EFFECT OF TEST CONDITIONS AND

PET SURFACE TREATMENT ON

MOISTURE BARRIER OF MULTILAYER
METALLIZED FILM STRUCTURES*

Lee Murrayy and Pat McCarry

Pechiney Plastic Packaging Inc., Flexible Packaging Division R&D,
Neenah, Wisconsin, USA

ABSTRACT: Water vapor transmission rate (WVTR) testing on multilayer

packaging films containing aluminum metallized polyester showed that barriers
can be adversely affected by exposures to high levels of humidity. While it is a
common industry practice to test and report results at 90% RH and 38
C, more
realistic test conditions provide a more accurate prediction of barrier
performance. WVTR results varied with the substrate surfaces beneath the
aluminum metal coatings and were also dependent on which sample surface was
exposed to the moist test gas. Modern test equipment and standard test methods
permit testing conditions that more closely resemble the end-use conditions.

KEY WORDS: WVTR, metallized PET, EVA, aluminum metallization, testing,

moisture barrier, sidedness, orientation, surface treatment.

INTRODUCTION

T HERE ARE INCREASING demands on the packaging industry to

develop films that are extremely good barriers to moisture.
These demands include the need for increased shelf life for dry food
products or the protection of extremely moisture sensitive medical
products, e.g. pharmaceuticals, test kits, and absorbable sutures.

*This article is based on a paper presented at TAPPIs PLACE Conference held in Boston,
Massachusetts on September 1114, 2002.
y
Author to whom correspondence should be addressed.

JOURNAL OF PLASTIC FILM & SHEETING, VOL. 19JANUARY 2003 55

8756-0879/03/01 005513 $10.00/0 DOI: 10.1177/875608703036003
2003 Sage Publications

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56 L. MURRAY AND P. MCCARRY

The moisture vapor barrier of packaging film is expressed in terms of

water vapor transmission rate (WVTR), which is the rate at which water
vapor flows normal to the surface under steady-state conditions, per
unit of area [1]. WVTR is reported in g/m2 day and is typically tested at
38
C and 90% RH, although other options are permitted [2] but they
must be stated in the report [3]. The most current test method is
described in TAPPI T557 pm-95, Water vapor transmission rate through
plastic film and sheeting using a modulated infrared sensor [1].
Water vapor transmission rate test conditions are often more severe
than the typical end use conditions for a package. For instance, a
moisture barrier package for a dry product would have a near 0% RH
condition inside the package but an average of 50% RH on the outside of
a package.
To correlate the WVTR measured at typical TAPPI conditions of 90%
RH, the packaging engineer can use a water vapor permeance
calculation to extrapolate this WVTR90%RH value to a WVTR value at
a different RH. The value of water vapor permeance is the ratio of
WVTR to the vapor pressure difference across the sample:
WVTR
Permeance where
P Ptest gas side  Psweep gas side

P
Permeance is typically expressed in units of g/m2  day  mmHg. To
extrapolate WVTR values made at one RH condition to WVTR values
at another RH condition, one must assume that WVTR is directly
proportional to the vapor pressure difference as defined by permeance.
For example, assume a film that has a WVTR of 1 g/m2  day as
measured at 90% RH. To calculate WVTR50%RH, first determine
permeance using the 90% RH values:

WVTR90%RH
Permeance
90%P

where P is the vapor pressure of water at the 38
C test temperature.

If the assumption is made that the WVTR is proportional to the vapor
pressure gradient, then WVTR50%RH can be calculated as:
WVTR90%RH
WVTR50%RH  50%P
90%P
The vapor pressures cancel leaving:
5
WVTR50%RH WVTR90%RH 0:56 WVTR90%RH
9

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 Moisture Barrier of Metallized Film Structures 57

