9 Polyolefins, Polyvinyls, and Acrylics

This chapter focuses on polymers made from • Linear low density polyethylene (LLDPE),
monomers that contain a carbon–carbon double polymers with densities ranging from 0.915 to
bond through which the polymer is made by addi- 0.935 g/cm3, contains comonomer.
tion polymerization as discussed in Chapter 2.1.1. An • Low density polyethylene (LDPE), polymers
alkene, also called an olefin, is a chemical compound with densities ranging from about 0.915 to
made of only carbon and hydrogen atoms contain- 0.935 g/cm3.
ing at least one carbon-to-carbon double bond. The • Medium density polyethylene (MDPE),
simplest alkenes, with only one double bond and no polymers with densities ranging from 0.926
other functional groups, form a homologous series to 0.940 g/cm3, may or may not contain
of hydrocarbons with the general formula CnH2n. The comonomer.
two simplest alkenes of this series are ethylene and
propylene. When these are polymerized, they form • High density polyethylene (HDPE), polymers
polyethylene (PE) and polypropylene (PP), which with densities ranging from 0.940 to 0.970 g/cm3,
are two of the plastics discussed in this chapter. A may or may not contain comonomer.
slightly more complex alkene is 4-methylpentene-1,
the basis of poly (methyl pentene), known under Additionally ultra high molecular weight polyeth-
Mitsui Chemicals trade name of TPX™. ylene (UHMWPE) typically has a molecular weight
If one of the hydrogens on the ethylene molecule 10 times that of HDPE.
is changed to chlorine, the molecule is called vinyl Fig. 9.3 shows the differences graphically. The
chloride, the basis of polyvinyl chloride (PVC), differences in the branches in terms of number and
commonly called PVC. There are many other vinyl length affect the density and melting points of some
monomers that substitute different functional groups of the types.
onto the carbon–carbon double bond. Vinyl alcohol Branching affects the crystallinity. A diagram
is a particularly important one. of a representation of the crystal structure of PE is
Acrylic polymers are also polymerized through the shown in Fig. 9.4. One can imagine how branch-
carbon–carbon double bond. Methyl methacrylate is ing in the polymer chain can disrupt the crystal-
the monomer used to make poly(methyl methacrylate). line regions. The crystalline regions are the highly
The structures of some of these monomers are ordered areas in the shaded rectangles of Fig. 9.4.
shown in Fig. 9.1, with polymer structures shown in A high degree of branching would reduce the size
Fig. 9.2. of the crystalline regions, which leads to lower
crystallinity.
Manufacturers and trade names: Dow Chemical
9.1 Polyethylene Dowlex®, Exopack® Sclairfilm®, DuPont Tyvek®;
LyondellBasell Alathon®, Petrolene; ExxonMobil™
PE can be made in a number of ways. The way it Enable™, Paxon™, Pax-Plus™, Exceed™; Chevron
is produced can affect its physical properties. It can Philips Marlex®; NOVA Chemicals Sclair®.
also have very small amounts of comonomers, which Applications and uses: (ULDPE) Heavy duty
will alter its structure and properties. sacks, turf bags, consumer bags, packaging
The basic types or classifications of PE, according for cheese, meat, coffee, and detergents, silage
the ASTM 1248, are: wrap, mulch films, extruded membranes, heat-
ing and water pipes, and injection-molded prod-
• Ultra low density polyethylene (ULDPE), ucts. (HDPE): Food packaging: dairy products
polymers with densities ranging from 0.890 to and bottled water, cosmetics, medical products
0.905 g/cm3, contains comonomer. and household chemicals, automotive gas tanks,
• Very low density polyethylene (VLDPE), 55 gallon drums, sheets, pipes, recreational items,
polymers with densities ranging from 0.905 to and geosynthetic materials. (UHMWPE): Hip and
0.915 g/cm3, contains comonomer. knee replacements.

Permeability Properties of Plastics and Elastomers

Copyright © 2017 Elsevier Inc. All rights reserved. 157
158 Permeability Properties of Plastics and Elastomers

Figure 9.1 Chemical structures of some monomers used to make polyolefins, polyvinyls, and acrylics.

Figure 9.2 Structures of polymers found in this chapter.

The data tables and graphs that follow will be in 9.1.2 Ultra low Density
the order of the basic types or classifications of PE Polyethylene
described in the first part of this section, except that
data on unspecified PE and data that cover the range Permeation data for ULDPE based plastics is
of PE molecular weights will be first. found in Tables 9.1–9.3.
Permeation data for PE is divided by type in the
following sections.
9.1.3 Linear Low Density
9.1.1 Unclassified Polyethylene Polyethylene
Permeation data for unclassified or unspecified PE Permeation data for PE--based plastics is found in
based plastics is found in Figs. 9.5–9.10. Tables 9.4 and 9.5.
9: Polyolefins, Polyvinyls, and Acrylics 159

Figure 9.3 Graphical depictions of polyethylene (PE) types.

9.1.5 Medium Density Polyethylene

Permeation data for MDPE based plastics is found
in Figs. 9.17–9.19 and Tables 9.13–9.19.

9.1.6 High Density Polyethylene

Permeation data for polyethylene based plastics is
found in Fig. 9.20 and Tables 9.20–9.31.

 π ⋅ de ⋅ L ⋅ p ⋅ t 
V = P ⋅  (9.1)
 e

Where: V, volume of permeating gas [cm3 (STP)];

P, permeability coefficient [cm3(STP)/m·bar·day];
de, outside diameter of the pipe (mm); L, length
Figure 9.4 Graphical diagram of PE crystal structure. of the pipe (m); p, partial pressure of the gas in
the pipe (bar); t, time (days); e, wall thickness of the
pipe (mm).

Note: Sclairfilm® is made from NOVA Chemicals

SCLAIR® Resin. 9.2 Polypropylene
The three main types of PP generally available:
9.1.4 Low Density Polyethylene
• Homopolymers are made in a single reactor
Permeation data for LDPE based plastics is found with propylene and catalyst. It is the stiffest of
in Figs. 9.11–9.16 and Tables 9.6–9.12. the three propylene types and has the highest
Figure 9.5 Permeability of gases versus the density of LyondellBasell Polyolefins PE films [1].

Figure 9.6 Water vapor transmission rate versus the density of LyondellBasell Polyolefins PE films [1].

Figure 9.7 Vapor transmission rate of various fuels versus the density of LyondellBasell Polyolefins PE films [1].
Figure 9.8 Vapor transmission rate of various solvents versus the density of LyondellBasell Polyolefins PE films [1].

Figure 9.9 Permeability of gases versus temperature of PE film [2].

Figure 9.10 Permeation of sulfur dioxide versus temperature through PE film [3].
162 Permeability Properties of Plastics and Elastomers

Table 9.1 Permeation of Oxygen at 23°C and 50% Table 9.5 Permeation of Carbon Dioxide and
Relative Humidity Through Dow Chemical Attane™ Nitrogen Through Exopack® Sclairfilm® SL1 and SL3
Blown Film [4] LLDPE Films [6]

Attane™ Grade 4201 4201 4202 Source Normalized Units,

Film thickness (mm) 0.02 0.05 0.02 Document Units, Permeability
Permeability Coefficient
Source document 716 711 695 Permeant Coefficient (cm3/ (cm3·mm/
unit, gas permeability Gas m ·day)
2
m2·day·atm)
(cm3·mil/100 in.2 day·atm)
Oxygen 150 3.81
Normalized units, per- 281 279 273
meability coefficient Carbon 1400 35.6
(cm3·mm/m2·day·atm) dioxide
Thickness: 0.0254 mm; test method: ASTM D3985.
Test method: ASTM F1249.

Table 9.2 Permeation of Carbon Dioxide at 23°C

and 50% Relative Humidity Through Dow Chemical tensile strength at yield. In the natural state (no
Attane™ Blown Film [4] colorant added) it is translucent and has excel-
lent see-through or contact clarity with liquids.
Attane™ Grade 4201 4202 In comparison to the other two types it has less
Film thickness (mm) 0.05 0.02 impact resistance, especially below 0°C.
Source document units, gas 3128 3340 • Random copolymer (homophasic copolymer)
permeability (cm3·mil/100 in.2 are made in a single reactor with a small amount
day·atm) of ethylene (<5%) added which disrupts the
Normalized units, permeability 1233 1312 crystallinity of the polymer allowing this type
coefficient (cm3·mm/m2·day·atm) to be the clearest. It is also the most flexible
with the lowest tensile strength of the three. It
Test method: ASTM F1249. has better room temperature impact than ho-
mopolymer but shares the same relatively poor
Table 9.3 Permeation of Water Vapor at 23°C and impact resistance at low temperatures.
50% Relative Humidity Through Dow Chemical • Impact copolymers (heterophasic copolymer),
Attane™ Blown Film [4] also known as block copolymers, are made in
Attane™ Grade 4201 4201 4202
a two reactor system where the homopolymer
matrix is made in the first reactor and then
Film thickness (mm) 0.02 0.05 0.02 transferred to the second reactor where ethyl-
Source document 1.58 1.39 2.15 ene and propylene are polymerized to create
units, gas permeability ethylene propylene rubber (EPR) in the form
(g·mil/100 in.2 day·atm) of microscopic nodules dispersed in the homo-
Normalized units, perme- 0.62 0.55 0.84 polymer matrix phase. These nodules impart
ability coefficient (g·mm/ impact resistance both at ambient and cold
m2·day·atm) temperatures to the compound. This type has
intermediate stiffness and tensile strength and
Test method: ASTM F1249.

Table 9.4 Permeation of Water and Oxygen Through Exopack® Sclairfilm® LX-1 Linear Low Density
Polyethylene (LLDPE) Film [5]

Source Document Units, Normalized Units, Water Oxygen Permeability

Water Transmission Transmission Rate Coefficient (cm3·mm/
Film Thickness (mm) Rate (g/m2·day) (g·mm/m2·day) m2·day·atm)
0.0762 4.7 0.36 236
0.0508 9.3 0.47 193
0.0381 12.4 0.47 236
Figure 9.11 Permeability coefficient versus reciprocal temperature of helium in low density polyethylene (LDPE) [8].

Figure 9.12 Diffusion coefficient versus reciprocal temperature of helium in LDPE [8].

Figure 9.13 Solubility coefficient versus reciprocal temperature of helium in LDPE [8].
Figure 9.14 Permeability coefficient versus reciprocal temperature of methane in LDPE [8].

Figure 9.15 Diffusion coefficient versus reciprocal temperature of methane in LDPE [8].

