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 · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere...

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Development of a novel oxygen scavenger film and its potential application in food packaging COST Action FP1405 Active and intelligent fibre-based packaging – innovation and market introduction Prof. Dr. Selcuk Yildirim
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Page 1:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Development of a novel oxygen scavenger film

and its potential application in food packaging

COST Action FP1405

Active and intelligent fibre-based packaging – innovation and market

introduction

Prof. Dr. Selcuk Yildirim

Page 2:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

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

Active layer

Food

Active Scavenging Systems

- Oxygen

- CO2

- Moisture

- Ethylene

- Odour

Active Releasing Systems

- Antimicrobial agent

- CO2

- Antioxidant

- Flavours

- Ethylene

Barrier layer

* 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.

*

Page 3:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Food Trends

• Increase in consumer demand* for

� natural high-quality foods less additives and without any

preservatives

� No harsh preservation process (non-processed or minimally

processed)

� fresh and convenient food products

• Acceptable shelf life and safe products

• Barrier properties reached their limits

• New packaging technologies

� Active packaging

3

* Innova Market Insights: Top Ten Trends for 2016

Page 4:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Oxygen Scavengers

Growth of aerobic

microorganismsOxidation O2

Discoloration

and rancidityMoulds and other

Spoilage organisms

Degraded appearance

and nutritional value

Impaired sensory

qualities

Lost freshness, unpleasant

taste and aroma

Reduced Shelf life

Page 5:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

PdPd

HH

HH

O

O H O OH OH

H2O

PdPd

H O

PdPd

O O

PdPd

H2O

PdPd

1. step 2. step 4. step3. step

Palladium Based Oxygen Scavenger

*Sängerlaub, S., Witzgall, S., & Müller, K. (2012). Palladium Based Oxygen Scavengers (Poster). In 5th international Symposium on Food Packaging.

Berlin.

*

Page 6:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Palladium Based Oxygen Scavenger

Lohwasser W, Wanner T. Composite system, used as packaging foil, bag foil or partially applied single foil, comprises substrate foil thin film and catalyst for

reduction of oxygen. European Patent, 1917139, 22/11/2005.

Yildirim S, Jammet JC, Lohwasser W. Multi-layer film. European Patent, 2236284, 6/10/2010.

H2

+ ½ O2

H2O

Pd

N2 H

2Active Label

Lebensmittel

O2

O2O

2N

2N2

N2

H2

H2

Lebensmittel

O2

O2

N2 H

2 H2

H2ON

2O

2N

2

Lebensmittel

N2

N2

N2

N2

N2

Page 7:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Effect of Coating Substrate on the Oxygen Scavenging Activity

Reduction in oxygen concentration in the measurement cell with PET/SiOx/Pd, PET/AlOx/SiOx/Pd, PLA/SiOx/Pd,

LDPE/SiOx/Pd and oPP/SiOx/Pd films using a palladium deposition thickness of 1.1 nm and SiOx pre-coating.

Mean values ± standard deviation (n=3).

7

Oxygen Scavenger

xSiOx

Palladium

Substrate

Best Substrates:

• PET

• PET/AlOx

• PLA

• LDPE

• oPP

Yildirim S, Röcker B, Rüegg N, Lohwasser W. Development of Palladium-based Oxygen Scavenger: Optimization of Substrate and Palladium

Layer Thickness. Packaging Technology and Science 2015. 28(8): pp. 710-718, DOI: 10.1002/pts.2134.

Page 8:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Effect of Palladium Deposition Thickness on the Oxygen Scavenging Activity

Reduction in oxygen concentration in the measurement cell with PET/SiOx/Pd films using Pd-deposition thicknesses of

0.3, 0.4, 0.7, 1.1 and 3.4 nm. Mean values ± standard deviation (n=3).

8

Oxygen Scavenger

xSiOx

Palladium

PET

Yildirim S, Röcker B, Rüegg N, Lohwasser W. Development of Palladium-based Oxygen Scavenger: Optimization of Substrate and Palladium

Layer Thickness. Packaging Technology and Science 2015. 28(8): pp. 710-718, DOI: 10.1002/pts.2134.

Page 9:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

A case study:

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. In Press.