Thus, for package design purposes, the packaging engineer can then
calculate how much moisture would enter the package over its desired
shelf life in a typical end use condition of 50% RH.
The major assumption for this method is that WVTR is directly
proportional to the vapor pressure differential across the sample. TAPPI
test method T557 pm-95 strongly notes that this relationship does
not apply for all cases. Factors such as concentration dependant
diffusion (non-Fickian behavior) or some other interaction between
moisture and the film or components of the film would prevent one from
making a valid adjustment of the test data to a different condition.
One packaging component that can be affected by moisture is aluminum
metallized polyester (met PET). Metallized film transmission rates
often show high levels of variability [4], some of which is due to
mechanical damage but a significant portion also due to test conditions.
Early test equipment [5] usually included a moist pad to apply 100% RH
to one side of a structure. Recent improvements to test equipment
allowed for instrument generated humidity differentials of up to 90%
RH. Even with 90% RH test gas, anomalous transmission rate
measurements occur.
The primary focus of this work was to compare the WVTR properties
of met-PET packaging films measured at a standard test condition of
90% RH and a more realistic value of 50% RH. In addition, the work
examined the effect of the surface treatment of the PET on which the
aluminum metal is deposited as well as the orientation of the sample
relative to the dry and wet side of the test.

EXPERIMENTAL

Products tested had the structure: 12
PET/treatment/metallization/

adhesive/EVA sealant. The PET was a heat resistant layer that can
resist the temperatures required to melt and fuse the ethylene vinyl
acetate copolymer (EVA) sealant. The aluminum metallization is a
barrier that keeps the package contents from gaining or losing moisture
during storage. The performance of a metal coating depends upon
several factors including:
. The thickness of metal as measured by surface resistivity or optical
density [6]
. The smoothness of the surface on which the metal is placed [7]
. The barrier properties of the coating or substrate on which the metal
is deposited. This property relates to the sideways diffusion of the
permeant molecules to the microscopic defects in the aluminum

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58 L. MURRAY AND P. MCCARRY

coating (bottlenecks for diffusion) where diffusion actually takes

place [8].
The optical density of the metallization was 3.0. The urethane
adhesives function is to hold the sealant to the met-PET. Two different
metallized PETs were used in the study. Sample 1 included a metallized
PET having corona treatment to anchor the aluminum to the PET.
Corona treatment is a widely used method of creating chemical
functionality through an oxidative process [9] utilizing activated
oxygen in the corona. Sample 2 included a metallized PET having a
chemical coating (referred to here as a chemical treatment). The chemical
treatment was believed to be a water-borne polyester copolymer [10]
applied at a low coating weight. These were, in some cases, experimental
variables. The results should not be considered representative of
commercial packaging films made by Pechiney Plastic Packaging.
Testing was carried out on three MOCON Permatran-W 3/31
modules controlled by a single computer running Permnet software.
All experiments were conducted at 38
C. The carrier gas was nitrogen
produced by a membrane nitrogen generator.
Prior to testing, all samples were inspected for metallization defects
such as scratches and pinholes using a light table. Test films were
positioned in the test equipment in one of the two ways. A package used
for a dry product would normally be mounted so that the moisture
would be to the outside of the package (PET in these cases) and the dry
sweep gas to the inside of the package (EVA in these cases). Alternately,
if packaging a moist product, WVTR testing would be conducted with
the moist test gas directed to the sealant (EVA).
The determination of water vapor transmission rate is performed on a
controlled area of a sample by exposing one side to moist test gas
(nitrogen) of known moisture concentration and the other to a dry sweep
gas (nitrogen). The sweep gas, flowing at a constant rate, picks up the
moisture moving through the sample. The sweep gas is directed to an
infrared detector that can measure the increased concentration of
moisture in the sweep gas. Blank readings are taken with dry sweep
gas passing over both sides of the specimen. Normally one cell of the
module is tested at a time (sweep gas is directed to the detector) while the
other is vented to the room. At a predetermined frequency, the flows
going to the detector and going to the room are switched via instrument
electronics. The blank corrected detector signal is logged versus time.
The experiment is complete when a steady state of transmission is
reached, i.e. when the signal no longer increases or decreases with
time. The experimental arrangement is diagrammed in Figure 1.

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 Moisture Barrier of Metallized Film Structures 59

Moist Test
Gas In

Side A Side B

Detector

Moist Test
Gas Out

Dry Nitrogen
Sweep Gas

Test Film Detail

Chemical or Corona Treatment 12 Polyester Film (PET) Al Metal Coating

Urethane Adhesive
50 EVA Sealant Film

Figure 1. Diagram of moisture vapor transmission rate test.

