker Beck 3 Research Fields
Innovative Biopackaging Development and Shelf life Packaging Materials Optimization of simulations Packaging Processes
- Shelf life simulations - Active Packaging - Biobased materials - Modified atmosphere packaging - Optimal packaging - Biodegradable - Antimicrobial films design materials - Controlled atmosphere - Oxygen Scavengers - Optimization of - Sustainable packaging packaging - Moisture Scavengers packaging development - Integration in food - Optimization of processing - High barrier materials storage cond.
- New packaging
processes
4 Content
1. Active Packaging
2. Development of Palladium based Oxygen Scavenging Label
Idea
Development
Industrialisation
3. Applications
5 Content
1. Active Packaging
2. Development of Palladium based Oxygen Scavenging Label
Idea
Development
Industrialisation
3. Applications
6 Active Packaging
Active Packaging: „..designed to deliberately incorporate components that would release or absorb substances into or from the packaged food or the environment surrounding the food“ Regulation (EC) No 1935/2004 A
* Yildirim S. Active Packaging for Food Biopreservation, in Protective Cultures, Antimicrobial Metabolites and Bacteriophages for Food and Beverage Biopreservation, Lacroix C (ed). Woodhead Publishing: Cambridge, 2011; 460-489. 7 Yildirim S., Röcker B., Pettersen M.K., Nygaard Julie N., Ayhan Z., Rutkaite R., Radusin T., Suminska P., Marcos B., Coma V., Active Packaging for Food Applications, Comprehensive Reviews in Food Science and Food Safety, 2018, 17: 165–199.
Vilela C., Kurek M., Hayouka Z., Röcker B. Yildirim S., Antunes M. D. C. Nygaard J. N. Pettersen M. K., Freirea, C. S. R. A concise guide to active agents for functional8 food packaging, Trends in Food Science & Technology, 2018, 80, 212-222 Content
1. Active Packaging
2. Development of Palladium based Oxygen Scavenging Label
Idea
Development
Industrialisation
3. Applications
9 Oxidation of Food
Growth of aerobic Oxidation O2 microorganisms
Discoloration Moulds and other and rancidity Spoilage organisms
Degraded appearance Impaired sensory Lost freshness, unpleasant and nutritional value qualities taste and aroma
Reduced Shelf life 10 Modified Atmosphere Packaging
- Gas Flushing
- Modified Atmosphere Packaging
Up to 3-5% residual oxygen11 Oxygen Scavengers
12 Palladium-based Oxygen Scavenger
1. 2. step 3. step 4. step H O 2 H step O O H2 O O O O O * H O H H H H O Pd Pd Pd Pd Pd
Nyberg C, Tengstål CG. Adsorption and reaction of water, oxygen, and hydrogen on Pd(100): Identification of adsorbed hydroxyl and implications for the catalytic H2–O2 reaction. The Journal of Chemical Physics 1984. 80(7): pp. 3463-3468, DOI: 10.1063/1.447102. 13 Pd Deposition Thickness
2.5 100 nm 50 nm 2.0 10 nm 5 nm
1.5
1.0
0.5
Oxygen Concentration [%] Concentration Oxygen
0.0 0 2 4 6 8 10 12 14 16 18 20 Time [h] PET/Pd
14 Patent: EP2236284, 2010, S. Yildirim, J.C-Jammet, W. Lohwasser Pd Coated Surface Analysis
100 nm 50 nm 20 nm 10 nm 5 nm
• Pd coated surfaces were analyzed using scanning electron microscopy
• 100 nm to 20 nm surface is flat
• A sponge like structure in 10 and 5 nm sample
• 10 nm sample is more dense than 5 nm sample
15 Palladium-based Oxygen Scavenging Label
Pd H2 + ½ O2 H2O
Yildirim S, Jammet JC, Lohwasser W. Multi-layer film. European Patent, 2236284, 6/10/2010. Effect of Coating Substrate on the Oxygen Scavenging Activity
Oxygen Scavenger
Palladium Substrate vs.
