1. Oxygen Permeation Measurements Across Films using OxySense® luminescence Technology Devinder Saini OxySense Inc S. Eastern Ave Suite 14G Las Vegas, Nevada x 3137

2. Introduction
Oxygen permeation into packages causes shelf-life issues within the food & beverage industry
Product spoilage due to ingress of Oxygen.
Oxygen can permeate into the package via transmission across the film, micro-pores, holes, inconsistent sealing, etc.
Oxygen transmission rates need to be determined before plastic are films used in packaging

3. Traditional OTR Measurement Techniques
Traditional techniques for measuring of oxygen permeation across films use coulometric or chemical cell sensors
The use of these sensors can be complicated
Typically a two part chamber is used with the test film separating the chambers
With oxygen flowing on one side and nitrogen flowing on the other side
The OTR is the amount of oxygen permeating across the test film over time

4. Typical OTR Measurement Setup
Permeation Chamber
Test film
Gas Flow
Gas Flow
Air/Oxygen
Nitrogen
Sensor

5. Traditional OTR Measurement Techniques
These sensors consume oxygen and convert it into an electrical signal
The instrument can be tricky to set up.
The flow rates on both sides of the film must be tightly controlled
A difference in pressure can cause erroneous OTR measurements
Before the OTR measurements can begin a base line at zero oxygen has to be established which can take up to 24 hours
Very few films can be tested using a single instrument
The cost per measurement is quite high as a large amount of gas is consumed

6. Traditional OTR Measurement Techniques
The flowing gas method is not representative of actual permeation conditions in real packages
In real packages there are no flowing gases
There is clearly a need for a better method to determine the OTR of films
This method needs to be cost effective and simple
It needs to be more representative of the actual conditions in a real package
There is such a method using fluorescence technology

7. Oxygen Measurement Using luminescence Technology
The measurement technique is based upon luminescence quenching of a luminescent dye immobilized in a polymer.
The dye absorbs light in the blue region of the spectrum and luminesces within the red region of the spectrum
This technology is used for Non-Invasive/non-destructive oxygen measurements in packages

8. Optical Oxygen, how does it work?
Fluorescence
Fluorescence Quenching
(Collisional, Dynamic)
lex < lem
t = fluorescence lifetime
Oxygen = Quencher
[Quencher] ~ Emission int.
[Quencher] ~ Fluoresc. Lifetime

9. Calibration of an Optical Oxygen Detector
Fluorescence Signals Oxygen Detector 0%
20%
40%
60%
80%
100% 5 10 15
Time in microseconds
Signal
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
Calibration Lines at
different Temperatures
0.0
0.5
1.0
1.5
2.0 50
100
150
200
250
300 pO 2
in mbar
1 / Time Constant in us -1
50 deg C
40 deg C
30 deg C
20 deg C
10 deg C

10. Oxygen Measurement Using Fluorescence Decay
Time
Fluorescence decay without oxygen
Fluorescence decay with oxygen
Light pulse

11. How does the fluorescence sensor work?
Time
Oxygen Sensitive
fluorescent coating
Fluorescence
Time
Time
Photo Detector

12. Performance OxySense vs. Gas Chromatograph

13. Sensor/Instrument Specifications
Non-destructive measuring technique
Multiple measurements on the same package
Fast measurement (< 0.1 second)
Accuracy at ambient, 5% of the reading
Reproducibility better than 1% (0.2% O2)
Detection limits, typically 15 ppb in water or 0.03% by volume in gas

14. Sensor/Instrument Specifications
Sterilization tested up to 150oC (1h), can withstand pasteurisation
Can be used in oil, water and air
Independent of pH (2-12) and salt concentration
No interference from other gases

15. Applications R&D Quality Control Shelf-Studies Oxidation Studies
Dissolved Oxygen Measurements
Oxygen Scavenger Studies
Permeation studies
In-line Leak Detection on Sealed Packages

16. Film Permeation Measurement Using Luminescence Technology
This luminescence sensing technology can be applied to Permeation measurements
Where an oxygen sensor can be placed in the test chamber on the nitrogen side of the film being measured
Once the sensor side of the film has been flushed with nitrogen the flow can be shut off
The oxygen side of the chamber can be filled with 100% oxygen or left open to the atmosphere (21% O2)

17. Permeation Chamber using Luminescence Oxygen Sensing
Nitrogen Out
Nitrogen In
Test Film
Sensor
Air/oxygen In
Air/Oxygen Out
Reader Pen from Instrument
Permeation Chamber

18. Permeation Chamber
Fluorescence Sensor

19. Film Permeation Measurement Using Luminescence Technology
The oxygen will permeate across the film and be measured by the oxygen sensor
The oxygen concentration is measured by reading the sensor using the OxySense instrument
The change in the oxygen concentration in the nitrogen side of the chamber over time yields the OTR
There are no flowing gases on either side of the chamber
This set up represents a more accurate representation of real packages

20. OxyOTR Permeation Measurement System

21. OTR Software

22. Comparison Tests
The new luminescence permeation measurement system was compared to MOCON Oxtran in third party tests conducted by PTI and the University of Florida
The OTRs of three films (Mylar, Oxygen barrier film and PET) were measured using both the Oxtran and the new luminescence OTR system
These tests were performed by an independent test lab (PTI)

23. Film Permeation Third Party Test Data
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

24. Comparison Tests
Further tests were conducted by the University of Florida
The OTRs of three films with Low, medium and high barriers were measured using both the Oxtran and the new luminescence OTR system

28. Package Permeation Measurement Using Luminescence Technology
The luminescence technology can also be easily applied to packages
In this case the sensing dot is attached to the inside of a bottle or a flexible package
The package is flushed and sealed and the oxygen measurements are made form the outside
The change in the oxygen concentration over time leads to an OTR

29. Conclusions
Results show that luminescence technology can be applied to making permeation measurements for Films as well as packages.
Third party tests show that results obtained using this technology are comparable to an Oxtran.
The use of this technology reduces costs as very little gas is used during the measurements
Multiple films can be measured using one instrument
The same instrument can be used for package permeation measurements at the same time