Oxygen Permeation Oxygen Permeation Measurements Across Films Measurements Across Films

using OxySense® using OxySense® luminescenceluminescence Technology Technology

Devinder Saini Devinder Saini OxySense Inc.OxySense Inc.

6000 S. Eastern Ave Suite 14G6000 S. Eastern Ave Suite 14GLas Vegas, Nevada 89119Las Vegas, Nevada 89119

www.oxysense.com

702 361 7921 x 3137702 361 7921 x 3137

IntroductionIntroduction

Oxygen permeation into packages causes shelf-life Oxygen permeation into packages causes shelf-life issues within the food & beverage industryissues within the food & beverage industry

Product spoilage due to ingress of Oxygen. Product spoilage due to ingress of Oxygen. Oxygen can permeate into the package via Oxygen can permeate into the package via

transmission across the film, micro-pores, holes, transmission across the film, micro-pores, holes, inconsistent sealing, etc. inconsistent sealing, etc.

Oxygen transmission rates need to be determined Oxygen transmission rates need to be determined before plastic are films used in packaging before plastic are films used in packaging

Traditional techniques for measuring of oxygen Traditional techniques for measuring of oxygen permeation across films use coulometric or permeation across films use coulometric or chemical cell sensorschemical cell sensors

The use of these sensors can be complicatedThe use of these sensors can be complicated Typically a two part chamber is used with the test Typically a two part chamber is used with the test

film separating the chambersfilm separating the chambers With oxygen flowing on one side and nitrogen With oxygen flowing on one side and nitrogen

flowing on the other sideflowing on the other side The OTR is the amount of oxygen permeating The OTR is the amount of oxygen permeating

across the test film over timeacross the test film over time

Traditional OTR Measurement Traditional OTR Measurement TechniquesTechniques

Typical OTR Measurement SetupTypical OTR Measurement Setup

Test film

Sensor

Nitrogen

Air/Oxygen

Gas Flow

Gas Flow

Permeation Chamber

Traditional OTR Measurement Traditional OTR Measurement TechniquesTechniques

These sensors consume oxygen and convert it into an These sensors consume oxygen and convert it into an electrical signalelectrical signal

The instrument can be tricky to set up.The instrument can be tricky to set up. The flow rates on both sides of the film must be tightly The flow rates on both sides of the film must be tightly

controlledcontrolled A difference in pressure can cause erroneous OTR A difference in pressure can cause erroneous OTR

measurementsmeasurements Before the OTR measurements can begin a base line at zero Before the OTR measurements can begin a base line at zero

oxygen has to be established which can take up to 24 hoursoxygen has to be established which can take up to 24 hours Very few films can be tested using a single instrumentVery few films can be tested using a single instrument The cost per measurement is quite high as a large amount of The cost per measurement is quite high as a large amount of

gas is consumedgas is consumed

Traditional OTR Measurement Traditional OTR Measurement TechniquesTechniques

The flowing gas method is not representative of actual The flowing gas method is not representative of actual permeation conditions in real packages permeation conditions in real packages

In real packages there are no flowing gasesIn real packages there are no flowing gases There is clearly a need for a better method to determine There is clearly a need for a better method to determine

the OTR of filmsthe OTR of films This method needs to be cost effective and simple This method needs to be cost effective and simple It needs to be more representative of the actual It needs to be more representative of the actual

conditions in a real packageconditions in a real package There is such a method using fluorescence technologyThere is such a method using fluorescence technology

Oxygen Measurement UsingOxygen Measurement Using luminescenceluminescence Technology Technology

The measurement technique is based upon The measurement technique is based upon luminescence quenching of a luminescent dye luminescence quenching of a luminescent dye immobilized in a polymer.immobilized in a polymer.

