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Journal of Testing and Evaluation, Vol. 39, No. 4

Paper ID JTE103318
Available online at: www.astm.org
TECHNICAL NOTE

Sara R. Halper1 and Randy M. Villahermosa1

Comparative Evaluation of the Moisture

Permeation of Polyurethane, Polyethylene,
and Fluoropolymer Tubing

ABSTRACT: Polymer tubing is used for a variety of applications such as the transport of dry nitrogen and other gases in order to purge systems
of moisture and other contaminants. While some polymer tubing are marketed for low-moisture applications, permeation data are often not reported
to aid in material selection. Tests were performed to compare moisture permeation for a variety of tubing materials that could be used in dry gas
purged systems. The results demonstrated that polyethylene and fluoropolymer tubing exhibited practically no moisture permeation, while polyure-
thane tubing exhibited a noticeable amount of moisture permeation. The results were compared with the moisture permeation of thin films. The
permeation was found to be influenced by many factors as dictated by the various results derived from different brands and different durometers
within the same brand. The effect of external relative humidity on permeation was also measured. Approximations can also be made on the internal
relative humidity based on the external relative humidity. These approximations can be used as well to determine the maximum possible moisture
exposure level outside the tubing or the purge time required for a specific application. The results could assist in material selection based on the
desired application.
KEYWORDS: polyurethane, polyethylene, fluoropolymer, tubing, moisture, humidity

Introduction has long been known as an excellent tubing material to prevent

moisture permeation, to withstand extreme temperatures, and to be
Nitrogen and other inert gases are often transported through tubing inert to most chemicals. However, the tubing is usually stiffer than
in order to purge systems of water and other contaminants. The tub- other types of polymer tubing, which may be a disadvantage. An-
ing can be made from a variety of materials. Metal is an excellent other drawback of fluoropolymers is that they are not as stable as
material for preventing moisture permeation and can withstand a other polymers when exposed to various types of radiation such as
variety of environmental conditions. However, polymer tubing is a UV [1,2].
popular alternative to metal because it is inexpensive and light- Polyethylene (PE) is also known to be impermeable to moisture
weight, and it can have great flexibility depending on the material and inert to a wide range of chemicals and environments. While not
used. However, polymer tubing can have certain drawbacks, such as as advantageous as fluoropolymers for reasons such as the potential
degradation due to chemical and environmental impacts. In addi- to crack if subjected to continual folding, PE is usually less expen-
tion, polymer tubing can be more permeable to various contami- sive to fabricate and is thus widely used. And while also not stable
nants including water. Polymer tubing currently is made from a va- to UV radiation, some PE tubing have been prepared with UV sta-
riety of materials and blends, with different manufacturing and bilizers to help protect them [3–6]. PE is fabricated in many forms
processing techniques that affect permeability. For certain applica- and is usually subdivided into classes by its density, with the most
tions such as space hardware, material restrictions are required, common being low-density polyethylene (LDPE) and high-density
such as no plasticizers or low-outgassing properties to minimize polyethylene (HDPE).
contamination. Certain types of materials also are known to be un- Polyurethane (PU), another type of material that is inert to many
able to withstand space environments such as high radiation, and different chemicals and environments, is available in two forms:
therefore cannot be used for most space applications. ether-based and ester-based. Ester-based PU has been shown to de-
grade with water because of the possible attack and breakdown of
Tubing Selection the ester link by a water molecule [7]. As a result, ester-based PUs
have been used for biodegradable materials [8]. In contrast to fluo-
There is a variety of types of polymer tubing for various applica- ropolymers and PE, PU tubing is reported to be able to withstand
tions. Fluoropolymers are one type of material seen in many appli- higher UV radiation [2].
cations. The most widely used types of fluorinated polymers in tub-
ing are polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA),
and fluorinated ethylene propylene (FEP). Fluoropolymer tubing Moisture Permeation Using Standard Test Methods
Manuscript received August 16, 2010; accepted for publication February 16, Standard test methods ASTM E96/E96M–05 (Standard Test Meth-
2011; published online March 2011. ods for Water Vapor Transmission of Materials) [9] and DIN
1
The Aerospace Corporation, P.O. Box 92957, M2-242, Los Angeles, CA 53122-1 (Determination of the Water Vapour Transmission Rate of
90009, e-mail: [email protected] Plastic Film, Rubber Sheeting, Paper, Board and other Sheet Mate-

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736 JOURNAL OF TESTING AND EVALUATION

TABLE 1—Permeability of different polymers measured using ASTM E96/

E96M–05 or DIN 53122-1 [11].

