Designation: F3136 − 15

Standard Test Method for

Oxygen Gas Transmission Rate through Plastic Film and
Sheeting using a Dynamic Accumulation Method1
This standard is issued under the fixed designation F3136; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope Packages Using Fluorescent Decay

1.1 This test method covers a procedure for determination 3. Terminology
of the transmission rate of oxygen gas through plastics in the
form of film, sheeting, laminates, coextrusions, coated or 3.1 Definitions:
uncoated papers or fabrics. 3.1.1 Oxygen Transmission Rate (OTR)—the quantity of
oxygen gas passing through a unit area of the parallel surfaces
1.2 This test method is not the only method for measure- of a plastic film per unit time under the conditions of test. The
ment of the oxygen transmission rate (OTR). There are other SI unit of transmission rate is the mol/(m2·s). The test condi-
methods of OTR determination that use other oxygen sensors tions including temperature, relative humidity and oxygen
and procedures. partial pressure on both sides of the film must be stated in the
1.3 The values stated in SI units are to be regarded as report.
standard. Commonly used metric units used to report Oxygen 3.1.1.1 Discussion—A commonly used unit of OTR is the
Transmission Rate are included in Terminology, Procedure, cm3 (STP)/(m2·day) at one atmosphere pressure difference
Precision and Bias sections and in the Calculation section of where 1 cm3 (STP) is 44.62 µmol, 1 atmosphere is 0.1013
the Appendix. MPa, and one day is 86.4 × 103s. The OTR in SI units is
1.4 This standard does not purport to address all of the obtained by multiplying the value in commonly used units by
safety concerns, if any, associated with its use. It is the 5.160 × 10-10.
responsibility of the user of this standard to establish appro- 4. Summary of Test Method
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. 4.1 The specimen is mounted as a sealed semi-barrier
between two chambers, which together make up the perme-
2. Referenced Documents ation apparatus. The sensing well which contains the oxygen
sensor is slowly purged by a stream of pure nitrogen or other
2.1 ASTM Standards:2 oxygen deficient gas mixture until the oxygen concentration
D3985 Test Method for Oxygen Gas Transmission Rate represents that of the purge gas. A commercial grade of
Through Plastic Film and Sheeting Using a Coulometric compressed nitrogen containing less than 0.05% oxygen is
Sensor recommended. A gas of known oxygen concentration, typically
E177 Practice for Use of the Terms Precision and Bias in air or pure oxygen, is directed into the opposite chamber, the
ASTM Test Methods driving well. Oxygen concentration in the sensing well con-
E691 Practice for Conducting an Interlaboratory Study to taining the oxygen sensor is measured periodically and the
Determine the Precision of a Test Method accumulating oxygen concentration recorded. The Oxygen
F2622 Test Method for Oxygen Gas Transmission Rate Transmission Rate (OTR) parameter is determined from the
Through Plastic Film and Sheeting Using Various Sensors slope of the logarithm of accumulated oxygen concentration in
F2714 Test Method for Oxygen Headspace Analysis of the sensing well versus time as described in 14.2.
5. Significance and Use
1
This test method is under the jurisdiction of ASTM Committee F02 on Flexible 5.1 The Oxygen Transmission Rate is an important deter-
Barrier Packaging and is the direct responsibility of Subcommittee F02.10 on
Permeation. minant of packaging functionality afforded by packaging
Current edition approved April 1, 2015. Published April 2015. DOI: 10.1520/ materials for a wide variety of packaged products including
F3136-15.
2
food, pharmaceuticals and medical devices. In some
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
applications, sufficient oxygen must be allowed to permeate
Standards volume information, refer to the standard’s Document Summary page on into the package. In others, the oxygen ingress must be
the ASTM website. minimized to maintain product quality.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