Figure 9.16 Permeation of oxygen, carbon dioxide, nitrogen, and water versus temperature through LDPE film [9].
9: Polyolefins, Polyvinyls, and Acrylics 165

Table 9.6 Permeation of Gases at 24°C Through Dow Chemical LDPE [7]

Source Document Units, Vapor Transmission Normalized Units, Vapor

Penetrant Rate (g·mil/100 in.2 day) Transmission Rate (g·mm/m2·day)
Oxygen 250–350 98–138
Nitrogen 100–200 39–79
Carbon dioxide 1000–2000 394–787

Table 9.7 Permeation of Solvent Vapors at 24°C Through Dow Chemical LDPE [7]

Source Document Units, Vapor Normalized Units, Vapor

Penetrant Transmission Rate (g·mil/100 in.2 day) Transmission Rate (g·mm/m2·day)
Methyl alcohol 6–8 2.4–3.1
Ethyl alcohol 2–4 0.8–1.6
n-Heptane 300–500 118–197
Ethyl acetate 30–300 11.8–118
Formaldehyde 2–5 0.8–2.0
Tetrachloroethylene 500–750 197–295
Acetone 10–40 3.9–15.8
Benzene (35°C) 600 236
Water 1–1.5 0.39–0.59

Table 9.8 Transport Coefficients of Helium in LDPE Polymer [8]

Permeability Co-
efficient, Source Permeability Coef- Diffusion Solubility
Document Units ficient, Normalized Coeffi- Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ cient (10−7 [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) cm2/s) cm3·MPa]
41 4 1.81 6.4 560 120 0.05
40 10 1.86 5.8 508 140 0.04
49 5 1.83 8.4 735 210 0.04
69 5 1.90 19 1660 210 0.08
78 4 1.82 25 2190 240 0.11
80 10 1.81 25 2190 260 0.09

Table 9.9 Transport Coefficients of Argon in LDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Diffusion Solubility
Document Units Normalized Coeffi- Coefficient
Tempera- Pressure Thickness [10−7·cm3 (STP)/ Units (cm3·mm)/ cient (10−7 [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) cm2/s) cm3·MPa]
42 10 1.90 2.19 192 5.65 0.39
61 10 1.89 5.82 510 14.2 0.41
79 10 1.85 14.2 1243 20.9 0.68
Table 9.10 Transport Coefficients of Nitrogen in LDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
70 10 1.88 5.1 446 20 0.26
80 10 1.82 7.4 648 24 0.31

Table 9.11 Transport Coefficients of Methane in LDPE Polymer [8]

Permeability Permeabil-
Coefficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
41 4 1.85 4.3 376 3.4 1.30
40 10 1.83 3.7 324 4.2 0.90
40 7.5 1.82 4.8 420 3.7 1.30
59 7.5 1.80 13 1138 10 1.20
80 4 1.83 29 2539 23 1.30
80 10 1.91 28 2451 22 1.30
77 7 2.75 32 2801 26 1.20

Table 9.12 Transport Coefficients of Carbon Dioxide in LDPE Polymer [8]

Permeability Coef- Permeabil-

ficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
40 4 1.83 22 27415 6.7 3.30
60 4 1.80 41 29166 19 2.20
76 4 2.16 64 30566 22 2.90

Figure 9.17 Permeability versus reciprocal temperature of methane in medium density polyethylene (MDPE) [8].
9: Polyolefins, Polyvinyls, and Acrylics 167

Figure 9.18 Diffusion versus reciprocal temperature of methane in MDPE [8].

Figure 9.19 Solubility versus reciprocal temperature of methane in MDPE [8].

Table 9.13 Permeation of Carbon Dioxide and Nitrogen Through Exopack® Sclairfilm® LWS-1 and LWS-2
Laminating MDPE Films [10]

Water Oxygen
Film Thickness Permeation Coefficient Permeation Coefficient
Grade (mm) (cm3·mm/m2·day·atm) (cm3·mm/m2·day·atm)
Sclairfilm® LWS-1 0.0508 0.26 132
Sclairfilm LWS-1
®
0.0381 0.27 133
Sclairfilm LWS-2
®
0.0508 0.26 132
Sclairfilm LWS-2
®
0.0381 0.27 133
168 Permeability Properties of Plastics and Elastomers

Table 9.14 Permeability, Diffusion and Solubility Coefficients of Carbon Dioxide in Extruded MDPE at 60°C and
4 MPa [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
61 3.95 1.71 1.58 138 1.09 1.45
61 4.0 1.64 1.60 140 1.10 1.46
60 4.0 1.71 1.54 135 1.01 1.52
60 4.1 1.65 1.51 132 1.14 1.32
60 4.1 1.71 1.61 141 1.03 1.56
60 4.4 1.71 1.67 146 1.14 1.47
60 4.4 1.64 1.57 137 1.24 1.27
60 4.5 1.71 1.69 148 0.99 1.70
60 4.5 1.64 1.60 140 1.15 1.40
60 4.0 1.73 1.60 140 0.97 1.65
60 4.0 1.66 1.63 143 1.03 1.59
60 4.0 1.73 1.62 142 0.99 1.63
61 4.0 1.65 1.66 145 0.98 1.70
61 4.0 1.72 1.66 145 0.93 1.78
62 3.9 1.64 1.67 146 1.00 1.68
62 3.9 1.73 1.68 147 0.99 1.70
61 4.1 1.64 1.68 147 0.94 1.78
61 4.0 1.73 1.61 141 0.99 1.62
61 4.0 1.64 1.60 140 1.06 1.55
Mean value 1.62 1.04 142
Standard deviation 5.0 × 10 –2
8.2 × 10 –2 0.15
Standard deviation % 3% 8% 9%

Table 9.15 Transport Coefficients of Carbon Dioxide in MDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness (10−7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa) (m2·day·atm) (10−7 cm2/s) cm3·MPa]
39 4 1.95 8.1 709 3.7 2.25
61 4 2.03 17 1488 10 1.65
80 4 1.95 29 2539 17 1.80
9: Polyolefins, Polyvinyls, and Acrylics 169

Table 9.16 Transport Coefficients of Methane in MDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
39 10 2.01 1.2 105 1.6 0.78
39 7 1.92 1.5 131 2.1 0.74
60 7 1.99 5 438 4.7 1.10
59 4 1.95 3.3 289 6.5 0.51
80 4 1.91 12 1051 11 1.10

Table 9.17 Transport Coefficients of Argon in MDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
42 10 1.97 1.10 96 3.03 0.36
60 10 1.97 2.17 190 7.95 0.27
79 10 1.92 4.63 405 14 0.33

Table 9.18 Transport Coefficients of Nitrogen in MDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness (10−7 cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa) (m2·day·atm) (10−7 cm2/s) cm3·MPa]
69 10 1.97 2.0 175 11 0.18
79 10 1.93 2.7 236 16 0.18

Table 9.19 Transport Coefficients of Helium in MDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
41 10 1.93 2.8 245 51 0.06
60 8 1.96 6.7 587 65 0.10
78 10 1.95 11 963 120 0.09
Figure 9.20 Permeation of gases versus temperature of high density polyethylene (HDPE) [15].

Table 9.20 Permeability Coefficient* for Pipes Made Table 9.21 Permeation of Gases Through Chevron
of LlyondellBasell Polyolefins HDPE at 20°C [11] Philips Marlex® HDPE

P, Permeability Coeffi- Permeability Coefficient

Permeant gas cienta (cm3/m·bar·day) Permeant gas (cm3·mm/m2·day·atm)
Nitrogen 0.018 Carbon dioxide 136
Air 0.029 Hydrogen 126
Carbon monoxide 0.036 Oxygen 44
Natural gas 0.056 Helium 97
Methane 0.056 Ethane 93
Argon 0.066 Natural gas 44
Oxygen 0.072 Freon 12
®
37
Ethane 0.089 Nitrogen 21
Helium 0.15 Test method: ASTM D1434 [12].
Hydrogen 0.22
Carbon dioxide 0.28
Sulfur dioxide 0.43
a
This permeation coefficient in Table 9.20 is designed for pipe
gas permeation calculations by Eq. (9.1).

Table 9.22 Permeation of Oxygen and Water Through NOVA Chemicals Sclair® HDPE Films

Source Document Units, Normalized Units, Wa- Oxygen Permeability

Sclair® Film Thick- Water Transmission Rate ter Transmission Rate Coefficient (cm3·mm/
Code ness (mm) (g/m2·day) (g·mm/m2·day) m2·day·atm)
15A 0.038 5.4 0.21 91
19A 0.038 3.4 0.13 65
19C 0.038 2.6 0.10 57
19G 0.038 2.8 0.11 62
19H 0.038 6.2 0.24 65
Test method: ASTM E96 and ASTM D3985 [13].
9: Polyolefins, Polyvinyls, and Acrylics 171

Table 9.23 Permeation of Hydrogen Versus Temperature and Pressure Through HDPE [14]

Temperature (°C) −15 25 68 −16 25 67 −18 25 67

Pressure gradient
(kPa) 1724 3447 6895
Source docu- 3.64 1.78 8.69 3.49 1.76 8.54 3.19 1.84 8.45
ment units, per- × 10−10 × 10−9 × 10−9 × 10−10 × 10−9 × 10−9 × 10−10 × 10−9 × 10−9
meability coef-
ficient (cm3·mm/
cm2·kPa·sec)
Normalized units, 31.9 156 761 30.6 154 748 27.9 161 740
permeability coef-
ficient (cm3·mm/
m2·day·atm)
Thickness: 0.030 mm; test method: mass spectrometry and calibrated standard gas leaks; developed by McDonnell Douglas Space
Systems Company Chemistry Laboratory.

Table 9.24 Permeation of Nitrogen Versus Temperature and Pressure Through HDPE [14]

Temperature (°C) −10 25 72 −19 25 69 −17 25 68

Pressure gradient
(kPa) 1724 3447 6895
Source docu- 1.81 1.77 1.98 1.08 1.6 1.46 1.13 1.68 1.71
ment units, per- × 10−11 × 10−10 × 10−9 × 10−11 × 10−10 × 10−9 × 10−11 × 10−10 × 10−9
meability coef-
ficient (cm3·mm/
cm2·kPa·sec)
Normalized units, 1.6 15.5 173 0.95 14.0 128 0.99 14.7 150
permeability coef-
ficient (cm3·mm/
m2·day·atm)
Thickness: 0.030 mm; test method: mass spectrometry and calibrated standard gas leaks; developed by McDonnell Douglas Space
Systems Company Chemistry Laboratory.

Table 9.25 Permeation of Oxygen Versus Temperature and Pressure Through HDPE [14]

Temperature (°C) −16 25 51 −15 25 52

Pressure gradient
(kPa) 1724 3447
Source document 5.75 × 10 −11
5.75 × 10 −10
2.49 × 10 −9
5.91 × 10 −11
5.64 × 10−10 2.03 × 10−9
units, perme-
ability coeffi-
cient (cm3·mm/
cm2·kPa·sec)
Normalized units, 5.0 50.3 218 5.2 49.4 178
permeability coef-
ficient (cm3·mm/
m2·day·atm)
Thickness: 0.030 mm; test method: mass spectrometry and calibrated standard gas leaks; developed by McDonnell Douglas Space
Systems Company Chemistry Laboratory.
172 Permeability Properties of Plastics and Elastomers

Table 9.26 Permeation of Ammonia Versus Temperature and Pressure Through HDPE [14]

Temperature (°C) −15 25 68

Pressure gradient (kPa) 965
Source document units, permeability coefficient 3.71 × 10−10 1.4 × 10−9 7.12 × 10−9
(cm3·mm/cm2·kPa·sec)
Normalized units, permeability coefficient (cm3·mm/m2·day·atm) 32.5 122.6 623
Thickness: 0.030 mm; test method: mass spectrometry and calibrated standard gas leaks; developed by McDonnell Douglas Space
Systems Company Chemistry Laboratory.

