Polymer Reviews

ISSN: 1558-3724 (Print) 1558-3716 (Online) Journal homepage: http://www.tandfonline.com/loi/lmsc20

Recent Updates on the Barrier Properties of

Ethylene Vinyl Alcohol Copolymer (EVOH): A
Review

Caroline Maes, Wout Luyten, Geert Herremans, Roos Peeters, Robert Carleer
& Mieke Buntinx

To cite this article: Caroline Maes, Wout Luyten, Geert Herremans, Roos Peeters, Robert
Carleer & Mieke Buntinx (2018) Recent Updates on the Barrier Properties of Ethylene
Vinyl Alcohol Copolymer (EVOH): A Review, Polymer Reviews, 58:2, 209-246, DOI:
10.1080/15583724.2017.1394323

To link to this article: https://doi.org/10.1080/15583724.2017.1394323

Accepted author version posted online: 24

Oct 2017.
Published online: 18 Jan 2018.

Submit your article to this journal

Article views: 351

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=lmsc20
POLYMER REVIEWS
2018, VOL. 58, NO. 2, 209–246
https://doi.org/10.1080/15583724.2017.1394323

REVIEW

Recent Updates on the Barrier Properties of Ethylene Vinyl

Alcohol Copolymer (EVOH): A Review
Caroline Maes a,b, Wout Luytena, Geert Herremansa, Roos Peetersb, Robert Carleerc,
and Mieke Buntinxb
a
Kuraray–Eval Europe NV, Haven 1053 Nieuwe Weg 1, Bus 10, Zwijndrecht, Belgium; bHasselt University,
Packaging Technology Center IMO-IMOMEC, Wetenschapspark 27, Diepenbeek, Belgium; cHasselt University,
Applied and Analytical Chemistry IMO-IMOMEC, Agoralaan Building D, Diepenbeek, Belgium

ABSTRACT ARTICLE HISTORY

The gas barrier properties of ethylene vinyl alcohol copolymer (EVOH) Received 26 June 2017
against oxygen, carbon dioxide and water vapor have been Accepted 15 October 2017
widely investigated in relation to different material characteristics, KEYWORDS
environmental conditions and new processing technologies. Recently, Ethylene vinyl alcohol
EVOH is gaining more attention as a barrier material against other gases copolymer; EVOH;
and organic substances such as aromas, flavors, fuels, chemicals (e.g., permeability; barrier
BTEX), and as a functional barrier, e.g., to avoid mineral oil migration. properties; functional barrier;
This review contains an update on permeability data of EVOH mineral oils; (volatile) organic
emphasizing its potential as a barrier material for new and versatile compounds
applications in food and pharmaceutical packaging, agriculture,
construction, automotive, etc.

1. Introduction
Ethylene vinyl alcohol copolymer (EVOH) was first commercialized by Kuraray under the trade-
mark EVALTM in 1972. The barrier properties of EVOH against oxygen had been investigated for
fifteen years and were found to be valuable. After Kuraray obtained the patent in 1971, they
started producing EVOH commercially. Later, Nippon Gohsei and Chang Chun also started their
commercial production of EVOH.[1–4] Kuraray is the largest producer of EVOH. Since 2001 they
have more than doubled their global production capacity from 45,000 tons to 92,000 tons in 2016
and a further expansion of 11,000 is planned in 2018, due a continued market growth.[5–7]
EVOH is a random copolymer with a semi-crystalline structure, consisting of ethylene and
vinyl alcohol monomer units. The synthesis of EVOH occurs in a two-step process as shown in
Fig. 1.[8,9] Vinyl alcohol is unstable and it cannot be isolated, therefore the first step is a copoly-
merization reaction between ethylene and vinyl acetate, which results into the random copoly-
mer ethylene vinyl acetate. In the second step polyethylene vinyl acetate is converted into EVOH
through a transesterificiation with methanol and as a side product methyl acetate is produced.
Nowadays, EVOH has gained worldwide recognition for its barrier properties against per-
manent gases such as oxygen (O2), carbon dioxide (CO2) and nitrogen (N2). Especially its

CONTACT Mieke Buntinx mieke.buntinx@uhasselt.be Hasselt University, Packaging Technology Center IMO-
IMOMEC, Martelarenlaan 42, 3500 Hasselt, Belgium.
© 2018 Taylor & Francis Group, LLC
210 C. MAES ET AL.