The experimental design included four test factors and two responses
(See the Appendix for a table of test conditions and associated WVTR
values):
Factors

1. Percent relative humidity of test gas (50% vs. 90% RH) The basic
thrust of this work was to determine if testing at 90% RH was an
objective way of measuring the moisture barrier properties of films
that would likely be used at less severe conditions.
2. Orientation (PET or EVA Sealant) of the sample to the moist test
gas The purpose of this factor was to change the concentration
gradient across the structure to test the sensitivity of various
components to water vapor. In some cases the sealant can provide
significant protection to the metallization by virtue of being a good
moisture barrier. In the case of the test film, the sealants WVTR was
20 g/m2 day while the PET, without the metal would have had a
WVTR of about 40 g/m2 day.

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60 L. MURRAY AND P. MCCARRY

3. Treatment (corona or chemical treatment) of the surface on which the

aluminum is deposited Based on variability noted earlier regarding
WVTR values with metallized-chemically treated PET, a comparison
was desired with metallized-corona treated PET. The ability to bond
the microscopic metal plates to the PET may be an important key to a
durable moisture barrier property.
4. Sequencing of the experiment In the normal course of operation, a
valve operates to change the destination of sweep gas with
transmitted moisture. As one cell is being monitored by the detector,
the other cell is being vented to the room as shown in Figure 1.
The change was made every hour with a sweep gas blank being taken
every other complete cycle. In the case of the proposed method, test
gas remained directed to one cell until steady-state was reached while
the sweep gas to cell B was purged to the room. When cell A reached
steady-state the valve was switched and testing begun on cell B.

Responses

1. WVTR (grams per square meter per day (g/m2 day). Tested at the
variable test humidity, 50 or 90% RH and evaluated as a function of
Permeance.
2. Time to reach steady-state.
A 24 designed experiment (known as DOEs or DOXs) was analyzed
using Design-Expert Version 6.0.3 software from Stat-Ease.

RESULTS AND DISCUSSIONS

WVTR Response

The statistical analysis yielded very significant relationships between

combinations of variables and Permeance as shown in Table 1.
Probability > F column values less than 0.05 are significant at the

Table 1. ANOVA analysis summary.

Factor Probability > F-Values F-Value

% RH 0.0001 24
Treatment under metal 0.0001 36
Side to moisture  % RH 0.054 4.1
% RH  treatment 0.0018 12

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 Moisture Barrier of Metallized Film Structures 61

95% confidence level. The chance of the model predicting all results
adjusted to a 90% test condition being the result of noise was less than
0.01%. The F-value in the ANOVA table is the ratio of model mean
square to the appropriate error mean square and is dependent on the
degrees of freedom. F-values above about 4.0 in this case represent 95%
significance of the factor.
The factors relative humidity, side to moisture and treatment under
metal were all important. The significance of these results can be
illustrated by comparing actual test results at 50% RH to those
computed from the 90% test result. This is done in Table 2. By using
a test condition of 90% RH, the actual WVTR of a test film at 50% RH is
overestimated by up to 116%. The shelf life of a dry product designed by
testing at 90% RH to last 2 years at a 50% RH Environment would, in
reality, survive to 4 years, 4 months based on a 116% error in
permeation rate projection. A less costly package may have done the
job. Laboratories using older test equipment and moist pads next to the
samples (100% RH test gas) can produce errors greater than those
stated here based on testing at our facility using these structures.
Conversely, testing at 50% RH would not properly characterize barrier
performance at 90% RH.
The relative humidity at which testing becomes nonlinear has
not been determined; but it would vary with the metallized structure.
This supports testing at appropriate conditions when predicted results
from traditional conditions such as 38
C and 90 or 100% RH are not
reliable.
The factor PET treatment under metal had a major influence
on WVTR by itself but also in combination with the other factors %
RH and side to moisture. In our case we believe that polyester copolymer
was applied as a thin layer on the PET from a water dispersion.
The broad brush of chemical treatment is too inclusive to apply to
all coatings or treatments and we make note here that chemical
treatments/coatings are not all alike and have different sensitivities
to humidity stress as imposed by test gas RH and film side to the
humidity.
Similarly the degree of corona treatment can vary. Converters
recognize that there are appropriate power levels to be applied for the
purpose of improving adhesion via increased surface energy. Previous
experiments in our laboratory showed that structures with aluminum
deposited on untreated PET had an even greater sensitivity to 90% RH
test gas than metallized chemically treated PET.
The factor dealing with the sequencing of testing (alternating
measurements between two samples versus testing one sample until