Table 9.27 Transport Coefficients of Helium in HDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
40 10 2.11 1.9 166 76 0.03
59 7.5 1.95 4.8 420 45 0.11
79 10 2.11 8.3 727 130 0.06

Table 9.28 Transport Coefficients of Argon in HDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10–7·cm3 (STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
61 10 1.72 0.76 67 4.47 0.17
80 10 1.74 2.06 180 7.77 0.27

Table 9.29 Transport Coefficients of Nitrogen in HDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
69 10 2.08 1.0 88 12 0.09
79 10 2.08 1.6 140 10 0.16

Table 9.30 Transport Coefficients of Methane in HDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
39 7 2.08 0.92 81 1.6 0.57
61 7 1.99 2.6 228 4.6 0.56
77 10 2.05 5.1 446 9.2 0.56
9: Polyolefins, Polyvinyls, and Acrylics 173

Table 9.31 Transport Coefficients of Carbon Dioxide in HDPE Polymer [8]

Permeability Co- Permeabil-

efficient, Source ity Coefficient, Solubility
Document Units Normalized Diffusion Coefficient
Tempera- Pressure Thickness [10−7·cm3(STP)/ Units (cm3·mm)/ Coefficient [cm3(STP)/
ture (°C) (MPa) (mm) cm·s·MPa] (m2·day·atm) (10−7 cm2/s) cm3·MPa]
40 4 2.01 5.5 481 4.0 1.40
60 4 2.09 9.6 840 8.2 1.20
81 4 2.07 19 1663 16 1.20

Figure 9.21 Water vapor transmission rate values of biaxially oriented polypropylene films with different relative
humidity at 23°C [19].

is quite cloudy. In general, the more ethylene • Random copolymer. Food, household chemi-
monomer added, the greater the impact resis- cals, beauty aid products, clear containers, and
tance with correspondingly lower stiffness and hot fill applications.
tensile strength. • Impact copolymers. Automotive, housewares,
film, sheet, profiles, high pressure resistance,
Oriented and multilayered films of PP are also medical trays, and thin-wall parts.
common.
Manufacturers and tradenames: Ineos polypro- Permeation data for PP based plastics is found in
pylene; LyondellBasell Adflex™, Mophen, Hostalen Figs. 9.21–9.24 and Tables 9.32–9.35.
PP; ExxonMobil™ Bicor™, OPPalyte; Dow Chemi-
cal; Flint Hill Resources  π ⋅ de ⋅ L ⋅ p ⋅ t  (9.2)
V = P ⋅ 
Applications and uses:  e

• Homopolymer. Thermoforming, slit film and Where, V, volume of permeating gas [cm3 (STP)];
oriented fibers, high clarity, housewares, sy- P, permeability coefficient [cm3(STP)/m·bar·day]; de,
ringes, and closures. outside diameter of the pipe (mm); L, length of the
174 Permeability Properties of Plastics and Elastomers

Figure 9.22 Water vapor transmission rate values of biaxially oriented polypropylene films from 10–40°C at 50%
relative humidity [19].

Figure 9.23 Oxygen transmission rate values of biaxially oriented polypropylene films measured at different
relative humidity and 23°C [19].

pipe (m); p, partial pressure of the gas in the pipe (bar); monomers to react that gives slightly different iso-
t, time (days); e, wall thickness of the pipe (mm). meric structure. This is shown in Fig. 9.25.
Most of the time, the adding monomer bonds to
the #4 or terminal carbon of the previous butadiene,
9.3 Polybutadiene resulting in a 1,4-addition of the previous butadiene
unit. The new double bond may have either a cis or
1,3-Butadiene is a hydrocarbon molecule that a trans isomer configuration. A smaller fraction of
has two carbon–carbon double bonds. Polybutadi- the time (perhaps 20%), the new monomer bonds to
ene (PB) can be formed from many 1,3-butadiene the #2 carbon of the previous butadiene, resulting in
monomers undergoing free radical polymerization a 1,2-addition of the previous butadiene unit. The
to make a much longer polymer chain molecule. But double bond between the #1 and #2 carbons turns
as discussed in Section 2.7, there many ways for the into a single bond in the previous butadiene unit, and
Figure 9.24 Oxygen transmission rate values of biaxially oriented polypropylene films measured at different
temperatures, at 50% relative humidity [19].

Table 9.32 Permeation of Various Gases Through Ineos Polypropylene [16]

Temperature Source Document Units, Permeability Normalized Units, Permeability

Permeant (°C) Coefficient × 10−10 (cm2/s cm Hg) Coefficient cm3·mm/m2·day·atm
Water 25 5.1 335
Oxygen 30 2.3 151
Carbon dioxide 30 3.5 230
Hydrogen 20 41.0 2692
Nitrogen 30 0.27 18

Table 9.33 Permeability Coefficienta for LlyondellBasell Polyolefins Polypropylene at Different Temperatures [17]

P, Permeability Coefficienta (cm3/m·bar·day)

Permeant Gas 25°C 30°C 40°C 50°C
Air 0.028 0.038 0.072 0.144
Nitrogen 0.017 0.024 0.052 0.104
Oxygen 0.76 0.1 0.204 0.368
Carbon dioxide 0.244 0.336 0.6 1.08
Hydrogen 0.64 0.72 1.12 1.88
Helium 0.7 0.88 1.2 1.76
Argon 0.66 0.84 0.164 0.32
This permeation coefficient in Table 9.33 is designed for pipe gas permeation calculations by Eq. (9.2).
a

Table 9.34 Permeation of Carbon Dioxide Through LlyondellBasell Adflex™ Polypropylene [18]

Source Document Units, Permeability Normalized Units, Permeability

Adflex™ Grade (cm3/100 in.2 day) Coefficient (cm3·mm/m2·day·atm)
Film thickness (mm) 0.025 0.050 0.025 0.050
Q401F 2200 960 865 754
KS089P 2250 1060 884 833
KS353P 5760 2750 2240 2162
176 Permeability Properties of Plastics and Elastomers

Table 9.35 Permeation of Oxygen Through LlyondellBasell Adflex™ Polypropylene [18]

Source Document Units, Permeability Normalized Units, Permeability

Adflex™ Grade (cm3/100 in.2 day) Coefficient (cm3·mm/m2·day·atm)
Film thickness (mm) 0.025 0.050 0.025 0.050
Q401F 100 45 39 35
KS089P 420 240 185 188
KS353P 980 475 377 373

Figure 9.25 Polybutadiene (PB) structural isomers.

the double bond between the #3 and #4 carbons re- 9.4 Polymethyl Pentene
mains intact in a short vinyl side group available for
branching or cross-linking. There are different cata- 4-methylpentene-1 based polyolefin is a light-
lysts available that can result in polymerization either weight, functional polymer that displays a unique
in the cis or the trans configurations. combination of physical properties and characteris-
The CAS number of PB is 9003-29-6. tics due to its distinctive molecular structure, which
Manufacturers and trade names: there are many includes a bulky side chain as shown in Fig. 9.2. PMP
manufacturers. possesses many characteristics inherent in tradition-
Applications and uses: PB is used synergistically al polyolefins such as excellent electrical insulating
as a blend component to improve and differentiate properties and strong hydrolysis resistance. Moreover,
the properties of polyolefins in packaging films or it features low dielectric, superb clarity, transparency,
nonwoven fabrics. Pressurized vessels, pressurized gas permeability, heat and chemical resistance and re-
beverage tubing, seals such as beverage closure lin- lease qualities. Its CAS number is 89-25-8.
ers, architectural seals, and gaskets, compression Manufacturers and trade names: Mit-
packaging films, peel seal, film modification, hot sui TPX™, Honeywell PMP; Chevron Philips
melt and polyolefin modification applications. It is Crystalor—discontinued.
also used in various parts of automobile tires. Its Applications and uses: it can be used for extruded
use in the tread portion of giant truck tires helps to and film products, injection molded, and blow mold-
improve the abrasion, that is, less wearing, and to ed application items, including:
run the tire comparatively cool. In the sidewall of
truck tires, the use of PB rubber helps to improve • paper coatings and baking cartons
fatigue to failure life due to the continuous flexing • release film and release paper
during run. As a result, tires will not blow out in • high frequency films
extreme service conditions. PB rubber is blended • microwave cookware
with Polystyrene to prepare High Impact Polysty-
rene (HIPS). • food packaging such as gas permeable pack-
Permeation data for PB-based plastics is found in ages for fruit and vegetables
Fig. 9.26. • LED molds
9: Polyolefins, Polyvinyls, and Acrylics 177

Figure 9.26 Permeation coefficients of nitrogen and helium versus temperature through PB rubber [20].

Table 9.36 Water Transmission rate at 38°C (100°F) and 100% Relative Humidity of Honeywell Series R PMP
Films [21]

Source Document Units, Vapor Normalized Units, Vapor Transmission

Product Code Transmission Rate (g/100 in.2·day) Rate (g/m2·day)
R100 5.85 91
R1180 0.5 7.8
R1500 3.9 60
R2000 3.0 47
Note: film thickness note specified.

Table 9.37 Gas Permeability of Mitsui TPX™ MX002 PMP [22]

Source Document Units, Normalized Units, Permeability

Gas Conditions Permeability (mol·m/(m2·s·Pa)) Coefficient (cm3·mm/m2·day·atm)
Moisture 40°C, 90% RH 3.20 × 10−13 62,800
Oxygen 23°C 9.40 × 10 −15 1,800
Nitrogen 23°C 2.33 × 10−15 457
Carbon dioxide 23°C 3.29 × 10−14 6,450

Data for polymethyl pentene (PMP) plastics are

found in Tables 9.36 and 9.37.

9.5 Cyclic Olefin Copolymer

Cyclic olefin copolymer (COC) is an amorphous
polyolefin made by reaction of ethylene and norborn-
ene in varying ratios. Its structure is given in Fig. 9.27.
The properties can be customized by changing the Figure 9.27 Chemical structure of cyclic olefin copo-
ratio of the monomers found in the polymer. Being lymers (COCs).
178 Permeability Properties of Plastics and Elastomers

amorphous it is transparent. Other performance ben- Table 9.39 Water Vapor Permeation at 38°C and
efits include: 90% Relative Humidity Through TOPAS Advanced
Polymers TOPAS® COC [24]
• low density
Vapor Trans-
• extremely low water absorption Film Layer Thickness mission
• excellent water vapor barrier properties Layers (mm) Rate (g2/day)
• high rigidity, strength, and hardness PVC/To- 0.060/0.240/0.030 0.14
• variable heat deflection temperature up to pas®/PVDC
170°C PP/Topas®/ 0.030/0.300/0.030 0.23
• very good resistance to acids and alkalis PP
PVC/ 0.035/0.240/0.035 0.28
Manufacturers and trade names: Mitsui Chemical Topas®/PVC
APEL, TOPAS Advanced Polymers, TOPAS®.
PP/Topas®/ 0.030/0.240/0.030 0.28
Applications and uses: TOPAS Advanced
PP
Polymers TOPAS® is used as a core layer in push-
through packaging (PTP), either in five layer co- PP/Topas®/ 0.030/0.190/0.030 0.35
extruded or three layer laminated film structures; PP
Flexible and rigid packaging for food and con- Test method: ASTM F1249.
sumer items; Syringes, vials, and other prefillable
containers.
Data for COC plastics are found in Tables 9.38 9.6 Ethylene–Vinyl Acetate
and 9.39.
Copolymer
Ethylene–vinyl acetate copolymer (EVA) is a co-
polymer of ethylene and vinyl acetate as shown in
Table 9.38 Water Vapor Permeation at 23°C and Fig. 9.28. Its CAS number is 24937-78-8. Resins
85% Relative Humidity Through TOPAS Advanced range in vinyl acetate content from 7.5 to 33 wt%.
Polymers TOPAS® COC [23] Some grades are available with antiblock and slip
additives. DuPont™ Elvax® grades vary by vinyl
Heat Deflection Water Vapor acetate content.
Topas® Temperature Transmission Rate Manufacturers and trade names: DuPont™
Grade (°C) (g·mm/m2·day) Appeel® and Elvax®, Celeanese EVA Performance
8077 75 0.023 Polymers Ateva®, Lanxess Levapren®, Baymond® L
and Levamelt®.
6013 130 0.035
Applications and uses: packaging, cap liners, pal-
6015 130 0.035 let stretch wrapping, bundling, liquid packaging, and
5013 150 0.030 as a sealant in barrier bags for primal and subprimal
6017 170 0.045 cuts of meat, medical packaging.
Data for EVA plastics are found in Figs. 9.29
Test method: DIN53122. and 9.30 and Tables 9.40–9.42.