Palladium SiOx Substrate
Yildirim S, Röcker B, Rüegg N, Lohwasser W. Development of Palladium-based Oxygen Scavenger: Optimization of Substrate and Palladium Layer Thickness. Packaging17 Technology and Science 2015. 28(8): pp. 710-718 Effect of Palladium Deposition Thickness on the Oxygen Scavenging Activity
Oxygen Scavenger
Palladium
SiOx Substrate
Best Substrates: • PET • PET/AlOx • PLA • LDPE • oPP
18
18 Effect of Coating Substrate on the Oxygen Scavenging Activity
Oxygen Scavenger
Palladium
SiOx Substrate
Best Substrates: • PET • PET/AlOx • PLA • LDPE • oPP
19 Oxygen Scavenging Activity in the Presence of Food
2,2
2,2
2,0 2,0 1,8 1,8 1,6 1,6 1,4 1,4 1,2 1,2 1,0 1,0 0,8 0,8 0,6
0,6 Oxygen concentration / vol.% vol.% / concentration Oxygen
Oxygen concentration / vol.% vol.% / concentration Oxygen 0,4 0,4 0,2 0,2 0,0 0,0 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160 Time / min Time / min Empty Packaging Ham Empty Packaging Potato Chips Roast Beef Cheese Potato Powder Milk Powder Peanuts Par-baked Buns Cereals Röcker B., Rüegg N., Glöss A. N., Yeretzian C., Yildirim S., Inactivation of Palladium-based Oxygen Scavenger by Volatile Sulphur Compounds Present in the20 Headspace of Packaged Food, Packaging Technology and Science, 2017, 30, 8, 427-442 Catalyst Poisoning by Volatile Sulphur compounds (VSCs)
Maxted EB. The Poisoning of Metallic Catalysts, in Advances in Catalysis, Frankenburg WG, Komarewsky VI, Rideal EK, Emmett PH, Taylor HS (ed). Academic Press,
1951 21
Bartholomew CH. Mechanisms of catalyst deactivation. Applied Catalysis A: General 2001. Volatile Sulphur Compounds (VSCs) in Foods
Beef Volatile sulphur compounds Pork Potato Roasted (Roast Cheese Bread (VSCs) (Ham) Chips Peanuts Beef)
Dimethyl sulphide (DMS) x x x x x
Dimethyl disulphide (DMDS) x x x x x x
Dimethyl trisulphide (DMTS) x x x x x
Furfuryl thiol (FFT) x x x x
Methional (MET) x x x x x x 22 Pd Scavenging Activity in the Presence of VSC
(1) Tray
(2) Palladium-coated film
(3) Sensor spot
(4) Glass petri dish + VSC-Solution
(5) Lidding film
23 Pd Scavenging Activity in the Presence of VSC
Buffer solution without VSC Buffer solution without VSC
2,2 2,2 DMS 1E-07 mmol/l DMS 1E-06 mmol/l 2,0 DMDS 1E-08 mmol/l 2,0 DMDS 1E-07 mmol/l 1,8 DMTS 1E-07 mmol/l 1,8 DMTS 1E-06 mmol/l 1,6 FFT 1E-06 mmol/l 1,6 FFT 1E-05 mmol/l MET 1E-05 mmol/l MET 1E-04 mmol/l 1,4 1,4 1,2 1,2 VSC concentration 1,0 1,0
Oxygen concentration / vol.% vol.% / concentration Oxygen increase by 1 order
0,8 of magnitude vol.% / concentration Oxygen 0,8 0,6 0,6 0,4 0,4 0,2 0,2 0,0 0,0 0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160 Time / min Time / min
Röcker B., Rüegg N., Glöss A. N., Yeretzian C., Yildirim S., Inactivation of Palladium-based Oxygen Scavenger by Volatile Sulphur Compounds24 Present in the Headspace of Packaged Food, Packaging Technology and Science, 2017, 30, 8, 427-442 Determination of Minimum Inhibitory Concentrations Range of VOC
VSC Buffer Solutions VSC Buffer Solutions
2,2 2,2 2,0 2,0 1,8 1,8 1,6 1,6 1,4 1,4 1,2
Oxygen concentration / vol.% vol.% / concentration Oxygen 1,2
1,0 vol.% / concentration Oxygen 1,0 0,8 Head Space Analysis 0,8 0,6 0,6 0,4 0,4 0,2 0,2 0,0 0 20 40 60 80 100 120 140 160 Food Products 0,0 2,2 0 20 40 60 80 100 120 140 160 Time / min 2,0 Time / min 1,8 1,6 1,4 1,2 1,0
Oxygen concentration / vol.% vol.% / concentration Oxygen 0,8 0,6 0,4 0,2 0,0 0 20 40 60 80 100 120 140 160 Time / min Empty Packaging Ham 25 Roast Beef Cheese Peanuts Par-baked Buns
25 Minimum Inhibitory Concentration Range of VOC
40 37,5 35 DMS 32,5 30
27,5
25 22,5 FFT 20
17,5 Absolute concentration / ppbv / concentration Absolute 15 DMDS 12,5 10 7,5 Methional 5 2,5 DMTS 0 Volatile Sulphur Compounds 26 27 28 Further VSC
29 Label Development
1. Step: 2. Step: SiOx/Pd-Coating Partial application of Adhesive Pd SiOx
Adhesive Pd Pd SiOx SiOx PET PET PET Adhesive* Adhesive* Adhesive* Silicone Silicone Silicone PET PET PET
3. Step: 4. Step: Application of FCM Punching
FCM FCM FCM Adhesive Adhesive Adhesive Pd AL Pd Pd SiOx SiOx SiOx PET PET PET Adhesive* Adhesive* Adhesive* Silicone Silicone carrier PET PET Silicone PET
30 Content
1. Research Group Food Packaging @ZHAW
2. Active Packaging
3. Development of Palladium based Oxygen Scavenging Label
Idea
Development
Industrialisation
4. Applications 31 Use of palladium based oxygen scavenger to prevent discoloration of ham
Hutter S., Rüegg N., Yildirim S., Use of palladium based oxygen scavenger to prevent discoloration of ham, Food Packaging and Shelf Life, 2016, 8, 56-62
32 Use of Palladium based Oxygen Scavenger to Prevent Oxidation in Linseed Oil
33 Faas N., Röcker B., Smrke S., Yeretzian C.,Yildirim S. Prevention of lipid oxidation in linseed oil using a palladium-based oxygen scavenging film, Food Pacakging and Shelf Life, to be submitted Use of Palladium based Oxygen Scavenger to Prevent Mould Growth of Bakery Products
Rüegg N, Röcker B. Yildirim S. Use of palladium based oxygen scavenger to prevent mould growth of bakery product. Manuscript in preperation 34 Acknowledgements
Research Group Food Packaging Nadine Rüegg Bettina Röcker Barbara Beck Simon Hutter Sanzio Rombini Maria Ebenreth Nicole Faas
Research Group Analytical Technologies Samo Smrke Alexia Glöss Chahan Yeretzian
35 Thank you very much for your attention
36