1
 F3136 − 15
5.2 Other ASTM Standard Methods to measure the oxygen effect is calibrated to oxygen concentration. This sensing
transmission rate are described in Standard Test Method D3985 technology is identical to the sensing technology described in
and Standard Test Method F2622. ASTM F2714.
7.1.1.5 The permeability apparatus shall incorporated suit-
6. Interferences able fittings for the introduction and exhaust of gases without
6.1 Any leakage within the permeation apparatus or significant loss or leakage.
mounted packaging film will affect results. A means to assess 7.2 It is necessary to control the temperature of the perme-
leakage is described in paragraph 9.2. ability apparatus during the test period. A simple heating/
6.2 The condition of the sample film must be noted such as cooling chamber regulated to 60.5°C, is adequate for this
wrinkles or other defects can affect results. purpose in which the apparatus is housed during the test period.
7.3 Flow meters having an operating range from 1 to 100
7. Apparatus cm3/min are required to monitor the flow rate of the nitrogen
7.1 Oxygen Gas Transmission Apparatus, as diagrammed in purge stream and, if used, the oxygen or compressed air
Fig. 1 with the following: circulation stream. Sufficiently low flow rates and/or balanced
7.1.1 Permeation Apparatus (diffusion cell) shall consist of pressures on each side of the film are required to avoid
two metal halves, which, when closed upon the test specimen, stretching the specimen which would modify the effective
will define a known gas transmission area. The volume of the sensing well volume.
sensing well containing the oxygen sensor must be accurately 7.4 An external light source provides sufficient light in the
known. appropriate wavelength to activate the oxygen sensor.
7.1.1.1 O-ring—A circular transmission area permits appli- 7.5 A light detector, and associated electronics, determines
cation of a static O-ring in a properly constructed O-ring the fluorescence decay constant, which is proportional to
groove in the side of the permeation apparatus that does not oxygen concentration.
contain the oxygen sensor. The test area of the sensing well is
considered to be that area established by the inside contact 7.6 A computer is used to calculate the oxygen concentra-
diameter of the compressed O-ring when the permeation tion at specified time intervals based on decay rates. The
apparatus is clamped shut. The area, A, can be obtained by oxygen transmission rate of the film is calculated from that
measuring the inside diameter of the imprint left by the O-ring data.
on the specimen after it has been removed from the permeation 8. Reagents and Materials
apparatus.
7.1.1.2 The sensing well of the permeation apparatus shall 8.1 Nitrogen enriched purge gas shall contain a known
have a flat raised rim. Since this rim is a critical sealing surface concentration of nitrogen. Commercial grade compressed ni-
against which the test specimen is pressed, it shall be smooth trogen (<0.05% oxygen), certified pure nitrogen gas, cryogeni-
and flat without radial scratches. cally stored nitrogen or nitrogen enriched gas produced using
7.1.1.3 The sensing well of the permeation apparatus shall on-site generators may be used.
have a low-permeability window transparent to wavelengths 8.2 Transmission gas shall be of a known oxygen concen-
used to activate and read the oxygen sensor which is mounted tration with an oxygen concentration at least 10% greater than
within the sensing well. the purge gas. Typically, commercial grade compressed
7.1.1.4 The oxygen sensor incorporates a fluorophore that oxygen, certified gas or air is used. Also, regulated compressed
fluoresces in response to a certain wavelength of light, but is air can be used or the driving well can simply be left open to
quenched in the presence of oxygen. The oxygen quenching ambient air.

FIG. 1 A Practical Arrangement of Components for the Measurement of Oxygen Transmission Rate Using an Optical Florescent Oxygen
Sensor and a Permeation Apparatus

2
 F3136 − 15

An acceptable Permeation Apparatus (aka Diffusion Cell) is available from OxySense, Inc., 6000 S. Eastern Ave., Suite 14G, Las Vegas, NV 89119, USA.
FIG. 2 Permeation Apparatus as described in this method (film specimen is shown adhered to the sensing well)