Figure 9.28 Structure of EVA polymers.

9: Polyolefins, Polyvinyls, and Acrylics 179

Figure 9.29 Permeation of oxygen versus vinyl acetate content through BASF AG Lupolen V EVA [27].

Figure 9.30 Permeation of water vapor versus vinyl acetate content through EVA [26].

Table 9.40 Permeation of Oxygen Through DuPont™ Elvax® EVA [25]

Vinyl Acetate Source Document Units, Gas Normalized units, Permeability

Grade Content (%) Permeability (cm3/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
3120 7.5 450 177
3121 A 7.5 580 228
3128 8.9 500 196
3130 12 400 157
3130 SB 12 570 224
3130 SBZ 12 570 224
3135 X 12 510 200

(Continued )
180 Permeability Properties of Plastics and Elastomers

Table 9.40 Permeation of Oxygen Through DuPont™ Elvax® EVA [25] (cont.)

Vinyl Acetate Source Document Units, Gas Normalized units, Permeability

Grade Content (%) Permeability (cm3/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
3135 SB 12 460 180
3150 15 500 196
3165 18 580 228
3165 SB 18 670 263
3169 18 500 196
3170 18 470 185
3170 SHB 18 535 210
Sample thickness (mm) 0.0254; test method ASTM D3985; material note SB: antiblock additive, SHB: slip additive and high antiblock additive.

Table 9.41 Permeation of Water Vapor Through DuPont™ Elvax® EVA [25]

Vinyl Acetate Source Document Units, Vapor Normalized Units, Vapor

Grade Content (%) Permeability (g/100 in.2 day) Transmission Rate (g·mm/m2·day)
3120 7.5 1.5 0.74
3121 A 7.5 1.5 0.74
3128 8.9 1.6 0.93
3130 12 2.3 1.1
3130 SB 12 2.2 1.1
3130 SBZ 12 2.2 1.1
3135 X 12 2.3 1.1
3135 SB 12 2.4 1.2
3150 15 3.3 1.6
3165 18 4.2 2.1
3165 SB 18 3.6 1.8
3169 18 3.4 1.7
3170 18 3.8 1.9
3170 SHB 18 3.7 1.8
Sample thickness (mm) 0.0254; material note SB: antiblock additive, SHB: slip additive and high antiblock additive; test method ASTM E96.

Table 9.42 Permeation of Carbon Dioxide and 9.7 Ethylene–Vinyl Alcohol

Oxygen Through Blown EVA Film [26]
Copolymer
Carbon
Ethylene–Vinyl Alcohol Copolymer (EVOH) is a
Penetrant dioxide Oxygen
copolymer of ethylene and vinyl alcohol. The struc-
Source document units, gas 11,000 1800 ture is shown in Fig. 9.31 and EVOH has a CAS
permeability (cm3·100 µm/ number of 26221-27-2. These materials are highly
m2·day·atm) crystalline, and are produced with various levels of
Normalized units, perme- 1100 180 ethylene content. See Table 9.43 for a description of
ability coefficient (cm3·mm/ EVAL™ Resins.
m2·day·atm) The predominant product line is Eval Company of
Features: 2.5 blow up ratio; sample thickness (mm): 0.05; vinyl
America (Kuraray) EVAL™. The general classes of
acetate content (%): 12.0; test method: ASTM D1434. the EVAL™ product line are shown in Table 9.43.
9: Polyolefins, Polyvinyls, and Acrylics 181

Figure 9.31 The structure of ethylene–vinyl alcohol copolymer (EVOH).

Table 9.43 EVAL™ Ethylene–Vinyl Alcohol Copolymer (EVOH) Polymer Grade Series [28]

EVAL™ Ethylene
Series Content (mol %) General Characteristics
L series 27 Has the lowest ethylene content of any EVOH, and is suitable as an
ultrahigh-barrier grade in several applications.
F series 32 Offers superior barrier performance and is widely used for automotive,
bottle, film, tube, and pipe applications.
T series 32 Specially developed to obtain good layer distribution in thermo-forming,
and has become the industry standard for multilayer sheet applications.
J series 32 Offers thermoforming results even superior to those of T, and can be used
for unusually deep-draw or sensitive sheet-based applications.
H series 38 Has a balance between high barrier properties and long-term run stabil-
ity. Especially suitable for blown film, special “U” versions exist to allow
improved processing and longer running times even on less sophisticated
machines.
E series 44 Has a higher ethylene content which allows for greater flexibility and even
easier processing. Different versions have been especially designed for
cast and blown film as well as for pipe.
G series 48 Has the highest ethylene content, making it the best candidate for stretch
and shrink film applications.

The films are often heat treated and oriented. These a mixture of PVB, polyvinyl alcohol (PVOH), and
processes can dramatically affect the properties. polyvinyl acetate segments as shown in the figure.
Manufacturers and trade names: Eval Com- The relative amounts of these segments are con-
pany of America (Kuraray) EVAL™, Soarus L.L.C trolled but they are generally randomly distributed
Soarnol®. through the molecular chain. The properties of the
Applications uses: rigid packaging for entrees, polymers can be optimized by controlling the ratios
edible oils, juice, cosmetics, pharmaceuticals, heat- of the three segments.
ing pipe, automotive plastic fuel tanks, packaging Manufacturers and trade names: GlasNovations
for condiments and toothpaste. Flexible packaging: KB®, DuPont™ Butacite®, Solutia Inc. Saflex®,
processed meats, bag-in-box, red meat, cereal, pesti- Sekisui S-Lec, Kuraray TROSIFOL®.
cides, and agrichemicals. Applications and uses: safety glass, architectural
Data for EVOH plastics are found in Figs. 9.32–9.40 glass.
and Tables 9.44–9.74. Data for PVB materials is given in Table 9.75.

9.8 Polyvinyl Butyral 9.9 Polyvinyl Chloride

Polyvinyl butyral (PVB) is considered to be an PVC is a flexible or rigid material that is chemi-
acetal and is formed from the reaction of an alde- cally nonreactive. Its chemical structure is shown in
hyde and alcohol. The structure of PVB is shown in Fig. 9.42. Rigid PVC is easily machined, heat formed,
Fig. 9.41, but it is generally not made in exactly this welded, and even solvent cemented. PVC can also
form. It is made in a way such that the polymer is be machined using standard metal working tools and
Figure 9.32 Permeation of oxygen versus temperature through EVAL™ EVOH films [28].

Figure 9.33 Permeation of oxygen versus temperature at various moisture absorption conditions through EVAL™
EVOH films [28].

Figure 9.34 Permeation of oxygen versus relative humidity at 20°C through EVAL™ EVOH resins [28].
Figure 9.35 Permeation of oxygen versus ethylene content of polymer at 20°C and different relative humidities
through EVAL™ EVOH films [28].

Figure 9.36 Permeation of carbon dioxide versus relative humidity at 20°C through EVAL F and EVAL E series
EVOH [29].

Figure 9.37 Permeation of oxygen versus film thickness at 25°C and 75% relative humidity through Nippon
Gohsei Soarnol® E3808 and ET3803 EVOH [38].
Figure 9.38 Permeation of oxygen versus ethylene content at 20°C through Nippon Gohsei Soarnol® EVOH [39].

Figure 9.39 Permeation of oxygen versus relative humidity at 20°C through Nippon Gohsei Soarnol® EVOH [40].

Figure 9.40 Permeation of oxygen versus temperature through Nippon Gohsei Soarnol® EVOH [41].
9: Polyolefins, Polyvinyls, and Acrylics 185

Table 9.44 Permeation of Oxygen at 20°C and 65% Relative Humidity Through Various EVAL™ EVOH Resin
Grades [28]

Source Document Units, Normalized Units,

Permeability Coefficient Permeability Coefficient
Grade Application (cm3·20 µm/m2·day·atm) (cm3·mm/m2·day·atm)
F101B Bottle, sheet, film 0.4 0.008
T101B Thermoformed sheet 0.5 0.01
H101B Bottle, sheet, film 0.7 0.014
E105B Sheet, film 1.5 0.03
F101A Without lubricant 0.4 0.008
F104B High melt flow rate 0.4 0.008
HU101B Blown film 0.7 0.014
EU105B Blown film 1.5 0.03
E151B Low melt flow rate 1.5 0.03
FP101B Pipe, with antioxidant 0.4 0.008
FP104B Pipe, with antioxidant 0.4 0.008
EP105B Pipe, with antioxidant 1.5 0.03
L101B Ultrahigh barrier 0.2 0.004
J102B Thermoforming 0.6 0.012
ES104B Stretch/shrink film 4 0.08
G156B Stretch/shrink film 3.2 0.064
Method: ASTM D3985.