Figure 1. Synthesis of EVOH is a two-step process: copolymerization of ethylene and vinyl acetate result-
ing in polyethylene vinyl acetate (a) followed by a transesterification with methanol, which results into
EVOH and methyl acetate as a side product (b).

outstanding oxygen barrier has made EVOH one of the most commonly used gas barrier
materials in multilayer food packages.[9–14] EVOH can also be used in clinical and pharma-
ceutical applications such as in parenteral nutrition bags and ampoules to increase shelf-
life.[15] However, the applications for EVOH as an oxygen gas barrier material reach further
than only food and pharma. Pipes for floor heating in the building industry, for example,
contain an EVOH layer to keep oxygen out and thus preventing the oxygen from travelling
to the boiler and causing corrosion.[16] In addition the radon barrier of EVOH is another
application in the construction sector, where it is used to decrease radon exposure and
improve the indoor air quality.[17]
The excellent barrier properties of EVOH are attributed to the strong inter- and intra-
molecular bonding caused by the polar hydroxyl groups present in the vinyl alcohol
unit.[9,10,14] These hydroxyl groups are also responsible for the moisture sensitivity because
water is easily absorbed due to the hydrophilic character of the polymer. Gradually, when
more water is absorbed, EVOH will be plasticized and the inter- and intra-molecular bonds
will weaken, causing a decrease in the barrier properties.[10] This plasticizing effect is the rea-
son why EVOH is mainly applied in multilayer structures. This same effect is also known to
occur with alcohols such as methanol and ethanol.[18] Nevertheless, even with its sensitivity
to humidity, EVOH remains one of the best gas barrier materials amongst polymers.[9]
More recently, there has been an increasing interest in EVOH as a barrier material against
organic substances such as chemicals, hydrocarbons (e.g., mineral oils and fuel), aromas, and
flavors. EVOH proved to be successful in fuel tanks to prevent fuel emission to the environ-
ment, in agricultural films to improve herbicide retention and in geomembrane films to
keep the methane release from landfills in check.[19–21] EVOH can also pose as a functional
barrier in food packaging as it offers good chemical resistance and prevents the migration
from chemical substances out of other materials into the packaging’s content.[22] In this
paper the recent findings on the barrier properties of EVOH copolymer towards different
molecules are summarized and reviewed.

2. Oxygen permeability of EVOH

EVOH has one of the lowest oxygen permeability coefficients amongst polymers, as shown
in Table 1. In this review, the oxygen permeability or oxygen permeability coefficient (PO2 )
 POLYMER REVIEWS 211

Table 1. Oxygen permeability (PO2 ) of commonly used polymers. Based on data from Kuraray co. Ltd.
(2017)[7], McKeen (2012),[21] Lange and Wyser (2003),[54] and Lagaron et al. (2004).[24]
Polymer PO2 [cm3.mm/(m2.day.atm)]

PVOH 1.5 a
EVOH32 6b
EVOH44 38 b
PVDC 10–300 c
PA 6 400–2,000 a
PET 1,000–5,000 c
PP 50,000–100,000 c
PS 100,000–150,000 c
LDPE 100,000–200,000 c
HDPE 40,000–100,000 c
a
Permeability at 23
C and 0% RH.
b
Permeability at 20
C and 65% RH.
c
Permeability at 23
C and 50% RH.

is the thickness and pressure normalized rate at which O2 passes through a material and will
be expressed in cm3.mm/(m2.day.atm), and the oxygen gas transmission rate (O2GTR) is the
actual amount of transmitted O2 measured for a certain package or film in cm3/(m2.day.
atm) with no thickness normalization under a pressure difference of 1 atm.[21,23] The PO2 of
EVOH containing 32 mol% ethylene (EVOH32) and EVOH containing 44 mol% ethylene
(EVOH44) measured at 20
C and 65% relative humidity (RH) according to the ISO 14663-2
standard is respectively 6 and 38 cm3.mm/(m2.day.atm).[7]
Poly(vinyl alcohol) (PVOH) has a lower oxygen permeability coefficient, i.e. 1.5 cm3.mm/
(m2.day.atm) at 23
C and 0% RH,[24] however, this polymer is difficult to process because of
its low thermal degradation point, which is about 150
C, while its melting temperature is
around 180–190
C. Apart from this, PVOH is also soluble in water, explaining its limited
use in packaging applications.[25] However, PVOH can be used as a coating on other plastics
to increase the barrier properties. Other barrier polymers are poly(vinylidene dichloride)
(PVDC), the polyamide nylon 6 (PA 6) and poly(ethylene terephthalate) (PET). These poly-
mers have a PO2 that is 1 to 3 orders of magnitude higher than EVOH. When compared to
the non-polar polymers such as low-density polyethylene (LDPE), high-density polyethylene
(HDPE), polypropylene (PP) and polystyrene (PS) the PO2 is over 3 orders of magnitude
higher than EVOH.[9,26] In the following sections several factors that influence the oxygen
permeability of EVOH will be discussed. These can be attributed to intrinsic factors of the
material itself as well as extrinsic factors such as environmental conditions and permeant
properties.[27]

2.1. Influence of material characteristics

First, the intrinsic material characteristics of EVOH, including chemical structure, crystallinity,
thickness, glass transition temperature and free volume that are related to the O2 barrier
properties are discussed.