8.3 Sealing Grease—High-viscosity silicone stop cock 11.2 Average thickness shall be determined 6 3 µm using a
grease or high-vacuum grease is required for sealing the calibrated dial gage (or equivalent) at a minimum of five points
specimen film in the diffusion cell. distributed over the entire test area. Maximum, minimum, and
average values shall be recorded. Sample thickness need not be
9. Precautions measured for determination of sample OTR only.
9.1 Temperature is a critical parameter affecting the mea- 11.3 If the test specimen is of an asymmetrical construction,
surement of OTR. Careful temperature control can help to the two surface shall be marked by appropriate distinguishing
minimize variations due to temperature fluctuations. During marks and the orientation of the test specimen within the
testing, the temperature shall be monitored and controlled to 6 permeation apparatus shall be reported.
0.5°C. Temperature variations should be minimized. The
average temperature and a range of temperatures during a test 12. Calibration
shall both be recorded.
12.1 General Approach—The oxygen sensor fluoresces
9.2 Oxygen that leaks into the sensing well through faulty when exposed to certain wavelengths of light. Oxygen
valves, fittings, or through an improperly sealed window can quenches the fluorescent decay response. The sensor apparatus
significantly affect the accuracy of the measurement. Periodic utilizes a light source to deliver light to the oxygen sensor
leak checks using impervious films such as metal foils with which, in turn, fluoresces. This light is measured by the
thicknesses ≥25 µm (with their expected permeations of zero) detector. The detector determines the exponential fluorescent
should be taken to identify suspected system leaks. Leak check response decay constant, which is calibrated to oxygen con-
permeation tests should be run at least every 3-6 months and centration.
each test should be run for a minimum of 12 hours.
12.2 Calibration—The sensor system is calibrated by mea-
10. Sampling suring oxygen concentration at two known values, typically air
10.1 Film samples used for the determination of OTR shall (20.9% oxygen) and pure nitrogen (0% oxygen). These values
be representative of materials for which the data are required. define a calibration curve from which unknown oxygen levels
Care shall be taken to ensure that samples are representative of may be determined. Alternatively, 2 gases of known concen-
conditions across the width and along the length of a roll of trations nearer to the level under test may prove to yield a
film. better calibration value (perhaps 3% and 0% oxygen).

11. Test Specimens 13. Procedure

11.1 Test specimens shall be representative of the material 13.1 Apply a thin layer of sealing grease (see 8.3) around
and shall be free of defects including wrinkles, creases, and the raised rim of the sensing well opposite the O-ring. Place the
pinholes, unless these are characteristics of the material being specimen on the greased surface, taking care to avoid wrinkles
tested and included in the material description. or creases. Close and secure the permeation apparatus.

3
 F3136 − 15
13.2 The system can be calibrated with the test specimen in levels at which to start and end recording data. As guidance, the
place. following table can be used.
13.2.1 Open both the inlet and outlet valves connected to the Barrier Level Range Start % End %
sensing well of the permeation apparatus. If using air as the Medium 2 to 100 cm3(STP)/(m2·day) 0.50 2.00
Poor greater than 100 cm3(STP)/(m2·day) 1.00 3.00
upper oxygen level calibration gas, there is no need to purge
the sensing well as it already contains air and readings from the 13.4.1 The time between oxygen concentration measure-
sensor can be taken immediately. If using other than air as the ments should be such that a minimum of 8-10 reading are taken
upper oxygen level calibration gas, then the sensing well must between the starting and ending oxygen points in the data
be purged with that gas. Purge the sensing well with the higher accumulation period.
oxygen level calibration gas at 5-10 cm3/min. Note that
whenever purging with a sample in the chamber, care must be 14. Calculation
taken to avoid stretching or bulging the film. A flow rate of
14.1 A computer and detection system will be required to
5-10 cm3/min with valves open has been determined to not
convert the decay time into partial pressure of oxygen using the
cause undue sample bulging or stretching. Oxygen concentra-
Stern Volmer equations.
tion should be monitored until the reported value does not
change. Expect to purge with at least 5 chamber volumes of gas 14.1.1 The fluorescent signal decay depends on the oxygen
(typically 5-10 minutes). Once the indicated concentration partial pressure (pO2). The typical fluorescent life time τ varies
remains steady, calibrate the oxygen sensor to this known between 1 µs in air (pO2 = 212 mbar at sea level) and 5 µs in
value. zero oxygen.
13.2.2 Purge the sensing well with the lower oxygen level 14.1.2 As the fluorescence decays, its lifetime can be
calibration gas (typically nitrogen) at a flow rate of 5-10 derived from the following equation.
cm3/min. Again, observe the indicated oxygen concentration
until it does not change. Once the concentration reading is
I
I0
5 exp S D
2t
τ
(1)
steady, calibrate the oxygen sensor to this known value. From
these two readings of calibrated/known gas concentrations, the where:
system can determine the calibration curve parameters (see I = fluorescent intensity at a certain time,
Section 14 below). By purging the sensing well with the lower I0 = fluorescent intensity at the start of the decay,
oxygen concentration lastly, the step also serves to prepare the t = time (µs), and
chamber for the commencing of the test. τ = fluorescence lifetime or time (TC).