Table 9.45 The effect of Orientation, Heat Treatment, and Relative Humidity on the Oxygen Transmission Rate
of EVAL™ F Series EVOH Resins [29]

Chill Roll Source Document Units, Normalized Units,

Temperature Heat Permeability Coefficient Permeability Coefficient
(°C) Orientation Treatment (cm3·25 µm/m2·day·atm) (cm3·mm/m2·day·atm)
Relative Humidity 0% RH 100% RH 0% RH 100% RH
50 None None 0.126 40.9 0.00315 1.0225
110 None None 0.118 33.8 0.00295 0.845
50 None 140 0.102 11 0.00255 0.275
50 Uniaxially 3 None 0.118 32.3 0.00295 0.8075
times
50 Uniaxially 3 140 0.094 3.9 0.00235 0.0975
times
50 Biaxially None 0.118 31.5 0.00295 0.7875
3×3
50 Biaxially 140 0.094 2.3 0.00235 0.0575
3×3
186 Permeability Properties of Plastics and Elastomers

Table 9.46 The Effect of Orientation, Heat Treatment,. and Relative Humidity on the Oxygen Transmission Rate
of EVAL™ E Series EVOH Resins [29]

Chill Roll Source Document Units, Normalized Units,

Temperature Heat Permeability Coefficient Permeability Coefficient
(°C) Orientation Treatment (cm3·25 µ/m2·day·atm) (cm3·mm/m2·day·atm)
Relative humidity 0% RH 100% RH 0% RH 100% RH
50 None none 1.18 11.8 0.0295 0.295
110 None none 1.02 9.4 0.0255 0.235
50 None 140 0.94 6.3 0.0235 0.1575
50 Uniaxially 3 none 1.02 10.2 0.0255 0.255
times
50 Uniaxially 3 140 0.94 3.1 0.0235 0.0775
times
50 Biaxially none 1.02 10.2 0.0255 0.255
3×3
50 Biaxially 140 0.94 2.4 0.0235 0.06
3×3

Table 9.47 Permeation of Fluorocarbons Through EVAL™ EVOH [30]

Source Document Units,

Permeability Coefficient Normalized Units, Permeability
(cm3·mil/m2·day·atm) Coefficient (cm3·mm/m2·day·atm)
Eval™ F Eval™ E
Fluorocarbon Temperature (°C) Series Series Eval™ F Series Eval™ E Series
HCFC-22 (R-22) 35 ND* ND*
HCFC-22 (R-22) 50 ND* ND*
HCFC-22 (R-22) 60 1.3 0.3
HCFC-22 (R-22) 65 4.1 0.1
CFC-12 (R-12) 70 0.24 8.0 0.006 0.2
HFC-134a 70 0.56 0.14
(R-134a)

Table 9.48 Permeation of Oxygen Versus Temperature at 0% Relative Humidity Through EVAL™ E Series
EVOH [29]

Temperature (°C) 5 23 35 50
Source document units, permeability 0.259 0.935 1.922 5.33
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.01 0.02 0.05 0.14
coefficient (cm3·mm/m2·day·atm)
9: Polyolefins, Polyvinyls, and Acrylics 187

Table 9.49 Permeation of Oxygen Versus Temperature at 0% Relative Humidity Through EVAL™ G Series
EVOH [29]

Temperature (°C) 5 23 35 50
Source document units, permeability 1.034 1.8 2.7 6.11
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.03 0.05 0.07 0.16
coefficient (cm3·mm/m2·day·atm)

Table 9.50 Permeation of Oxygen Versus Temperature at 0% Relative Humidity Through EVAL™ H Series
EVOH [29]

Temperature (°C) 5 23 35 50
Source document units, permeability 0.09 0.395 0.94 2.6
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.0024 0.01 0.02 0.07
coefficient (cm3·mm/m2·day·atm)

Table 9.51 Permeation of Oxygen Versus Temperature at 0% Relative Humidity Through EVAL™ K Series
EVOH [29]

Temperature (°C) 5 23 35 50
Source document units, permeability 0.09 0.395 0.94 2.6
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.0024 0.01 0.02 0.07
coefficient (cm3·mm/m2·day·atm)

Table 9.52 Permeation of Oxygen Versus Temperature at 0% Relative Humidity Through EVAL™ L Series
EVOH [29]

Temperature (°C) 5 23 35 50
Source document units, permeability 0.022 0.095 0.231 0.637
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.00039 0.0024 0.01 0.02
coefficient (cm3·mm/m2·day·atm)

Table 9.53 Permeation of Oxygen Versus Temperature at 0% Relative Humidity Through EVAL™ F Series
EVOH [29]

Temperature (°C) 5 23 35 50
Source document units, permeability 0.045 0.2 0.48 1.34
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability coeffi- 0.0012 0.01 0.01 0.03
cient (cm3·mm/m2·day·atm)
188 Permeability Properties of Plastics and Elastomers

Table 9.54 Permeation of Several Gasses at 0% Relative Humidity Through Various EVAL™ EVOH Grades [28]

Source Document Units, Permeability Normalized Units, Permeability

Coefficient (cm3·20 µm/m2·day·atm) Coefficient (cm3·mm/m2·day·atm)
Temperature Eval™ Eval™ Eval™ Eval™ Eval™ Eval™
Permeant (°C) F101B H101B H105B F101B H101B H105B
Nitrogen 25 0.017 0.13 0.00034 0.0026
Oxygen 25 0.27 1.23 0.0054 0.0246
Carbon 25 0.81 7.1 0.0162 0.142
dioxide
Helium 25 160 410 3.2 8.2
Argon 35 1.6 0.032
Argon 50 0.5 3.5 7.0 0.01 0.07 0.14
Krypton 50 0.4 1.0 1.8 0.008 0.02 0.036

Table 9.55 Permeation of Carbon Dioxide, Nitrogen, and Helium at 0% Relative Humidity and Different
Temperatures Through EVAL™ E Series EVOH [29]

Penetrant Carbon Dioxide Nitrogen Helium

Temperature (°C) 5 23 35 23 35 5 23 35
Source document units, permeability 0.87 3.32 7.72 0.124 0.232 102.3 368.9 551.8
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.02 0.08 0.2 0.0031 0.01 2.6 9.37 14.02
coefficient (cm3·mm/m2·day·atm)

Table 9.56 Permeation of Carbon Dioxide, Nitrogen, and Helium at 0% Relative Humidity and Different
Temperatures Through EVAL™ F Series EVOH [29]

Penetrant Carbon Dioxide Nitrogen Helium

Temperature (°C) 5 23 35 23 35 5 23 35
Source document units, permeability 0.155 0.496 1.023 0.015 0.031 41.8 144.1 212.3
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.0039 0.01 0.03 0.0004 0.0008 1.06 3.66 5.39
coefficient (cm3·mm/m2·day·atm)

Table 9.57 Permeation of Carbon Dioxide, Nitrogen, and Helium at 0% Relative Humidity and Different
Temperatures Through EVAL™ H Series EVOH [29]

Penetrant Carbon Dioxide Nitrogen Helium

Temperature (°C) 5 23 35 23 35 5 23 35
Source document units, permeability 0.263 1.04 3.32 0.062 0.124 71.3 257.3 381.3
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.01 0.03 0.08 0.0016 0.0031 1.81 6.54 9.37
coefficient (cm3·mm/m2·day·atm)
9: Polyolefins, Polyvinyls, and Acrylics 189

Table 9.58 Permeation of Oxygen Versus Relative Humidity Through EVAL™ EF-XL Biaxially Oriented EVOH
Film [31]

Temperature (°C) 35 20 20 20
Relative Humidity (%) 0 65 85 100
Test method JIS Z1707 ASTM D3985
Source document Units permeability 0.03 0.02 0.07 0.39
coefficient (cm3·mil/100 in.2·day)
Normalized units, permeability 0.01 0.01 0.03 0.15
coefficient (cm3·mm/m2·day·atm)
Sample thickness (mm) 0.015.

Table 9.59 Permeation of Oxygen Versus Relative Humidity at 20°C Through EVAL™ EF-XL, EVAL™ EF-F,
and EF-E Series EVOH Film [32]

Eval ™ Grade EF-XL EF-F EF-E EF-XL EF-F EF-E EF-XL EF-F EF-E EF-XL EF-F EF-E
Relative humidity (%) 0 65 85 100
Source document 0.02 0.02 0.16 0.01 0.02 0.08 0.04 0.08 0.17 0.23 1.0 0.52
units, perme-
ability coefficient
(cm3·mil/100 in.2·day)
Normalized perme- 0.01 0.01 0.06 0.004 0.01 0.03 0.02 0.03 0.07 0.09 0.39 0.2
ability coefficient
(cm3·mm/m2·day·atm)

Table 9.60 Oxygen Permeability at 20°C and 0% RH Versus Orientation and Heat Treatment Through
EVAL™-E Series EVOH [29]

Chill Roll Temperature (°C) 50 110 50 50 50 50 50

Heat treatment (°C) None None 140 None 140 None 140
Orientation None None None Uniaxially Uniaxially Biaxially Biaxially
(3 times) (3 times) (3×3) (3×3)
Source document units, 1.18 1.02 0.94 1.02 0.94 1.02 0.94
permeability coefficient
(cm3·25 µm/m2·day·atm)
Normalized units, 0.03 0.026 0.024 0.028 0.024 0.028 0.024
permeability coefficient
(cm3·mm/m2·day·atm)

Table 9.61 Oxygen Permeability at 20°C and 100% RH Versus Orientation and Heat Treatment Through
EVAL™-E Series EVOH [29]

Chill Roll Temperature (°C) 50 110 50 50 50 50 50

Heat treatment (°C) None None 140 None 140 None 140
Orientation None None None Uniaxially Uniaxially Biaxially Biaxially
(3 times) (3 times) (3×3) (3×3)
Source document units, permeability 11.8 9.4 6.3 10.2 3.1 10.2 2.4
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.299 0.24 0.16 0.28 0.079 0.28 0.06
coefficient (cm3·mm/m2·day·atm)
190 Permeability Properties of Plastics and Elastomers

Table 9.62 Oxygen Permeability at 20°C and 0% RH Versus Orientation And Heat Treatment Through
EVAL™-F Series EVOH [29

Chill Roll Temperature (°C) 50 110 50 50 50 50 50

Heat treatment (°C) None None 140 None 140 None 140
Orientation None None None Uniaxially Uniaxially Biaxially Biaxially
(3 times) (3 times) (3×3) (3×3)
Source document units, permeability 0.008 0.0076 0.0066 0.0076 0.0006 0.0076 0.0061
coefficient (cm3·25 µm/m2·day·atm)
Normalized units, permeability 0.126 0.118 0.102 0.118 0.094 0.118 0.094
coefficient (cm3·mm/m2·day·atm)

Table 9.63 Oxygen Permeability at 20°C and 100% RH Versus Orientation And Heat Treatment Through
EVAL™-F Series EVOH [29]

Chill Roll Temperature (°C) 50 110 50 50 50 50 50

Heat treatment (°C) None None 140 None 140 None 140
Orientation None None None Uniaxially Uniaxially Biaxially Biaxially
(3 times) (3 times) (3×3) (3×3)
Source document units, 40.9 33.8 11 32.3 3.9 31.5 2.3
permeability coefficient
(cm3·25 µm/m2·day·atm)
Normalized units, permeability 1.02 0.87 0.28 0.83 0.1 0.79 0.06
coefficient (cm3·mm/m2·day·atm)

Table 9.64 Organic Solvents at 20°C Through EVAL™ EF-E, EVAL™ EF-F, and EVAL™ EF-XL Series EVOH
Film [32]

Grade EF-F EF-E EF-XL EF-F EF-E EF-XL EF-F EF-E EF-XL
Penetrant Chloroform Xylene Kerosene
Source document units, 0.1 0.16 0.006 0.054 0.074 0.016 >0.001 0.0025 0.001
vapor transmission rate
(g·mil/100 in.2·day)
Normalized vapor trans- 0.04 0.06 0.0024 0.02 0.03 0.01 >0.0004 0.00098 0.0004
mission rate (g·mm/m2·day)

Table 9.65 Organic Solvents at 20°C and 65% Relative Humidity Through Biaxially Oriented EVAL™ EF-XL
Series EVOH Film [32]

Methyl Ethyl
Penetrant Chloroform Xylene Ketone Kerosene
Source document units, vapor 0.01 0.03 0.02 <0.003
transmission rate (g/100 in.2·day)
Normalized vapor transmission 0.002 0.007 0.005 <0.0007
rate (g·mm/m2·day)
Sample thickness (mm) 0.015.
9: Polyolefins, Polyvinyls, and Acrylics 191

Table 9.66 Organic Solvents at 20°C and 65% Relative Humidity Through EVAL™ E Series EVOH Film [32]