2.1.1. Ethylene content

The structure of EVOH copolymer is key for understanding its outstanding barrier
properties. EVOH consists of ethylene and vinyl alcohol monomer units. The vinyl
alcohol units are responsible for the exceptional gas barrier properties due to the
212 C. MAES ET AL.

Figure 2. Oxygen permeability at 20
C, 65% RH according to ISO 14663-2 and water vapor permeability at
40
C, 0/90% RH according to ASTM E96-E as a function of the ethylene content in EVOH. Based on data
from Kuraray co. Ltd. (2017).[7]

inter- and intra-molecular bonding caused by the hydroxyl groups; although these units
are also known to be soluble in water and to be quite difficult to process. The ethylene
units, on the other hand, display good water resistance, yet have one of the poorest gas
barrier properties in polymers. The combination of both monomer units leads to a pro-
cessable thermoplastic copolymer with excellent gas barrier properties, but it remains
sensitive to water.[9,28] The oxygen barrier of EVOH improves at lower ethylene mol%
content as shown in Fig. 2 by the dotted line.[10,29]
Oher material characteristics like the melting point (Tm) and the glass transition tempera-
ture (Tg), which are also important for the processability of EVOH, are dependent on the
ethylene content. Both Tm and Tg decrease with an increasing ethylene content as can be
seen in Table 2, making the polymer less brittle and easier to process. EVOH with a higher
ethylene content is more suitable for thermoform, stretch and shrink applications, whereas
EVOH with a lower ethylene content is used in flexible and ultra-high barrier applications.[7]
To achieve good barrier properties a particular EVOH composition range is required. EVOH
is not considered a high barrier resin if the ethylene content is over 50 mol%, owing to char-
acteristic higher PO2 (Fig. 2).[30]

2.1.2. Crystallinity
The barrier properties of EVOH are also attributed to the inherent high degree of the poly-
mer’s crystallinity. The semi-crystalline structure is typically represented by crystals or crys-
talline domains, which are dispersed in an amorphous matrix. The barrier properties of the

Table 2. Melting point (Tm) and glass transition temperature (Tg) of EVOH with different ethylene content.
Based on data from Kuraray co. Ltd. (2017).[7]
Ethylene content (mol%) Tm (
C) Tg (
C)

27 190 63
32 183 60
38 172 56
44 165 53
48 157 50
 POLYMER REVIEWS 213

polymer are also related to the size and distribution of the crystals.[31] When the ethylene
content is below 40 mol%, the crystals are monoclinic similar to those in PVOH. At higher
ethylene content (over 80 mol%) the crystals have an orthorhombic structure like in PE
(polyethylene). Intermediate compositions show a mixture of both structures and have a
minimal crystallinity level.[32] However, not only the polymer composition but also the crys-
tallization conditions, such as the cooling rate, can affect the crystal structures. Samples with
low ethylene contents also show orthorhombic crystals when they are quenched, opposed to
slowly cooled samples, which present a monoclinic lattice. The degree of crystallinity also
varies with the cooling rate. It decreases when the cooling rate increases and leads to crystal
imperfections.[33] Armstrong (2008)[34] demonstrated that EVOH has a rapid crystallization
rate as opposed to other thermoplastic polymers and therefore it is difficult to control the
degree of crystallinity during cooling from melt state. The fastest crystallization rate for
EVOH32 was observed at 140
C. To effectively decrease the PO2 by maximizing the degree
of crystallinity slower cooling from the Tm close to 140
C, or long reheating at 140
C is rec-
ommended to allow the chains more time to arrange into a crystalline order. Alvarez et al.
(2003)[35] reported an increasing degree of crystallinity (48%, 56% and 60% respectively)
after isothermal crystallization of EVOH32, EVOH38 and EVOH44 with increasing ethylene
content, but the crystallization rate was low. The samples were melted for 10 min at 250
C,
then cooled to the crystallization temperature (Tc) at 250
C/min and maintained here for
20 min to allow complete crystallization. Rwei et al. (2015),[36] on the other hand, found that
the degree of crystallinity decreased with increasing ethylene content. The results for
EVOH32, EVOH38 and EVOH44 were respectively 46.6%, 41.8% and 40.0%. However, the
crystallization conditions of these samples were not mentioned. This decrease in crystallinity
was earlier confirmed by Ketels (1989)[37] and demonstrates a correlation between the ethyl-
ene content and the PO2 . It is suggested that the permeation of low weight molecules such as
permanent gases generally occurs through the amorphous regions of the copolymer; the
crystalline regions in the polymer create a more irregular tortuous diffusion path, making it
more difficult for permanent gases to pass through.[24,38] Fig. 3 illustrates the inverse rela-
tionship between the degree of crystallinity and the PO2 of five EVOH32 samples measured