Page 10:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Packaging:

– Commercial cooked cured ham

– High barrier EVOH tray and film

– Gas: Modified atmosphere (MA): 2% O2, 5% H2, 93% N2, normal atmosphere (NA)

– With and without scavenger (25 cm2)

Storage:

– 4±1°C, 21 days

– Illumination (1’000 lx): 24 h/d, 8 h/d or dark

Analyses:

– Colour: *a (redness), *L (lightness) (CR-410, Minolta)

– Headspace oxygen concentration (Fibox 4 trace, PreSens)

Material & Methods

Page 11:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Changes in headspace oxygen

concentrations Modified atmosphere:

– Samples with scavenger stay <0.05 % O2

– Illuminated, without scavenger: decrease beacause of discoloration reaction

Normal atmosphere:

– Decrease starting after ~5 days, probably due to microbial growth

Page 12:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Discoloration of Ham

Changes in redness:

– No loss in redness for sample with scavenger, even though it was illuminated 24 h/d

– Even slight increase in redness, compared to dark stored samples

– Illuminated samples show pronounced discoloration, significant after 2 h

Page 13:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Discoloration of Ham

after 1 day of storage after 21 days of storage

Page 14:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Discoloration of Ham

Page 15:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

A case study:

Use of palladium based oxygen scavenger to

prevent mould growth of bakery product

Rüegg N, Blum T., Ebenreth M., Yildirim S. Use of palladium based oxygen scavenger to prevent mould growth of bakery product. Manuscript in preperation

Page 16:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Experimental Set-up

Par-baked bread Toast bread Gluten free bread

Normalatmosphere (NA) MAP

(93 vol. % N2 ,2 vol. % O2 ,5 vol. % H2)

+ Scavenger

(MAP +Active Label)

Modified atmosphere (MAP)

(93 vol. % N2 ,2 vol. % O2 ,5 vol. % H2)

No inoculation, Stress test

Aspergillus niger (9,7 x 103 KBE)

Storage

25 °C, 50 % RH16

Page 17:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Experimental Set-up

Par-baked bread Toast bread Gluten free bread

Normalatmosphere (NA) MAP

(93 vol. % N2 ,2 vol. % O2 ,5 vol. % H2)

+ Scavenger

(MAP +Active Label)

Modified atmosphere (MAP)

(93 vol. % N2 ,2 vol. % O2 ,5 vol. % H2)

No inoculation, Stress test

Aspergillus niger (9,7 x 103 KBE)

Storage

25 °C, 50 % RH17

Page 18:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Par-backed bread, NA

18

Page 19:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

19

Par-backed bread, NA

Page 20:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

20

Par-backed bread, MAP

Page 21:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

21

Par-backed bread, MAP

Page 22:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

22

Par-backed bread, MAP + Active Label

Page 23:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

23

Par-backed bread, MAP + Active Label

Page 24:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Toast Bread

Time [d]

0 2 4 6 8 10 12 14 16 18 20

Oxyg

en c

oncentr

ation [vol.%

]

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

9.0

12.0

15.0

18.0

21.0

Mould

y sam

ple

s [%

]

0

20

40

60

80

100

O2-MAP + Active Label

O2-MAP

O2-NA

Mould growth -

MAP + Active Label

Mould growth - MAP

Mould growth - NA

Page 25:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Gluten Free Bread

Time [d]

0 2 4 6 8 10 12 14 16 18 20

Oxyg

en c

oncentr

ation [vol.%

]

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

9.0

12.0

15.0

18.0

21.0

Mould

y sam

ple

s [%

]

0

20

40

60

80

100

O2-MAP + Active Label

O2-MAP

O2-NA

Mould growth -

MAP + Active Label

Mould growth - MAP

Mould growth - NA

Page 26:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …
Page 27:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Acknowledgements

27

Nadine Rüegg

Bettina Röcker

Susanna Miescher

Simon Hutter

Maria Ebenreth

Page 28:  · Packaging: Commercial cooked cured ham High barrier EVOH tray and film Gas: Modified atmosphere (MA): 2% O 2, 5% H 2, 93% N 2, normal atmosphere (NA) …

Thank you for your attention

28

Prof. Dr. Selcuk Yildirim

Institute of Food and Beverage Innovation

Campus Reidbach Postfach

Wädenswil

Switzerland

[email protected]

Tel: +41 58 934 56 31


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