Methyl Ethyl
Penetrant Chloroform Xylene Ketone Kerosene
Sample thickness (mm) 0.02 0.032 0.02 0.032 0.02 0.032 0.02 0.032
Source document units, vapor 0.2 0.06 0.09 0.04 0.31 0.03 <0.003 <0.003
transmission rate (g/100 in.2·day)
Normalized, vapor transmission 0.06 0.03 0.03 0.02 0.12 0.01 <0.001 <0.002
rate (g·mm/m2·day)

Table 9.67 Organic Solvents at 20°C and 65% Relative Humidity Through EVAL™ F Series EVOH Film [32]

Methyl Ethyl
Penetrant Chloroform Xylene Ketone Kerosene
Sample thickness (mm) 0.02 0.032 0.02 0.032 0.02 0.032 0.02 0.032
Source document, vapor 0.13 0.3 0.07 <0.003 0.25 0.02 <0.003 <0.003
transmission rate (g/100 in.2·day)
Normalized, vapor transmission 0.04 0.2 0.02 <0.002 0.08 0.01 <0.001 <0.002
rate (g·mm/m2·day)

Table 9.68 Permeation of Water Vapor at 40°C and 90% Relative Humidity Through EVAL™ EF-XL, EVAL™
EF-F, and EVAL™ EF-E Series EVOH Film [31]

Grade EVAL™ EF-XL EVAL™ EF-F EVAL™ EF-E

Sample thickness (mm) 0.015 0.015 0.02
Source document, vapor 3 6 2
transmission rate (g/100 in.2·day)
Normalized, vapor transmission 1.2 2.4 0.8
rate (g·mm/m2·day)

Table 9.69 Permeation of Water Vapor at 40°C and 90% Relative Humidity Through EVAL™ L, EVAL™ F,
EVAL™ H, EVAL™ K, EVAL™ E, and EVAL™ G Series EVOH [29]

Grade EVAL™ L EVAL™ F EVAL™ H EVAL™ K EVAL™ E EVAL™ G

Source document, vapor trans- 124 58.9 32.6 32.6 21.7 21.7
mission rate (g·25 µm/m2·day)
Normalized, vapor transmission 3.2 1.5 0.8 0.8 0.6 0.6
rate (g·mm/m2·day)
Test method JIS Z0208.

Table 9.70 Permeation of d-Limonene at 20°C and 65% Relative Humidity Through EVAL™ EVOH [33]

Material Grade EVAL™ SERIES F EVAL™ SERIES E EVAL™ 5% EVAL™ 7%

Source document vapor 0.002 0.003 98 113.5
permeability (g·mil/100 in.2·day)
Normalized Vapor Permeability 0.00098 0.0015 48 55.6
(g mm/m2-day)
192 Permeability Properties of Plastics and Elastomers

Table 9.71 Permeation of Various Gases at 20°C Through Nippon Gohse Soarnol® EVOH [34]

Ethylene Carbon
Product Grades Content (mol %) Nitrogen Oxygen Dioxide Helium Hydrogen
Source document units (cm ·20 µm/m ·day·atm)
3 2

D2908a, DT2903 29 0.018 0.23 0.49 110 27

DC3212a, DC3203F 32 0.024 0.3 0.62 120 32
E3808 , ET3803
a
38 0.041 0.53 1.3 180
A4412 , AT4406 , AT4403
a a
44 0.1 1.2 4.4 320 195
Normalized units (cm ·mm/m ·day·atm)
3 2

D2908 , DT2903
a
29 0.00036 0.0046 0.0098 2.2 0.54
DC3212 , DC3203F
a
32 0.00048 0.006 0.0124 2.4 0.64
E3808 , ET3803
a
38 0.00082 0.0106 0.026 3.6
A4412 , AT4406 , AT4403
a a
44 0.002 0.024 0.088 6.4 3.9
Cast film, others blown film.
a

Table 9.72 Water Vapor Permeation Rate at 40°C and 95% Relative Humidity Through Nippon Gohse Soarnol®
EVOH [35]

Source Document Source Document

Ethylene Units, Permeation Rate Units, Permeation Rate
Product Grades Content (mol %) (g·30 µm/m2 day) (g·mm/m2·day)
D2908a, DT2903 29 37–70 11–21
DC3212 , DC3203F
a
32 32–58 10–17
E3808 , ET3803
a
38 23–35 7–11
A4412 , AT4406 , AT4403
a a
44 12–25 3.6–7.5
Film thickness: 0.03 mm
a
Cast films, others blown film.

Table 9.73 Liquid Permeation Rate of Chloroform and Kerosene at 20°C Through Nippon Gohse Soarnol®
EVOH [36]

Source Document Source Document

Units, Permeation Rate Units, Permeation Rate
Ethylene
(mg·20 µm/cm2·day) (g·mm/m2·day)
content
Product Grades (mol %) Chloroform Kerosene Chloroform Kerosene
DC3212 , DC3203F
a
32 0.2 <0.005 0.0124 <0.001
A4412 , AT4406 , AT4403
a a
44 0.31 <0.005 0 <0.001
a
Cast films, others blown film.

finished to close tolerances and finishes without great There are three broad classifications for rigid PVC
difficulty. PVC resins are normally mixed with other compounds: Type II, CPVC, and I. Type II differs
additives such as impact modifiers and stabilizers, from Type I due to greater impact values, but lower
providing hundreds of PVC based materials with a chemical resistance. CPVC has greater high tem-
variety of engineering properties. perature resistance. These materials are considered
9: Polyolefins, Polyvinyls, and Acrylics 193

Table 9.74 Liquid Permeation Rate of Chlorofluorocarbon R-22 at 30 and 50°C Through Nippon Gohse
Soarnol® EVOH [37]

Source Document Units, Source Document Units,

Ethylene
Permeation Rate (g·100 µm/m2·day) Permeation Rate (g·mm/m2·day)
Content
Product Grades (mol %) 30°C 50°C 30°C 50°C
D2908a, DT2903 29 4.6 8.2 0.46 0.82
DC3212 , DC3203F
a
32 7.5 14.1 0.75 1.41
E3808 , ET3803
a
38 13.5 22.1 1.35 2.21
A4412 , AT4406 ,
a a
44 18.5 27.8 1.85 2.78
AT4403
a
Cast films, others blown film.

Figure 9.41 Structure of polyvinyl butyral (PVB).

Table 9.75 Permeation of Gases at 25°C Through PVB Membranes [42]

Source Document Units, Normalized Units, Permeability

Permeant gas Permeability Coefficient (Barrer) Coefficient (cm3·mm/m2·day·atm)
Oxygen 0.771 50.6
Argon 0.463 30.4
Nitrogen 0.133 7.4

Applications and uses: building siding, fence, and

packaging are major markets for PVC. Rigid grades
are blown into bottles and made into sheets for ther-
moforming boxes and blister packs. Flexible PVC
compounds are used in food packaging applications
because of their strength, transparency, process-
Figure 9.42 Structure of polyvinyl chloride (PVC). ability, and low raw material cost. PVC film can be
used in Marine/Boat Windows, Recreational Vehicle
“unplasticized,” because they are less flexible than Windows, Tents and Awning Windows, Industrial
the plasticized formulations. PVC has a broad range curtains/Enclosures, Spray Booths, Rack Covers,
of applications, from high volume construction re- Weld Screens and Partitions, Clean Rooms, Golf
lated products to simple electric wire insulation and Cart Covers, Binder Covers, Tags and Sign Holders,
coatings. Menus, Apparel and Clothing, Packaging, Bags.
Manufacturing and trade names: Polyone Geon™, Data for PVC plastics is found in Figs. 9.43–9.45
Fiberloc™, VPI LLC Mirrex®. and Tables 9.76 and 9.77.
Figure 9.43 Permeation of carbon dioxide and hydrogen versus temperature through Polyone Geon™ 101-EP-
100 PVC film with varying levels of diethylhexyl phthalate plasticizer [44].

Figure 9.44 Permeation of oxygen versus temperature through PVC film [45].

Figure 9.45 Permeation of oxygen versus plasticizer level and temperature through PVC film [43].
9: Polyolefins, Polyvinyls, and Acrylics 195

Table 9.76 Permeation of Water Vapor at 38°C and 90% Relative Humidity Through VPI Mirrex® 1025 PVC [43]

Source Document, Vapor Trans- Normalized Units, Vapor Transmis-

Film thickness (mm) mission Rate (g·mm/100 in.2 day) sion Rate (g·mm/m2·day)
0.190 0.0608 0.94
0.254 0.0610 0.95
0.305 0.0610 0.95
Test method: ASTM F372.

Table 9.77 Permeation of Oxygen at 23°C and 100% Relative Humidity Through VPI Mirrex® PVC

Source Document, Permeability Normalized Units, Permeability

Film thickness (mm) Coefficient (cm3·mm/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
0.190 0.304 4.7
0.254 0.305 4.7
0.305 0.305 4.7
Test method: Mocon Oxtran.

9.10 Polyvinyl Alcohol • nontoxic

• high tensile strength, flexibility
PVOH (PVA, or sometimes PVAL) is a water-
soluble polymer. Its structure is shown in the middle • high oxygen and aroma barrier.
of Fig. 9.41.
Polyvinyl alcohol has: Manufacturers and trade names: Kurray POVAL®,
Wacker Chemie AG POLYVIOL® Solutions, Sekisui
• excellent film forming, emulsifying, and adhe- Chemical Co., Ltd.
sive properties Applications and uses: water soluble packaging
such as dishwasher tabs, carbon dioxide barrier in
• resistance to oil, grease, and solvent plastic bottles, chemical resistant gloves, 3D printing.
• odorless Data for PVOH plastics is found in Figs. 9.46–9.49.

Figure 9.46 Water vapor transmission rate of the biaxially oriented PVOH films with different RH at 23°C [19].
Figure 9.47 Water vapor transmission rate of biaxially oriented PVA films from 10–40°C at 50% RH [19].

Figure 9.48 Oxygen transmission rate of the biaxially oriented PVA films measured at different RH and 23°C [19].

Figure 9.49 Oxygen transmission rate of the biaxially oriented PVA films measured at different temperature, ca.
50% RH [19].
9: Polyolefins, Polyvinyls, and Acrylics 197

that set the products apart from others. First it is opti-

cally clear and colorless. It has a light transmission
of 92%. The 4% reflection loss at each surface in un-
avoidable. Second its surface is extremely hard. They
are also highly weather resistant. Polymethyl meth-
Figure 9.50 Structure of PVDC homopolymer. acrylate has a CAS Number of 9011-14-7.
Acrylic resins are available as homopolymer (pri-
marily Polymethyl methacrylate), copolymer, and
9.11 Polyvinylidene Chloride terpolymer.
Polyvinylidene Chloride (PVDC) resin, the structure Applications and uses: optical parts, display items,
of which is shown in Fig. 9.50, is usually a copolymer of tube and profile extrusion, automotive rear lights and
vinylidene chloride with vinyl chloride or other mono- dashboard lenses, extruded sheet, copying equipment
mers. Dow Plastics vinyl chloride and vinylidene chlo- and lighting diffusers, UV protective films for exte-
ride, Saran™, is usually supplied as a white, free flow- rior laminates.
ing powder. PVDC has a CAS number of 9002-85-1. Manufacturers and trade names: Lucite Inter-
Manufacturers and trade names: Dow Saran™. national, Lucite Diakon and Perspex®, Evonik In-
Applications and uses: monolayer films (Saran™) dustries LLC Plexiglas®, Acrylite®, Europlex® and
for food wrap and medical packaging, coextruded Rohaglas®, Arkema Oroglas, Rowland Technologies,
films and sheet structures as a barrier layer in medi- Inc. SolaTuf®, Mitsubishi Rayon Co., Ltd Shinkolite®,
cal, and packaging including fresh red meats, cheese, Altuglas International Plexiglas; Novacor.
and sausages. Coatings are applied to containers to Data for polyacrylic-based plastics is found in
prevent gas transmission. Figs. 9.55 and 9.56 and Tables 9.84 and 9.85.
Data for PVDC plastics is found in Figures 9.51–9.53
and Tables 9.78–9.83.
9.13 Acrylonitrile–Methyl Acrylate
Copolymer
9.12 Polyacrylics
Acrylonitrile–methyl acrylate copolymer (AMA) is
While a large number of acrylic polymers are a copolymer of acrylonitrile and methyl acrylate. The
manufactured, polymethyl methacrylate (PMMA) is generalized structure of AMA is shown in Fig. 9.57.
by far the most common. The structure of PMMA It is a mixture of the acrylonitrile group and methyl
is shown in Fig. 9.54. Nearly everyone has heard of group, with the ratio of the two groups affecting the
Plexiglas®. PMMA has two very distinct properties properties. AMA has a CAS number of 24968-79-4.