13.3 Initiate the test with the specimen mounted as a sealed 14.1.3 The software calculates the time constant τ from the
semi-barrier between the two halves of the permeation appa- a least squares fit of the fluorescence signals generated by the
ratus. chemical coating on the oxygen sensor and from the time
13.3.1 The sensing well which contains the oxygen sensor is constant the oxygen concentration is calculated. The relation-
slowly purged (5-10 cm3/min) by a stream of nitrogen until the ship between the oxygen partial pressure and the measured
sensing well is either essentially free of oxygen or to a known fluorescence lifetime (time constant) is given by the Stern
reduced oxygen level (based on indicated oxygen concentra- Volmer Equation.
tion reading shown by the instrument). Close the inlet valve of τ0
the sensing well prior to the outlet valve to eliminate pressure 5 11K SV ·pO 2 (2)
τ
within the sensing well.
where:
13.3.2 A gas of known oxygen concentration, typically
100% oxygen, is applied to the driving well at a rate of τ = time constant at current concentration,
approximately 5-10 cm3/min for 5-10 minutes. The driving τ0 = time constant in the absence of oxygen,
well may be sealed off after flushing by closing the inlet valve KSV = Stern-Volmer constant, and
pO2 = oxygen partial pressure in mbar.
first then the outlet valve. Alternatively, if air (20.9% oxygen)
is to be used as the driving gas, the valves can be left open. As 14.1.4 This linear Stern Volmer equation is transposed in the
stated previously, care must be taken to prevent any pressure software to;
differential on either side of the film specimen which may 1
distort it, changing the sensing well volume. TC
5 A·pO 2 1B (3)
13.3.3 Oxygen concentration in the sensing well is mea-
sured periodically at time increments sufficient to indicate a where:
small gain in oxygen with each reading (changes of 0.05% TC = time constant at current oxygen concentration in µs,
oxygen have been found satisfactory between readings). A = slope of Stern Volmer line, and
13.3.4 The test should continue until such time as the B = intercept of Stern Volmer line.
experimenter is satisfied that the indicated increase in oxygen 14.1.5 The calibration process determines the slope and
concentration during the test period is consistent with results intercept (dA and dB) of the Stern Volmer line for a low and a
obtained from previous periods. high oxygen concentration. These values are used by the
13.4 Start/End Points—The permeation of the sample and computer system to convert fluorescent decay data into oxygen
the permeation precision sought will determine the oxygen concentration (pO2).

4
 F3136 − 15
TABLE 1 Oxygen Transmission Rate (cm3 (STP)/(m2·day))
Repeatability Reproducibility
Standard Standard Repeatability Reproducibility
A
Material Average Deviation Deviation Limit Limit
x̄ sr sR r R
PE/nylon/PE 28.61 2.74 5.51 7.67 15.43
72 µm PET 68.33 6.01 10.31 16.83 28.87
3 mil PE 2289 256.1 320.7 717.1 898.1
A
The average of the laboratories’ calculated averages.

