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Page 1: Combined Oxygen Scavenger and Oxygen Indicator – Accm.ytally.com/fileadmin/user_upload/downloads/saengerlaub2.pdf · Combined Oxygen Scavenger and Oxygen Indicator – A ... of

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Page 2: Combined Oxygen Scavenger and Oxygen Indicator – Accm.ytally.com/fileadmin/user_upload/downloads/saengerlaub2.pdf · Combined Oxygen Scavenger and Oxygen Indicator – A ... of

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Combined Oxygen Scavenger and Oxygen Indicator – A Method for Monitoring the Integrity of Packages and the Functioning of Oxygen Absorbers

Sven Sängerlaub, Dr. Gertraud Goldhan

Cold Chain Management 3rd International Workshop June 2-3, 2008, Bonn, Germany

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

Page 4: Combined Oxygen Scavenger and Oxygen Indicator – Accm.ytally.com/fileadmin/user_upload/downloads/saengerlaub2.pdf · Combined Oxygen Scavenger and Oxygen Indicator – A ... of

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

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1. Motivation for Use of Active and Intelligent Packaging

Trend towards:- low-processed foodstuffs

- modified composition: highly sensitive components, e.g. natural food dyes

- consumers are increasingly critical towards food additives, e.g. antioxidants - increasing use of transparent plastic packaging

Objective:

- food safety, information

- preserving nutrient-providing food

components (vitamin, antioxidants)

- extension of shelf-life

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1. Expedient Combinations of Active / Intelligent Packaging

Expedient Combinations:- O2-scavenger / O2-indicator- H2O-scavenger / H2O-indicator- ethylene scavenger / ethylene indicator- antimicrobial package / spoilage indicator

Combined Systems should:- absorb oxygen

- monitor functionality of active system and

- monitor the integrity of the package

���� incorporation in packaging material

food max. tolerable O2-uptake

(mg O2 / kg)beer 1 – 4wine 3milk 8steril. vegetable 15ketchup 15fruit juice 20roasted coffee 110emmentaler cheese 500

Source: Heiss

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

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iron based

polyolefin based

sulphite based

Nylon-6

PET-copolyester

palladium (on fleece)

iron based

glucose

Substrate

different additives / moisture

photoinitiator+cobalt salts / UV-irradiation

- / moisture

- / thermal irradiation

cobalt / thermal irradiation

palladium / MAP with H2

hygroscopic salts / moisture

self working

glucose oxidase / moisture

Catalysis / Activation

inlay

incorporated in polymers

sachets

Scavenger

2. Oxygen Scavengers on the Market

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2. New developed Oxygen Scavengers

New developments in the area of oxygen scavengers

Fraunhofer worked on scavengers on the basis of:

� Gallic Acid (Fraunhofer IVV)

� Transparent Hybrid Polymers (Fraunhofer ISC)

ACOSIC -A project supported by the European Commission.

- Application as lacquers or as adhesion layers

Successful production of prototypes or samples

Results were generated in the EU-project ACOSIC: www.acosic.com

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2. Gallic Acid Based Scavenger: Reaction Mechanism

Source: Tulyathan V. et al.: Oxygen Uptake by Gallic Acid as a Model of Similar Reactions in Wines, J. Agric. Food Chem., 37, 1989, 844-849

ACOSIC -A project supported by the European Commission.

4 OH-

Gallic Acid (3,4,5-trihydroxybenzoic acid)

- natural occurring in gallnuts, tea leaves (in form of tannins), oak bark

- is oxidised in a alkaline environment

- activation of the base by moisture

- gallic acid based scavenger: promising for biodegradable packages

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2. Gallic Acid Based Scavenger: Film Coating

ACOSIC -A project supported by the European Commission.

two component polyurethane adhesives

gallic acid

solvent

coating on basic substrate

The system is suitable for coating and printing.

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2. Gallic Acid Based Scavenger: Functional Characterisation

0

50

100

150

0 2 4 6 8 10 12 14 16

t / d

O2-a

bso

rpti

on

/ m

ass

s

cav

en

ge

r

[cm

3 O

2/g

Sca

v.]

0

100

200

300O

2 -ab

sorp

tion

/ are

a [cm

³ O2 / m

² film

]

PE / EVOH / PE(CaO) / scavenging layer (adhesive) / PEfoamed

PE / EVOH / PE(CaO) / scavenging layer (adhesive) / PEfoamed

ACOSIC -A project supported by the European Commission.

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2. Hybrid Polymer Based Scavenger: Functional Characteris.

Composition: Silicate-backbone, catalyst, photoinitiator, antioxidant

Chemical reaction: Photo-initiated, metal catalyzed oxidation of oxidisablesubstance bonded chemically to a silicate backbone.

ACOSIC -A project supported by the European Commission.