The dye absorbs light in the blue region of the The dye absorbs light in the blue region of the spectrum and luminesces within the red region of the spectrum and luminesces within the red region of the spectrumspectrum

This technology is used for Non-Invasive/non-This technology is used for Non-Invasive/non-destructive oxygen measurements in packagesdestructive oxygen measurements in packages

Optical Oxygen, how does it work?Optical Oxygen, how does it work?

Fluorescence QuenchingFluorescence Quenching

(Collisional, Dynamic)(Collisional, Dynamic)FluorescenceFluorescence

Oxygen = QuencherOxygen = Quencher

[Quencher] ~ Emission int.[Quencher] ~ Emission int.

[Quencher] ~ Fluoresc. [Quencher] ~ Fluoresc. LifetimeLifetime

exex < < emem

= fluorescence = fluorescence

lifetime lifetime

Calibration of an Optical Oxygen Calibration of an Optical Oxygen DetectorDetector

Calibration Lines atdifferent Temperatures

0.0

0.5

1.0

1.5

2.0

0 50 100 150 200 250 300

pO 2 in mbar

1 /

Tim

e C

on

stan

t in

us-1

50 deg C40 deg C30 deg C20 deg C10 deg C

Fluorescence Signals Oxygen Detector

0%

20%

40%

60%

80%

100%

0 5 10 15

Time in microseconds

Sig

nal

0.0%2.1%4.2%6.3%8.4%10.5%12.6%14.7%16.8%18.9%21.0%

Increasing Oxygen Level

Oxygen Measurement Using Oxygen Measurement Using Fluorescence DecayFluorescence Decay

Time

Fluorescence decay without oxygen

Fluorescence decay with oxygen

Light pulse

 

Time

How does the fluorescence sensor How does the fluorescence sensor work?work?

Time

Oxygen Sensitivefluorescent coating

Photo Detector

Fluorescence

Time

PerformancePerformanceOxySense vs. Gas ChromatographOxySense vs. Gas Chromatograph

0

5

10

15

20

25

0 5 10 15 20 25

%O2 GC

%O

2 O

XY

Vials in the dark

Pouches in the dark

Vials in the light

Pouches in the light

Sensor/Instrument SpecificationsSensor/Instrument Specifications

Non-destructive measuring technique Non-destructive measuring technique Multiple measurements on the same packageMultiple measurements on the same package Fast measurement (< 0.1 second)Fast measurement (< 0.1 second) Accuracy at ambient, 5% of the readingAccuracy at ambient, 5% of the reading Reproducibility better than 1% (0.2% OReproducibility better than 1% (0.2% O22)) Detection limits, typically 15 Detection limits, typically 15 ppbppb in water or in water or

0.03% by volume in gas0.03% by volume in gas

Sensor/Instrument SpecificationsSensor/Instrument Specifications

Sterilization tested up to 150Sterilization tested up to 150ooC (1h), can C (1h), can withstand pasteurisationwithstand pasteurisation

Can be used in oil, water and airCan be used in oil, water and air Independent of pH (2-12) and salt concentrationIndependent of pH (2-12) and salt concentration No interference from other gasesNo interference from other gases

ApplicationsApplications

R&DR&D Quality ControlQuality Control Shelf-StudiesShelf-Studies Oxidation StudiesOxidation Studies Dissolved Oxygen MeasurementsDissolved Oxygen Measurements Oxygen Scavenger StudiesOxygen Scavenger Studies Permeation studiesPermeation studies In-line Leak Detection on Sealed PackagesIn-line Leak Detection on Sealed Packages

Film Permeation Measurement Film Permeation Measurement

Using Using LuminescenceLuminescence Technology Technology This luminescence sensing technology can be applied This luminescence sensing technology can be applied

to Permeation measurementsto Permeation measurements Where an oxygen sensor can be placed in the test Where an oxygen sensor can be placed in the test

chamber on the nitrogen side of the film being chamber on the nitrogen side of the film being measuredmeasured

Once the sensor side of the film has been flushed with Once the sensor side of the film has been flushed with nitrogen the flow can be shut offnitrogen the flow can be shut off