Thickness, Vapor Transmission Rate,

Material mm 共g · mm兲 / 共m2 · day兲 Test Method
FEP 0.025 0.175 ASTM E96/E96M–05
PFA 0.05 0.1 ASTM E96/E96M–05
PTFE 0.2 0.241, 0.30 DIN 53122-1 FIG. 1—Setup used to control the humidity outside of the tubing while monitor-
LDPE Multiple 0.23–0.59 Multiple ing the humidity level inside of the tubing.
HDPE Multiple 0.1–0.19 Multiple
PU Multiple 0.94–3.43 ASTM E96/E96M–05
mance Plastics, Akron, OH), and a PE/fluoropolymer mixed tubing
(Chemfluor® Duality™) were also selected for comparison. Accord-
ing to the manufacturers, some of the tubing have antistatic proper-
rials by Gravimetry) [10] have been used to measure the water ties while others have moisture-resistant properties. All tubing
vapor permeability of various thin film polymers, as highlighted in samples were obtained with the same approximate dimensions of
Table 1 [11]. The water vapor transmission rate for the measured 1/4 in. inner diameter and 3/8 in. outer diameter.
fluoropolymers was reported to be very low at 0.1– 0.3 The water absorption has been measured by some manufactur-
共g · mm兲 / 共m2 · day兲. The water vapor transmission rate for LDPE ers for the tubing above following ASTM D570-98 and were re-
and HDPE was reported to be 0.1– 0.59 共g · mm兲 / 共m2 · day兲. Fi- ported as follows: Tygothane® 1.12 %, POLLY-TUBE™ 0.15 %,
nally, the water vapor transmission rate for PU was the highest re- and Chemfluor® ⬍0.01 %. The water absorption of the material
ported, at 0.94– 3.43 共g · mm兲 / 共m2 · day兲. follows the same trend as the water vapor transmission rate re-
Other standard test methods related to water absorption/ ported in Table 1, with PUs being higher than PEs and fluoropoly-
transmission such as ASTM D570-98 (Standard Test Method for mers.
Water Absorption of Plastics) [12] and ASTM F1249-06 (Standard
Test Method for Water Vapor Transmission Rate Through Plastic
Film and Sheeting Using a Modulated Infrared Sensor) [13] may Moisture Permeation Measurements
provide some useful information as well when determining the ef-
fects of moisture on a material. To measure the moisture permeation through the tubing, a special
We were interested in the effects of humidity on tubing materials setup was designed to monitor the humidity inside of the tubing and
and found that these standards did not provide adequate results for control and monitor the humidity outside the tubing (Fig. 1). The
our specific application, and thus a new experiment was designed. test setup consisted of a clear acrylic box with fittings on opposite
ASTM E96/E96M–05 and ASTM F1249-06 have been used exten- sides for a nitrogen line (outside) and the tubing (inside). The nitro-
sively to test commercial packing and products but are best suited gen flow through the inside of the tubing was not pressurized but
for thin films and not the curved closed shape of tubing. Other was controlled using flow meters (MKS Instruments, Andover,
methods such as ASTM D570-98 have been utilized and reported MA) and was kept constant at a rate of 1000 SCCM (SCCM de-
by some manufacturers to measure the moisture absorption of the notes cubic centimeter per minute at STP). Humidity probes (HMP
tubing materials, but absorption is only related to moisture perme- 50, Vaisala, Helsinki, Finland) were also attached to the fittings to
ation and is not a direct correlation, as some materials might absorb monitor the humidity inside the tubing and outside of the tubing.
but not permeate moisture at the same rate. Finally, some methods The HMP 50 humidity probes were selected because they are por-
also utilize static measurements, whereas we were interested in air table, could be integrated into the system easily, and have a large
flowing through the tubing material, not a static environment. measurement range of 0–98 % relative humidity (RH). They have a
reported accuracy of ±3% RH, but we found that we were able to
monitor very small changes in humidity, and we found that mea-
surements were repeatable across many probes and under many
Experimental conditions with much better accuracy than reported. We also were
more interested in a change in humidity versus the exact value. A
Tubing Selection and Analysis LabVIEW program was written to control the flow meters and
monitor the humidity probes. The nitrogen gas was supplied from a
FRE-STAT® (Freelin-Wade Co., McMinnville, OR) is an antistatic LN2 boil-off and was not purified further. The moisture content of
ether-based PU tubing, which, according to the technical data the nitrogen source was measured to be ⬃1.5 % RH. The humidity
sheet, is best for low-humidity environments. This may be attrib- outside the tubing was generated by either flowing in nitrogen
uted to the antistatic properties of the polymer and not specifically through a bubbler or by placing a saturated salt solution in the box.
to the PU material itself. FRE-STAT® has been used in space sys- All tests were performed at room temperature 共⬃25° C兲.
tems such as in the Geostationary Satellites (GOES) XRS/EUV in- As a control, flexible metal tubing was analyzed first. The metal
struments. Like other brands, it is available in a wide assortment of tubing was purged internally and externally with dry nitrogen, and
colors and is currently available in two different durometers: 85A then the outside of the tubing was exposed to high humidity. As
and 90A. Various colors and durometers of FRE-STAT® were se- expected, no detectable amount of humidity change was observed
lected for analysis and comparative studies. Other PU tubing mate- inside of the tubing as the humidity outside of the tubing was in-
rials were also analyzed, consisting of Ether-PUR FLEX 84 (FLEX creased.
Tubing Products, Union Springs, NY) and Tygothane® (Saint- Each type of tubing was cut to a length of 140 cm and dried
Gobain Performance Plastics, Akron, OH). A PE tubing material under nitrogen for a period of days. The final internal RH after dry-
(POLLY-TUBE™, Freelin-Wade Co., McMinnville, OR), a fluo- ing was measured to be around 1.5 %, which was approximately the
ropolymer tubing material (Chemfluor®, Saint-Gobain Perfor- same as the external RH, and was used to create a baseline value.