Source: Fraunhofer ISC

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

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Working groups: - VTT Finland: “Ink composition and oxygen indicator” – redox dye, printable indicator

- University of Strathclyde: redox dye methylene blue; UV-activated

- University of Ottawa: zeolite fixed indicator; UV-activated

- Fraunhofer IGB (Project ACOSIC): enzyme-catalysed system

3. Oxygen Indicators on the Market, Working Groups

Tablet with O2-indicator: Ageless-Eye

before reaction with O2 after reaction with O2

Task of an oxygen indicator:- Indication of exceeding an oxygen threshold, e.g. caused by a damage of the package.

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3. New Developed Oxygen Indicators

ACOSIC -A project supported by the European Commission.

design proposal for an oxygen indicator

Fraunhofer worked on indicators on the basis of:

- Methylene Blue (Fraunhofer ISC)

- Gallic Acid (Fraunhofer IVV)

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Manufacturing process Methylene Blue Based Indicator:

lacquer

adding indicator

+ additives

coating film

inclose film under oxygen free atmosphere

discolouring

UV

O2 no O2no O2

O2

recolouringO2

3. New Developed Oxygen Indicators: Methylene Blue Based

Source: Fraunhofer ISC

ACOSIC -A project supported by the European Commission.

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3. New Developed Oxygen Indicators: Methylene Blue Based

PET/SiOx/ Indicator (lab scale):

wavelength [nm]300 400 500 600 700 800

0

1

2

ab

sorp

tio

n [

a. u

.]

oxygen concentration threshold

before discoloration

directly after discoloration

5 d air contact

18 h after removing from cell

4 d in a cell (2 % oxygen)

Source: Fraunhofer ISC

ACOSIC -A project supported by the European Commission.

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3. New Developed Oxygen Indicators: Gallic Acid Based

ACOSIC -A project supported by the European Commission.

Printed oxygen indicator based on gallic acid:

Manufacturing:

• Incorporation of gallic acid in lacquers• Printing of lacquer with gallic acid

Initialisation: humidity + alkaline additives

before reaction with O2

after reaction with O2

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

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4. Combination of Oxygen Scavenger and Indicator, Demands

contact layer / sealing layer (inside)

barrier layer (outside)

adhesion layer: two component polyurethane adhesive oxygen indicator dotintermediate layer with alkaline substance

oxygen scavenging layer (gallic acid based) and adhesion layer

- high oxygen permeability, - a high water vapour transmission rate is needed, if the system is activated by moisture,

- migration of decomposition products must be avoided

- high UV-transmission rate of the layers

Contact layer:

UV-activated system:

- oxygen scavenger is not a substitution for a barrier layer

Barrier layer:

ACOSIC -A project supported by the European Commission.

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

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0,0

0,5

1,0

1,5

2,0

0 10 20 30

cheesemeat sausage

5. Oxygen Consumption of Food

O2-c

on

cen

trati

on

[%

]

Cheese and meat sausage – oxygen absorptionAdaptation of scavenger characteristic and oxygen consumption of food. � O2-scavenger must absorb oxygen faster than food.

Weight: (40 .. 50) g

headspace: 100 cm³

temperature: 5 °C

ACOSIC -A project supported by the European Commission.

time [days]

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0,0

0,5

1,0

1,5

2,0

0 5 10 15 20

t / d

O2-c

on

cen

trati

on

in

th

e h

ead

space

[%

]

sliced cheese filled in a tray sealed with a conventional lid

sliced cheese filled in a tray sealed with a lid containing the gallic acidbased scavenger and indicator

initial oxygen concentration

Cheese – effect of the O2-scavenger in MAP package� lid with novel O2-scavenger on the basis of gallic acid

Weight cheese: 100 g

headspace: 40 cm³

temperature: 5 °C

Effect of O2-scavenger to

reduce residual oxygen.

5. Filled Packages

ACOSIC -A project supported by the European Commission.

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Outline

1. Motivation for the Employment of Combined Oxygen Scavenger and Oxygen Indicator

2. Developed Oxygen Scavengers

3. Developed Oxygen Indicators

4. Combination of Oxygen Scavenger and Oxygen Indicator

5. Testing of Filled Packages

6. Summary

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6. Summary

� The combination of O2-scavenger and O2-indicator is reasonable to scavenge oxygen and to simultaneously monitor the functioning of the O2-scavenger and the integrity of the package.

� During the project ACOSIC prototypes of new O2-scavengers –lacquers and adhesives – and new O2-indicators were developed

and combined.

� The O2-scavenger and O2-indicator has to be adapted to the food –

the O2-scavenger should absorb the oxygen faster than the food.

� Further application areas for other combined systems like humidity absorber and humidity indicator or antimicrobial package and spoilage indicator are beneficial.

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Thank you for your attention.