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 62
L. MURRAY
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AND
P. MCCARRY
Table 2. Average values (g/m2 day) obtained with side to moisture and treatment under metal (Avg 6 s, n 5 4, test
sequence options pooled).
Side to PET 90% RH 50% RH Extrapolation from Error by
Moisture Treatment Test Value Test Value 90 to 50% RH Extrapolation
(%)

EVA Sealant Chemical Avg. 1.25
0.19 Avg. 0.32
0.09 Avg. 0.69
0.11 116
PET Chemical Avg. 0.99
0.21 Avg. 0.34
0.02 Avg. 0.55
0.11 62
EVA Sealant Corona Avg. 0.83
0.05 Avg. 0.30
0.03 Avg. 0.46
0.03 53
PET Corona Avg. 0.60
0.08 Avg. 0.30
0.02 Avg. 0.34
0.04 13
 Moisture Barrier of Metallized Film Structures 63

steady state is achieved) did not prove to be an important factor in the

final WVTR. However, the time to achieve steady state was an
experiment response that significantly related to sequencing when the
sample was positioned with EVA to the moist gas. The ANOVA table
showed seven factors and interactions that created a very significant
model. There was only a 0.01% chance that a model F-Value could have
occurred due to noise. Figure 2 is an interaction plot for the factors side
to moisture, and test sequence for the response, equilibration time (h) at
90% RH with metallization on chemically treated PET. Note that when
EVA was toward the test gas, steady state was achieved in 169 h
compared to only 14 h using the continuous method. The data also
shows that at 50% RH, the equilibration time was shorter and less
variable as shown in Table 3.
In testing the WVTR of the structure containing polyester #2 at 90%
RH it was noted that the length of the nonsteady-state period lasted
over 100 h in some cases. In all cases, we tested until the locus of
data points was no longer increasing. To determine the time at which
steady-state was reached, a ruler was placed horizontally along the

Time to Reach Steady-State

90% RH, Sample 2 (Chemical Treatment)

200
175
150
125
Hours 100
75
50
25
0
EVA to EVA to PET to PET to
Moisture, Moisture, Moisture, Moisure,
Alternating Continuous Alternating Continuous
Figure 2. Effect of test sequence and side toward moisture on equilibration time.

Table 3. Time to reach equilibration by test gas

humidity (Average 6 s, n 16).
Test Gas Humidity Time to Reach
(% RH) Steady State (h)

50 16
8
90 70
59

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64 L. MURRAY AND P. MCCARRY

steady state portion of the plot of WVTR versus time. The point at which
the increasing WVTR values reached the steady-state line defined by
the ruler was the point at which steady-state was reached. The increases
in transmission rate were often gradual and not easily seen above
the noise level of the instrument. The transmission rate of samples
tested over extended numbers of hours differed from the 48-h
measurement by 5% or less which represented changes in the range
of 0.01 g/m2 day. The significance of this change would be dictated by
the end use shelf-life requirement of the material and product.

CONCLUSIONS

Testing at traditional test conditions of 90% RH and 38
C can result in

unrealistic estimates of a metallized packages performance. The
distortion of barrier performance varies with test gas humidity, PET
treatment under the metal coating, and the protection that other
moisture barrier layers in the structure provide to the metal coating.
Former test methods called for testing WVTR at 38
C/90% RH. More
moderate humidity and temperatures may be used under ASTM and
TAPPI test methods [11]. For some applications, structures that tolerate
the high humidity and temperatures are required. The approach taken
may depend on the product, the flexible packaging film being used, and
the probable environment for its distribution, storage and end use.
Testing for 48 h on a Permatran-W 3/31 at 90% RH provided
sufficiently reproducible data for the two structures tested. The ability
to see and evaluate the equilibration data while the experiment is in
progress is recommended when testing aluminum metallized barrier
film structures.

ACKNOWLEDGMENTS

We wish to thank the following people: Sue Rothlesberger and

Rosemary Baker, members of the Permeation Committee who produced
the test results. Dave Maki of MOCON who participated in the
development of the test plan including the modified test sequence.
Sue Schaefer and Steve Willis for providing the samples used for
testing. Finally, we wish to thank Chad Mueller, Manager of Materials
Research and Characterization, for the technical advice and support in
pursuing this study.