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 HALPER AND VILLAHERMOSA ON COMPARATIVE EVALUATION OF THE MOISTURE PERMEATION OF TUBING 737

TABLE 2—Tubing materials selected for analysis along with physical properties.

Manufacturer/Brand Material Properties Durometer

Freelin-Wade/FRE-STAT® PU/ether-based, blue color Antistatic 85A
Freelin-Wade/FRE-STAT® PU/ether-based, clear color Antistatic 85A
Freelin-Wade/FRE-STAT® PU/ether-based, black color Antistatic 90A
Saint-Gobain/Tygothane® PU/ester-based 82A
FLEX™/Ether-PUR FLEX 84 PU/ether-based Water resistant 84A
Freelin-Wade/POLLY-TUBE™ LDPE Moisture resistant 44D
Saint-Gobain/Chemfluor® FEP 55D
Saint-Gobain/Chemfluor® Duality™ FEP inner lining/LDPE exterior 45D

Humid nitrogen or air was then introduced to the outside of the and used to determine a change in RH (Fig. 3). The two
tubing. The humidity outside of the tubing and flowing through the FRE-STAT® 85A samples had the highest moisture permeation.
inside of the tubing was monitored continually for a period of days The higher durometer FRE-STAT® 90A did have a lower moisture
to weeks to observe the permeation increase and the final moisture permeation compared to FRE-STAT® 85A, while the change in tub-
permeation saturation value. When the humidity inside of the tub- ing color of the FRE-STAT® 85A had a minimal effect on the mois-
ing reached a saturation point, dry nitrogen was then introduced to ture permeation. However, the lower moisture permeation for
the outside of the tubing to monitor the desorption as well. FRE-STAT® 90A is not related to density, because the density of
FRE-STAT® 85A was also exposed to humidity levels of 35 %, the tubing was actually calculated to be slightly less than
50 %, 60 %, 75 %, and 85 % RH to measure the humidity depen- FRE-STAT® 85A. However, unlike FRE-STAT® 90A, which had a
dence on the internal moisture permeation. The same procedure as higher durometer and a lower moisture permeation compared to
above was used to monitor the permeation. FRE-STAT® 85A, the durometers of Tygothane® and Ether-PUR
FLEX were reported to be 82A and 84A, respectively, and they
both had lower moisture permeations. There appear to be many fac-
Results and Discussion tors that influence the moisture permeation of the material, and
therefore each specific brand and type would have to be tested
against other materials to determine the moisture permeation and
Moisture Absorption/Permeation and Desorption find the desired properties for a specific system.
The PU, PE, and fluoropolymer tubing listed in Table 2 were all Ester-based PUs are reported to degrade with water. However, in
analyzed at equal lengths and approximate diameters. A high RH the short time that Tygothane® was subjected to high-humidity en-
environment of ⬃70 % RH inside the test chamber was used. As vironments, the material did not appear to degrade and actually had
can be seen in Fig. 2, all the PU tubing (FRE-STAT®, Tygothane®, lower moisture permeation compared to the FRE-STAT® 85A ma-
and Ether-PUR FLEX) experienced noticeable moisture perme- terials. Although Ether-PUR FLEX is listed as water resistant (ac-
ation as the humidity outside of the tubing increased. The baseline cording to some vendors), it had high moisture permeation relative
value for each material was subtracted from the saturation value to the other types of materials. The water resistivity must be refer-