Figure 9.51 Oxygen transmission rate at 20°C versus relative humidity for Dow Saranex™ PVDC [47].
198 Permeability Properties of Plastics and Elastomers

Figure 9.52 Permeation of hydrogen sulfide versus temperature through Dow Saran™ PVDC [48].

Figure 9.53 Permeation of water oxygen, carbon dioxide, and nitrogen versus temperature through PVDC [49].

Table 9.78 Permeation of Oxygen at 23°C and 75% Relative Humidity Through Dow Saran™ Films [46]

Saran™ Thickness Source Document Units, Permeability Normalized Units, Permeability

Grade (mm) Coefficient (cm3·mil/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
469 0.10 0.04
516 0.10 0.04
525 0.10 0.04
MA 119 0.08 0.03
MA 123 0.08 0.03
(Continued)
9: Polyolefins, Polyvinyls, and Acrylics 199

Table 9.78 Permeation of Oxygen at 23°C and 75% Relative Humidity Through Dow Saran™ Films [46] (cont.)

Saran™ Thickness Source Document Units, Permeability Normalized Units, Permeability

Grade (mm) Coefficient (cm3·mil/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
MA 134 0.08 0.03
313 1.2 0.47
867 1.1 0.43
F239 0.01375 0.61 0.013
F239 0.025 0.35 0.0138
F278 0.01375 0.35 0.0075
F278 0.025 0.20 0.0079
F310 0.01375 1.5 0.032
F310 0.025 0.83 0.033
F271 0.01375 0.7 0.0149
F271 0.025 0.35 0.0138
F279 0.01375 0.35 0.0074
F279 0.025 0.20 0.00786
F281 0.01375 0.28 0.0059
F281 0.025 0.15 0.0059
Test method: ASTM D1434.

Table 9.79 Permeation of Oxygen at 23°C and 50% Relative Humidity Through Dow Saranex™ Films [46]

Source Document Units, Normalized Units,

Permeability Coefficient Permeability Coefficient
Saranex™ Grade Thickness (mm) (cm3·mil/100 in.2·day·atm) (cm3·mm/m2·day·atm)
451 0.038 0.50 0.296
450 0.025 0.85 0.33
23P 0.051 0.75 0.612
Test method: ASTM D1434.

Table 9.80 Permeation of Gases Through Dow Saranex™ 21 Films [46]

Source Units, Normalized Units,

Temperature Relative Permeability Coefficient Permeability Coefficient
Permeant (°C) Humidity (%) (cm3/m2·day·atm) (cm3·mm/m2·day·atm)
Carbon dioxide 23 10 21.7 0.95
Nitrogen 23 10 1.55 0.07
Oxygen 22 4 13 0.57
Air 23 10 1.6 0.07
Thickness: 0.044 mm; test method: ASTM D1434.
200 Permeability Properties of Plastics and Elastomers

Table 9.81 Permeation of Water Vapor at 38°C and 90% Relative Humidity Through Dow Saranex™ Films [46]

Saran™ Thickness Source Document Units, Vapor Normalized Units, Vapor Trans-
Grade (mm) Transmission Rate (g/100 in.2·day) mission Rate (g·mm/m2·day)
451 0.038 0.33 0.194
450 0.025 0.35 0.140
553 0.076 0.33 0.194
23P 0.051 0.25 0.199
Test method: ASTM E96.

Table 9.82 Permeation of Water Vapor at 38°C and 90% Relative Humidity Through Dow Saran™ Films [46]

Saran™ Thickness Source Document Units, Vapor Trans- Normalized Units, Vapor Trans-
Grade (mm) mission Rate (g·mil/100 in.2 day) mission Rate (g·mm/m2·day)
469 0.13 0.06
516 0.13 0.06
525 0.13 0.06
MA 119 0.05 0.025
MA 123 0.05 0.025
MA 134 0.05 0.025
313 0.27 0.13
867 0.20 0.10
F239 0.01375 0.76 0.255
F239 0.025 0.38 0.228
F278 0.01375 0.43 0.140
F278 0.025 0.21 0.126
F310 0.01375 2.8 0.913
F310 0.025 1.3 0.786
F271 0.01375 0.6 0.197
F271 0.025 0.3 0.183
F279 0.01375 0.43 0.140
F279 0.025 0.21 0.126
F281 0.01375 0.41 0.134
F281 0.025 0.20 0.118
Test method: ASTM E96.

Table 9.83 Permeation of Gases at 23°C and 90% Relative Humidity Through Dow Saran™ Films [46]

Source Document Units, Permeability Normalized Units, Permeability

Permeant Gas Coefficient (cm3·mil/100 in.2·day·atm) Coefficient (cm3·mm/m2·day·atm)
Oxygen 0.17 0.00425
Nitrogen 0.04 0.001
Carbon dioxide 0.25 0.00625
Air 0.07 0.00175
Thickness: 0.025 mm; test method: ASTM D1434, ASTM F1249.
9: Polyolefins, Polyvinyls, and Acrylics 201

Figure 9.54 Structure of PMMA.

Figure 9.55 Permeation of hydrogen and argon versus temperature through polyethyl methacrylate [51].

Figure 9.56 Permeation of carbon dioxide and oxygen versus temperature through polymethyl methacrylate [20].
202 Permeability Properties of Plastics and Elastomers

Table 9.84 Permeation of Oxygen, Nitrogen, and Carbon Dioxide at 25°C Through Lucite Diakon® Polymethyl
Methacrylate [50]

Source Document Units, Permeability Normalized Units, Permeability

Permeant Coefficient [cm3 (STP)·25 µm/m2·day·atm] Coefficient (cm3·mm/m2·day·atm)
Nitrogen 60 1.5
Oxygen 230 5.8
Carbon dioxide 1700 43
Film thickness: 25 µm.

Table 9.85 Permeation of Water Vapor at 25°C and 75% Relative Humidity Through Lucite Diakon® Polymethyl
Methacrylate [50]

Source Document Units, Vapor Transfer Rate Normalized Permeability Units, Vapor Transfer
(g·25 µm/m2·day) Rate (g·mm/m2·day)
68 1.7
Film thickness: 25 µm.

Manufacturers and trade names: INEOS Barex®.

Applications include:
• Food packaging. Processed meats, fish, cheese,
spices, sauces, extracts, and juice concentrates.
• Medical packaging. Pharmaceutical, transder-
mal patches.
• Personal care. Cosmetic packs, mouth-wash,
perfume.
Figure 9.57 Structure of AMA segments.
Data for AMA based plastics is found in Figs. 9.58
and 9.59 and Tables 9.86 and 9.87.

Figure 9.58 Permeation of carbon dioxide and oxygen versus relative humidity through acrylonitrile–methyl ac-
rylate copolymer (AMA) [53].
9: Polyolefins, Polyvinyls, and Acrylics 203

Figure 9.59 Permeation of oxygen versus temperature through AMA [54].

Table 9.86 Permeation of Gases at 73°F (23°C) and 100% Relative Humidity Through INEOS Barex® AMA [52]

Source Document Units, Permeability Normalized Units, Permeability

Grade/Permeant Coefficient (cm3·mil/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
Barex® 210 extrusion grade
Oxygen 0.8 0.3
Nitrogen 0.2 0.08
Carbon dioxide 1.2 0.45
Barex 210 film grade
®

Oxygen 0.8 0.3

Nitrogen 0.2 0.08
Carbon dioxide 1.2 0.45
Barex 214 calendar grade
®

Oxygen 1.2 0.45

Nitrogen 0.3 0.12
Carbon dioxide 1.4 0.52
Barex 218 extrusion grade impact modified
®

Oxygen 1.6 0.6

Nitrogen 0.4 0.16
Carbon dioxide 1.6 0.6
Test method: ASTM D3985.
204 Permeability Properties of Plastics and Elastomers

Table 9.87 Permeation of Water Vapor at 100°F (38°C) and 90% Relative Humidity Through INEOS Barex®
AMA (per ASTM F1249-90) [53]

Source Document Units,

Vapor Transmission Rate Normalized Units, Vapor
Grade (g·mil/100 in.2 day·atm) Transmission Rate (g·mm/m2·day)
Barex® 210 extrusion grade 5.0 2.0
Barex® 210 film grade 5.0 2.0
Barex® 214 calendar grade 6.3 2.5
Barex 218 extrusion grade
®
7.5 3.0
impact modified

9.14 Ionomers • chemical resistance

• transparency/clarity
An ionomer is a polymer that comprises repeat
units of both electrically neutral repeating units and a • melt strength
fraction of ionized units. Two types are discussed in • direct adhesion of epoxy and polyurethane fin-
the following sections. ishes, to metal, glass, and natural fibers by heat
lamination.
Manufacturers and trade names: DuPont™
9.14.1 Ionomer—Ethylene Acrylic Surlyn® and Bexloy® (ethylene–methacrylic acid);
Acid Copolymer Exxon Iotek™ (ethylene–acrylic acid); Goodrich
Hycar® (butadiene–acrylic acid)-discontinued; Dow
Starting with selected various grades of copolymers
Amplify™ (Ethylene-acrylic acid).
such as ethylene/methacrylic acid, manufacturers add
Applications and uses: Packaging films and seal-
zinc, sodium, lithium, or other metal salts. Acid neu-
ants, glass coatings, and abrasion resistant surfaces
tralization (for instance of the methacrylic acid in an
(particularly golf ball covers).
ethylene methacrylic acid copolymer) results in the
Data for ethylene acrylic acid copolymer (EAA)
formation of ion clusters (hence the general term,
ionomers is found in Tables 9.88–9.91.
“ionomer”) within the resulting polymer matrix. The
chemical structure of this process is shown in Fig. 9.60.
The ionomer resins incorporate many of the per- 9.14.2 Ionomer—Perfluorosulfonic
formance features of the original ethylene based co-
polymers, such as chemical resistance, melting range,
acid
density, and basic processing characteristics. However Two types of fluoroionomers are common:
with the alteration forming the ionomer resin, the per-
formance is significantly enhanced in such areas as: • copolymer of tetrafluoroethylene and sulfonyl
fluoride vinyl ether (SFVE)
• low temperature impact toughness • copolymer of tetrafluoroethylene and Perfluoro-
• abrasion/scuff resistant sulfonic acid (PFSA) CAS number 66796-30-3

Figure 9.60 Structure of ethylene acrylic acid copolymer (EAA) ionomers.