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 Moisture Barrier of Metallized Film Structures 65

APPENDIX

Experimental Design for Primary DOX

Moist Side Percent RH Surface Sequence g/m2 day Steady State h

PET 50 Chemical Alternating 0.33 12
PET 50 Chemical Alternating 0.34 18
PET 50 Chemical Continuous 0.33 20
PET 50 Chemical Continuous 0.37 12
Sealant 50 Chemical Alternating 0.18 4
Sealant 50 Chemical Alternating 0.33 8
Sealant 50 Chemical Continuous 0.38 16
Sealant 50 Chemical Continuous 0.37 17
PET 50 Corona Alternating 0.29 10
PET 50 Corona Alternating 0.28 6
PET 50 Corona Continuous 0.33 10
PET 50 Corona Continuous 0.31 33
Sealant 50 Corona Alternating 0.32 28
Sealant 50 Corona Alternating 0.27 27
Sealant 50 Corona Continuous 0.33 17
Sealant 50 Corona Continuous 0.28 11
PET 90 Chemical Alternating 0.71 90
PET 90 Chemical Alternating 0.99 119
PET 90 Chemical Continuous 1.19 55
PET 90 Chemical Continuous 1.08 170
Sealant 90 Chemical Alternating 1.02 168
Sealant 90 Chemical Alternating 1.49 170
Sealant 90 Chemical Continuous 1.27 21
Sealant 90 Chemical Continuous 1.21 6
PET 90 Corona Alternating 0.69 50
PET 90 Corona Alternating 0.64 63
PET 90 Corona Continuous 0.51 9
PET 90 Corona Continuous 0.57 6
Sealant 90 Corona Alternating 0.83 69
Sealant 90 Corona Alternating 0.76 84
Sealant 90 Corona Continuous 0.72 25
Sealant 90 Corona Continuous 0.75 14

Test Gas RH (%) Treatment Average Variance

50 Pooled 0.316 0.0022
50 Chemical 0.329 0.0119
50 Corona 0.303 0.0005
90 Pooled 0.902 0.0809
90 Chemical 1.121 0.0525
90 Corona 0.683 0.0113

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66 L. MURRAY AND P. MCCARRY

REFERENCES

1. TAPPI Test Method T 557 pm-95, Section 3.3.

2. TAPPI Test Method T523 requires that the results be reported at one of two
conditions conforming to T 465 (38
C, and 90/2% RH) or T 488 (23
C, and
50/2% RH).
3. ASTM F-1249 -90 (Reapproved 1995), as well as TAPPI Methods T 523 and
T 557, require reporting test conditions of temperature and humidity.
4. Data included in this report as well as personal communication with
converters, suppliers, and in-house packaging engineers.
5. Water vapor test equipment produced by MOCON (formerly Modern
Controls, Inc.) between 1968 and 1994 without variable humidity generation
capability.
6. A minimum optical density (O.D.) is a common specification for metallized
films.
7. Moosheimer, U. et al. (1999). Permeation of oxygen and moisture through
vacuum web coated films, Society of Vacuum Coaters, 42nd Annual Technical
Conference Proceedings, ISSN 0737-5921.
8. Kelly, R.S.A. (1987). High Barrier Metallized Laminates for Food Packaging,
J. Plastic Film & Sheeting, 3: 41.
9. Mount III, E.M. (March 2001). Plasma Pretreatment for Metallizing
Packaging Film, Converting Magazine.
10. Culbertson, E.C. and Rudd, D. (1991). Adhesion on Plastic Substrates,
Polymers Paint Colour Journal, 181: 4291.
11. TAPPI Test Method T557 pm-95 and ASTM 1249-01 place no restrictions on
the test gas humidity or temperature to be used. In the report requirements,
those conditions and the time to equilibrium are to be reported.

BIOGRAPHIES

Lee Murray

Lee Murray received his BSChem from Davis & Elkins College in 1965
and his MS in Organic Chemistry from West Virginia University in
1967. His experience in flexible packaging has spanned over 26 years,
much of it at American National Can Company. He is currently a
Research Fellow in the Materials Research and Characterization group
of Pechiney Plastic Packaging Company.

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 Moisture Barrier of Metallized Film Structures 67

Patricia McCarry

Patricia McCarry received her BSChem from the University of

Wisconsin, Oshkosh in 1985. In her span of 16 years in packaging
research, Pat has primarily worked on polymer and organic chemistry.
She is currently a Research Associate in the Materials Research and
Characterization group of Pechiney Plastic Packaging.

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