FIG. 2—RH measured flowing through the inside of the tubing after exposure to an external ⬃70 % RH environment (left) and after exposure to dry nitrogen again
(right).

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738 JOURNAL OF TESTING AND EVALUATION

FRE-STAT® 90A, which appeared to have a slower desorption

compared to 85A and compared to the other materials that had ap-
proximately the same total moisture permeation. As noted above,
the densities of FRE-STAT® 90A and 85A are similar, and there-
fore density is not a factor in the desorption rate; thus, there are
other factors that are influencing the desorption rate of the materi-
als.
As seen from the difference in the change of RH for just the few
PU materials tested, an extensive survey would have to be per-
formed to try to correlate the various changes in chemical and
physical properties between the tubing materials and the absorption
and desorption rates to try to determine the influencing factors. The
results might be hindered, though, by the unreported trade secrets
of manufacturing the materials. However, the results do correlate
with the water vapor transmission rate as measured by standard test
FIG. 3—Maximum RH inside the tubing when exposed to an external ⬃70 % methods.
RH environment.

ring to its resistance to degradation rather than to water permeation. Humidity Dependence of Polyurethane Tubing
In contrast to the PU tubing, the fluoropolymer- and PE-based Multiple humidity levels were used to expose the FRE-STAT® 85A
tubing POLLY-TUBE™, Chemfluor®, and Chemfluor® Duality™ all to determine its effect on the moisture permeation of the tubing. As
appeared to be unaffected by the increase in external humidity (Fig.
can be seen in Fig. 4, when the external humidity level increased,
3). In comparison, the results for water vapor transmission rate ob-
the internal RH of the tubing increased as well. We then attempted
tained from the standard test methods listed in Table 1 are compa-
to fit the data to various types of plots. The permeation was deter-
rable with the observed moisture permeation from this experiment.
mined not to be linear with respect to RH 共R2 = 0.920兲, but an expo-
After the PU tubing reached what appeared to be a saturation
value after being exposed to a prolonged period of time at the de- nential plot provided a more accurate fit 共R2 = 0.992兲. This is in
sired external RH, the exterior of the tubing was then exposed to agreement with theoretical data of moisture permeation through
dry nitrogen again to monitor the desorption. Ascertaining the de- other types of materials but not in agreement with the linear rela-
sorption rate of the tubing material is useful for determining how tionship established for moisture absorption of some types of ma-
long the tubing needs to be purged before it can be used. While all terials [16,17]. The exponential equation might be used to predict
the PU materials absorbed/permeated moisture on the order of the internal RH of this specific tubing material for a given external
hours to days, all of the materials desorbed/dried at a faster rate RH. An approximate maximum value could also be determined,
(Fig. 2). This has been seen in other types of materials, such as PU given that the RH cannot go above 1 (100 % RH). However, the
foams, and is attributed to many different factors [14,15]. However, equation does not take into account the length of the tubing and
this could also be due to the fact that dry nitrogen is being flowed many other varying factors, such as the different properties of the
internally and externally, whereas during absorption, humidity is different brands of material. If more exact results are desired, some
being flowed externally only. of the standard test methods might provide numerical values that
All materials desorbed moisture at a similar rate except for could be correlated with other materials.

FIG. 4—Internal RH measured flowing through the FRE-STAT® 85A tubing at various external humidity levels (left) and the RH inside the tubing compared with the
external RH inside the box (right).

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 HALPER AND VILLAHERMOSA ON COMPARATIVE EVALUATION OF THE MOISTURE PERMEATION OF TUBING 739

Conclusions [4] Basfar, A. A., Ali, K. M. I., and Mofti, S. M., “UV Stability
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