14.2 The oxygen permeation is calculated as shown below. 14.3 See Appendix X1 for an example of an OTR calcula-
A linear regression from the plot of the accumulation ratio tion based on oxygen ingress accumulation during the pre-
calculated from data collected between the starting and ending defined test period.
points as suggested in 13.4 is used to determine the oxygen
permeation. 15. Report
14.2.1 The fundamental equation used to derive OTR is: 15.1 Report the following information:
~pDriving
O2 2 p Sensing initial
O2 ! OTR·Area 15.1.1 A description of the test specimen, including each of
ln Driving Sensing time5t 5 ·time (4) its component layers or coatings, and the film orientation (i.e.
~pO2 2 p O2 ! Volume
which side of the structure is facing the oxygen sensor).
where: 15.1.2 The average thickness of the test specimens as
pO2Driving = partial pressure oxygen in driving well, determined in 11.2 and the standard deviation of the thickness
pO2Sensinginitial = partial pressure oxygen in sensing well at values.
time 0, 15.1.3 The permeation apparatus used.
pO2Sensingtime=t = partial pressure oxygen sensing well at any 15.1.4 The barometric pressure, temperature, date, and time
time t, for each measurement.
OTR = oxygen transmission rate, 15.1.5 The oxygen permeation as calculated in 14.2 based
Area = film specimen area, on the dynamic oxygen accumulation data.
Volume = volume of sensing well, and
Time = unit time. 16. Precision and Bias
14.2.2 Therefore, the slope of the plot of the left hand side 16.1 The precision of this test method is based on an
versus time is used to calculate OTR as follows: interlaboratory study conducted in 2014. Four laboratories
? Slope ? ·Volume participated in this study. Each of the four laboratories reported
OTR 5 (5) five replicates of three different plastic films, being tested for
Area
oxygen permeability. Every test result reported represents an
where: individual determination. Except for the use of only four
OTR = oxygen transmission rate, laboratories, Practice E691 was followed for the design and
Slope = slope of the described calculated variable versus analysis of the data; the details are given in RR:F02-10393
time, 16.1.1 Repeatability (r)—The difference between repetitive
Volume = volume of the sensing well, and results obtained by the same operator in a given laboratory
Area = film specimen area. applying the same test method with the same apparatus under
14.2.3 The oxygen transmission rate, OTR, is determined in constant operating conditions on identical test material within
cm 3 O STP short intervals of time would in the long run, in the normal and
2
units of m 2 ·day when time is reported in days, Area in m2
correct operation of the test method, exceed the following
and chamber volume in cm3. values only in one case in 20.
14.2.4 It is also possible to invert the accumulation ratio in 16.1.1.1 Repeatability can be interpreted as the maximum
order to plot relative accumulation over time. For example: difference between two results, obtained under repeatability
~ p ODriving 2 p OSensing time5t
! conditions, that is accepted as plausible due to random causes
2 2
ln (6) under normal and correct operation of the test method.
~ p ODriving
2
2 p OSensing
2
initial
!
16.1.1.2 Repeatability limits are listed in Table 1.
where: 16.1.2 Reproducibility (R)—The difference between two
pO2Driving = partial pressure oxygen in driving well, single and independent results obtained by different operators
pO2Sensinginitial= partial pressure oxygen in sensing well at applying the same test method in different laboratories using
time 0, different apparatus on identical test material would, in the long
pO2Sensingtime=t = partial pressure oxygen sensing well at any run, in the normal and correct operation of the test method,
time t. exceed the following values only in one case in 20.
14.2.4.1 This provides the same magnitude for slope, but
with an opposite sign. Using the absolute value of the resulting 3
Supporting data have been filed at ASTM International Headquarters and may
slope as shown above ensures estimation of OTR with the be obtained by requesting Research Report RR:F02-1039. Contact ASTM Customer
proper, positive sign. Service at [email protected].