The oxygen side of the chamber can be filled with The oxygen side of the chamber can be filled with 100% oxygen or left open to the atmosphere (21% 100% oxygen or left open to the atmosphere (21% OO22))

Permeation Chamber using Permeation Chamber using LuminescenceLuminescence Oxygen Sensing Oxygen Sensing

Nitrogen Out

Nitrogen In

Test Film

Sensor

Air/oxygen In

Air/Oxygen Out

Reader Pen from Instrument

Permeation Chamber

Permeation ChamberPermeation Chamber

Fluorescence Sensor

Film Permeation Measurement Using Film Permeation Measurement Using LuminescenceLuminescence Technology Technology

The oxygen will permeate across the film and be The oxygen will permeate across the film and be measured by the oxygen sensormeasured by the oxygen sensor

The oxygen concentration is measured by reading the The oxygen concentration is measured by reading the sensor using the OxySense instrumentsensor using the OxySense instrument

The change in the oxygen concentration in the The change in the oxygen concentration in the nitrogen side of the chamber over time yields the nitrogen side of the chamber over time yields the OTROTR

There are no flowing gases on either side of the There are no flowing gases on either side of the chamberchamber

This set up represents a more accurate representation This set up represents a more accurate representation of real packagesof real packages

OxyOTR Permeation Measurement OxyOTR Permeation Measurement SystemSystem

OTR SoftwareOTR Software

ComparisonComparison TestsTests

The new The new luminescenceluminescence permeation permeation measurement system was compared to measurement system was compared to MOCON Oxtran in third party tests conducted MOCON Oxtran in third party tests conducted by PTI and the University of Floridaby PTI and the University of Florida

The OTRs of three films (Mylar, Oxygen The OTRs of three films (Mylar, Oxygen barrier film and PET) were measured using barrier film and PET) were measured using both the Oxtran and the new luminescence both the Oxtran and the new luminescence OTR systemOTR system

These tests were performed by an independent These tests were performed by an independent test lab (PTI)test lab (PTI)

Film PermeationFilm PermeationThird Party Test DataThird Party Test Data

Film OxyOTR™ (ml/m2/Day) MOCON® (ml/m2/Day)

Mylar 8.4 9.9

PET 11.6 12.0

Oxygen Barrier Film 3.6 3.5

Tests performed by PTI

ComparisonComparison TestsTests

Further tests were conducted by the University Further tests were conducted by the University of Floridaof Florida

The OTRs of three films with Low, medium The OTRs of three films with Low, medium and high barriers were measured using both and high barriers were measured using both the Oxtran and the new luminescence OTR the Oxtran and the new luminescence OTR systemsystem

Package Permeation Measurement Using Package Permeation Measurement Using LuminescenceLuminescence Technology Technology

The luminescence technology can also be The luminescence technology can also be easily applied to packageseasily applied to packages

In this case the sensing dot is attached to the In this case the sensing dot is attached to the inside of a bottle or a flexible package inside of a bottle or a flexible package

The package is flushed and sealed and the The package is flushed and sealed and the oxygen measurements are made form the oxygen measurements are made form the outsideoutside

The change in the oxygen concentration over The change in the oxygen concentration over time leads to an OTRtime leads to an OTR

ConclusionsConclusions Results show that Results show that luminescenceluminescence technology can be technology can be

applied to making permeation measurements for applied to making permeation measurements for Films as well as packages. Films as well as packages.

Third party tests show that results obtained using this Third party tests show that results obtained using this technology are comparable to an Oxtran. technology are comparable to an Oxtran.

The use of this technology reduces costs as very little The use of this technology reduces costs as very little gas is used during the measurements gas is used during the measurements

Multiple films can be measured using one instrumentMultiple films can be measured using one instrument The same instrument can be used for package The same instrument can be used for package

permeation measurements at the same timepermeation measurements at the same time