9: Polyolefins, Polyvinyls, and Acrylics 205

Table 9.88 Permeation of Oxygen Through DuPont™ Surlyn® Zinc Ion Type Ionomer Film [55]

Source Document Units, Permeability Normalized Units, Permeability

Grade Coefficient (cm3/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
1650 220 174
1652 180 142
1702 175 138
1705 170 134
F1706 185 146
F1801 215 170
F1855 295 233
Blown Film, Thickness (mm): 0.051.

Table 9.89 Permeation of Oxygen Through DuPont™ Surlyn® Sodium Ion Type Ionomer Film [54]

Source Document Units, Permeability Normalized Units, Permeability

Grade Coefficient (cm3/100 in.2 day·atm) Coefficient (cm3·mm/m2·day·atm)
1601 265 209
1603 190 150
F1605 200 158
1707 165 130
F1856 290 229
Blown Film, Thickness (mm): 0.051.

Table 9.90 Permeation of Water Vapor Through DuPont™ Surlyn® Sodium Ion Type Ionomer Film [54]

Source Document Units, Vapor Normalized Units, Vapor

Grade Transmission Rate (g/day·100 in2) Transmission Rate (g·mm/m2·day)
1601 0.8 0.63
1603 0.65 0.51
F1605 0.8 0.63
1707 0.8 0.63
F1856 1.2 0.95
Blown Film, Thickness (mm): 0.051.

Table 9.91 Permeation of Water Vapor Through DuPont™ Surlyn® Zinc Ion Type Ionomer Film [54]

Source Document Units, Vapor Normalized Units, Vapor

Grade Transmission Rate (g/day·100 in2) Transmission Rate (g·mm/m2·day)
1650 0.75 0.59
1652 0.6 0.47
1702 0.7 0.55
1705 0.7 0.55
F1706 0.7 0.55
F1801 0.7 0.55
F1855 1 0.79
Blown Film, Thickness (mm): 0.051.
206 Permeability Properties of Plastics and Elastomers

[4] Attane™ Data Sheets, Dow Chemical Com-

pany, May 2000.
[5] Sclairfilm® Specifications sheets, Exopack®,
2010.
[6] Sclairfilm® Polyolefin Film—SL-1 and SL-3
Laminating Film, supplier technical report (H-
27763), DuPont Canada, 1990.
[7] Permeability of Polymers to Gases and Vapors,
Figure 9.61 The chemical structure of DuPont™ supplier technical report (P302-335-79, D306-
Nafion®. 115-79), Dow Chemical Company, 1979.
[8] Flaconnèche, B, Martin, J, Klopffer, MH. Per-
meability, diffusion and solubility of gases in
Table 9.92 Permeation of Nitrogen Through Solvay
Solexis AQUIVION™ [56] PFSA Membranes
polyethylene, polyamide 11 and poly(vinylidene
fluoride). Oil Gas Sci. Technol.—Rev. IFP, vol.
Tempera- Permeation Coefficient 56. 2001, No. 3, pp. 261–278.
Grade ture (°C) (cm3·mm/m2·day·atm) [9] Wood-adams, P. Permeation: essential factors
E87 80 110 for permeation; course notes, physical chem-
istry of polymers, Concordia University. In:
120 455 Polymer, 2006; pp. 1–16.
E79 80 65 [10] Sclairfilm® Polyolefin Film—LWS-1 and
120 430 LWS-2 Film, supplier technical report, DuPont
Canada, 1990.
Membrane thickness (mm): 0.135. [11] Technical Manual—Materials used in Pipe
Extrusion Hostalen, Lupolen and Hostalen PP
Nafion® is a perfluorinated polymer that contains products Processing and Applications, Basell
small proportions of sulfonic or carboxylic ionic Polyolefins, 2005.
functional groups. Its chemical structure is shown [12] Engineering Properties of Marlex® Resins, PE
in Fig. 9.61. In this case the acid end group is sul- TSM-1, Chevron Philips, 2002.
fonic functional group but it may also be a carboxylic [13] Sclair® Specification Sheets, NOVA Chemicals,
functional group. M+ is either a metal cation in the 2010.
neutralized form or an H+ in the acid form. [14] Adam, SJ, David, CE. Permeation measure-
Manufacturers and trade names: Solvay Solexis ment of fluoropolymers using mass spectrom-
AQUIVION™, DuPont™ Nafion®. etry and calibrated standard gas leaks, 23rd
Applications and uses: Chlor-alkali production International SAMPE Technical Conference,
cell membrane, Proton exchange membrane (PEM) Conference Proceedings, SAMPE, 1991.
for fuel cells and water electrolyzer applications, ion [15] Halar® ECTFE, Fluoropolymer Coatings for
selective sensors. Cleanroom Exhaust Duct Systems, Solvay So-
Data for fluoroionomers is found in Table 9.92. lexis, 2003.
[16] Ineos Typical Engineering Properties of Poly-
propylene, 2010.
[17] Technical Manual—Materials used in pipe ex-
References trusion hostalen, lupolen and hostalen pp prod-
ucts processing and applications, Basell Poly-
[1] Polyethylene Products and Properties, Basell olefins, 2005.
Polyolefins, 2002. [18] BOPP Film, Polypropylene, Form No. 022 PPe
[2] Brubaker DW, Kammermeyer K. Separation 10/01, Basell Polypropylene, 2001.
of gases by means of permeable membranes. [19] Chen M, Wang Y, Wang L, Yin S. Effects of
Permeability of plastic membranes to gases. Temperature and Humidity on the Barrier Prop-
Ind. Eng. Chem. 1952;44:1465–74. erties of Biaxially-oriented Polypropylene and
[3] Felder RM, Spence RD, Ferrell JK. Permeation Polyvinyl Alcohol Films. J. Appl. Packaging
of sulfur dioxide through polymers. J. Chem. Res. 2014;6:1, Article 5. Available at: http://
Eng. Data 1975;20:235–42. scholarworks.rit.edu/japr/vol6/iss1/5.
9: Polyolefins, Polyvinyls, and Acrylics 207

[20] Wood-adams, P., 2006. Permeation: essential [39] Ethylene Content and OTR, Soarnol® Techni-
factors for permeation; course notes, physical cal Note, Nippon Gohsei, 2003.
chemistry of polymers, Concordia University. [40] Relative Humidity and OTR, Soarnol® Techni-
In: Polymer, pp. 1–16. cal Note, Nippon Gohsei, 2003.
[21] Honeywell R Series PMP datasheet, 12/2006. [41] Temperature and OTR, Soarnol® Technical
[22] Polymethyle Pentane (PM) TPX™, Mitsui Note, Nippon Gohsei, 2003.
Chemicals, 2011. [42] Haraya K, Hwang S. Permeation of oxygen, ar-
[23] Topas® Cyclic Olefin Copolymer (COC) prod- gon and nitrogen through polymer membranes.
uct brochure, 2006. J MembrSci 1992;71:13–27.
[24] Zürcher, Jörg, Topas COC in Pharmaceutical [43] Mirrex® product data sheet, VPI, 2010.
Blister Packs, 2004. [44] (1)Brubaker DW, Kammermeyer K. Separa-
[25] Elvax® Selector Guide, Form No. H-42042, tion of gases by means of permeable mem-
DuPont™ Packaging, 2001. branes. Permeability of plastic membranes to
[26] Japan Synthetic Rubber JSR RB, supplier de- gases. Ind. Eng. Chem. 1952;44(6):1465–74.
sign guide, Japan Synthetic Rubber Company. [45] (1)Aiba S, Ohashi M, Huang S. Rapid
[27] Lupolen, Lucalen Product Line, Properties, determination of oxygen permeability of poly-
Processing, supplier design guide [B 581e/ mer membranes. Ind. Eng. Chem. Fundam.
(8127) 10.91], BASF Aktiengesellschaft, 1991. 1968;7(3):497–502.
[28] EVAL™* Ethylene Vinyl Alcohol Copolymer [46] Saran™ F Resins Superior Barrier for Packag-
Explained, EVAL™ Europe, 2002. ing, Form No. 190-00305-199X SMG, Dow
[29] Gas Barrier Properties of EVAL™ Resins— Plastics, 1999.
Technical Bulletin No. 110, supplier techni- [47] EVAL™ Ethylene Vinyl Alcohol Copolymer
cal report, EVAL™ Company of America, Explained, EVAL™ Europe, 2002.
Rev 07-00. [48] Heilman W, Tammela V, Meyer J, Stannett
[30] Chemical and Solvent Barrier Properties of V, Szwarc M. Permeability of polymer films
EVAL™ Resins Technical Bulletin No. 180, to hydrogen sulfide gas. Ind. Eng. Chem.
supplier technical report, rev.07/00. EVAL™ 1956;48:821–4.
Company of America, 2001. [49] P. Wood-adams, Permeation: Essential factors
[31] EVAL™ Film Properties Comparison, supplier for permeation; Course Notes, Physical Chem-
technical report, Kuraray Co., Ltd. istry of Polymers, Concordia University, in:
[32] EVAL™ Films the Ultimate Laminating Film Polymer, 2006pp. 1-16.
for Barrier Packaging Applications—Techni- [50] Lucite® Diakon® Technical Manual (DTM/
cal Bulletin No. 160, supplier technical report, E/2Ed/Dec02), www.lucitesolutions.com,
EVAL™ Company of America. 2002.
[33] Flavor and Aroma Barrier Properties of [51] Stannett V. The transport of gases in syn-
EVAL™ Resins Technical Bulletin No. 190, thetic polymeric membranes — an historic
supplier technical report, rev. 07-00, EVAL™ perspective. Journal of Membrane Science.
Company of America. 1978;3(2):97–115.
[34] Various Gases Barrier Property of Soarnol®, [52] Ineos Barex Specification Sheets, June 2006.
Soarnol® Technical Note, Nippon Gohsei, [53] 621 Ways to Succeed–1993–1994 Materi-
2003. als Selection Guide, supplier technical report
[35] Water Vapor Permeability and Moisture (304-00286-1292X SMG), Dow Chemical
Absorption/Water Absorption, Soarnol® Tech- Company, 1992.
nical Note, Nippon Gohsei, 2003. [54] Barex Barrier Resins–Barrier Properties, sup-
[36] Organic Solvent Barrier Property of “Soar- plier technical report (Bx-555), BP Chemicals
nol®”, Soarnol® Technical Note, Nippon Inc., 1992.
Gohsei, 2003. [55] Surlyn Ionomer Resin Selector Guide, suppli-
[37] Chlorofluorocarbon (R-22;CHCLF2) Barrier er technical report [E-48623 (1/90)], DuPont
Property, Soarnol® Technical Note, Nippon Company, 1986.
Gohsei, 2003. [56] AQUIVION™ Low-EW PFSA Mem-
[38] Thickness and OTR, Soarnol® Technical Note, branes Product Description, Solvay Solexis,
Nippon Gohsei, 2003. Yl01E004, 2008.