5
 F3136 − 15
16.1.2.1 Reproducibility can be interpreted as the maximum with considerably greater or smaller frequency than the 95%
difference between two results, obtained under reproducibility probability limit would imply. The repeatability limit and the
conditions, that is accepted as plausible due to random causes reproducibility limit should be considered as general guides,
under normal and correct operation of the test method. and the associated probability of 95% as only a rough indicator
16.1.2.2 Reproducibility limits are listed in Table 1. of what can be expected.
16.1.3 The above terms (repeatability limit and reproduc- 16.2 Bias—At the time of the study, there was no accepted
ibility limit) are used as specified in Practice E177. reference material suitable for determining the bias for this test
16.1.4 Any judgment in accordance with statements 16.1.1 method, therefore no statement on bias is being made.
and 16.1.2 would normally have an approximate 95% prob- 16.3 The precision statement was determined through sta-
ability of being correct, however the precision statistics ob- tistical examination of 60 results, from four laboratories, on
tained in this ILS must not be treated as exact mathematical three types of film.
quantities which are applicable to all circumstances and uses.
The limited number of materials tested and laboratories report- 17. Keywords
ing results guarantees that there will be times when differences 17.1 dynamic accumulation; fluorescence; OTR; oxygen
greater than predicted by the ILS results will arise, sometimes transmission rate; permeability; permeation; plastic film

APPENDIX

(Nonmandatory Information)

X1. CALCULATION OF OXYGEN GAS TRANSMISSION RATE USING DYNAMIC ACCUMULATION DATA

X1.1 Calculation of oxygen transmission rate for a given where:

sample is described below. The fundamental equation used to OTR = oxygen transmission rate,
derive OTR is: Slope = slope of the described calculated variable versus
time,
~ p ODriving
2
2 p OSensing
2
initial
! OTR·Area Volume = volume of the sensing well, and
ln 5 ·time (X1.1)
~ p ODriving
2
2 p OSensing
2
time5t
! Volume
Area = film specimen area.
where: 2 cm 3 O STP
X1.1.2 OTR is determined in units of m 2 ·day when time
pO2Driving = partial pressure oxygen in driving well,
pO2Sensinginitial = partial pressure oxygen in sensing well at is reported in days, Area in m and sensing well volume in cm3.
2

time 0,
pO2Sensingtime=t = partial pressure oxygen sensing well at any X1.2 As an example, assume the data in Table X1.1 was
time t, obtained using a permeability apparatus with a sample surface
OTR = oxygen transmission rate, area of 20 cm2 (0.0020 m2) and an sensing well volume of 6
Area = film specimen area, cm3.
Volume = volume of sensing well, and
Time = unit time. X1.2.1 This same data is presented in graphical form in Fig.
X1.1 with a linear regression line added to determine its slope.
X1.1.1 Therefore, the slope of the plot of the left hand side
versus time is used to calculate OTR as follows: X1.2.2 The oxygen transmission rate (OTR) is determined
from the given slope of the linear regression line as follows:
OTR 5
? Slope?·Volume (X1.2) OTR = 0.0129 day-1 × 6 cm3 / 0.002 m2 = 38.6 cm3 O2 STP/(m2·day)
Area

TABLE X1.1 Oxygen Accumulation Data with Calculation

Calculated Column for Plot
Oxygen
Date and Days from
Concentration s p ODriving 2 p OSensing
2 2
initial
d
Time Start (days) ln
(%) s p ODriving 2 p OSensing
2 2
time5t
d

Day 1 05:12 0.00 0.10 0.0

Day 1 12:04 0.29 0.50 0.004012
Day 1 20:00 0.62 0.75 0.006528
Day 2 08:00 1.12 1.40 0.013098
Day 2 14:00 1.37 1.90 0.018182
Day 2 21:00 1.66 2.20 0.021245

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 F3136 − 15

FIG. X1.1 Plot of Oxygen Accumulation Data

X1.3 The determination of the oxygen concentration within oxygen on the fluorophore is accomplished using automated
the permeation apparatus by measuring the quenching effect of sensors and a computer system as described in 14.1.

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