Figure 3. Oxygen permeability of EVOH32 at 20
C, 100% RH (after stretching and/or receiving a heat
treatment of 140
C), as a function of the crystallinity. Adapted with permission from Armstrong (2002).[86]
214 C. MAES ET AL.

at 20
C and 100% RH. A decrease of a factor of 17 is noted from 27% to 70% crystallinity.
The variation in crystallinity is often related to the processing conditions to which the mate-
rial is subjected and will be discussed later.[9,11,13]

2.1.3. Thickness
The thickness of the EVOH layer is another factor which contributes to the barrier perfor-
mance. EVOH is usually applied in multilayer structures as a thin barrier layer, its thickness
depending on the application. In food packaging, an EVOH layer of only a few micrometers,
usually less than 10 mm, is sufficient as a barrier, whereas in floor heating pipes, the EVOH
layer has a thickness of about 50–100 mm (lab data from EVAL Europe nv). In general, it
can be stated that the thickness of the barrier layer is inversely proportional to its O2GTR
(Fig. 4), although very thin structures may show inconsistent O2GTR values due to structural
changes or surface phenomena.[23] The effect of the material thickness on the permeability is
especially important in thermoformed packaging, because of the non-uniform material dis-
tribution during thermoforming. However, it should be noted that other parameters such as
orientation and (re)crystallization can partly counteract the effect of thinning on the perme-
ability of thermoformed packaging.[39] This will be addressed more in depth later in this
paper.

2.1.4. Glass transition temperature and free volume

Another parameter which impacts the barrier is Tg, referring to the temperature at which a
transition from a “glassy” state to a “rubbery” state of the polymer occurs.[40] Below this tem-
perature, the chain mobility is low, yet above the glass transition temperature there is enough
thermal energy for the polymer to become more viscous by overcoming the intra- and inter-
molecular bonds. It is argued that the permeation of gas molecules occurs due to cooperative
movement of the gas molecules and the polymer chain segments.[41,42] EVOH has a high
glass transition temperature between 50 and 63
C, depending on the ethylene content (48
and 24 mol% ethylene, respectively) (Table 2), which is far above room temperature. Low
oxygen barrier materials like PE and PP usually have a Tg below room temperature.

Figure 4. Oxygen transmission rate of EVOH27, EVOH32, EVOH38 and EVOH44 at 20
C, 65% RH and atmo-
spheric pressure as a function of the thickness. Based on data from Kuraray co. Ltd. (2017).[7]
 POLYMER REVIEWS 215

However, Lagaron et al. have shown that the Tg can strongly be reduced to below freezing
point through the uptake of water, methanol or other molecules with a plasticizing effect on
EVOH. In addition to the high Tg, EVOH also has little free volume due to its strong cohe-
sive energy.[9,18] Yeh et al. (2006) reported that the fractional free volume for EVOH32,
EVOH44 and EVOH48 was respectively 6.1, 7.3, and 8.0%.[43] Ito et al. (2009) found that
the free volume cavity size ranged from 0.04 to 0.07 nm3 for ethylene contents varying from
28 to 44 mol%.[29] Muramatsu et al. (2003) reported that the free volume cavity size for
EVOH29 varied with the RH, first decreasing when the RH increased from 0% to about 25%
caused by the water molecules filling up the free volume cavities, and then increasing at
higher RH to values above those of 0% RH due to the plasticizing effect of water on
EVOH.[44]

2.2. Influence of environmental parameters

2.2.1. Temperature
The temperature is an important environmental factor, which influences the permeability of
polymers. When the temperature increases, the permeability will also increase, due to an
increase in the diffusion rate of the gas molecules through the polymer. The solubility, how-
ever, decreases at higher temperatures, but the effect on the diffusion rate is significantly
larger, resulting in an increase in permeability. The temperature dependence is expressed in
the Arrhenius eq. (1), where permeability coefficient (P0) and activation energy (Ep) are
characteristics attributed to a certain material and permeant pair. This equation is used to
model the permeability coefficient P over a moderate temperature range as can be seen in
Fig. 5 for the oxygen permeability of EVOH32 and EVOH44 at 0% RH.
P D P0 e ¡ Ep 6 RT
(1)

The units of P and P0 are usually cm3.mm/(m2.day.atm). Ep is expressed in kJ/mol, tem-

perature (T) in K and R is the universal gas constant 8.3144 £ 10¡3 kJ/(mol.K). The Ep can

Figure 5. Oxygen permeability (0% RH) of EVOH32 and EVOH44 as a function of the temperature. Based
on data from Kuraray co. Ltd. (2017).[7]
216 C. MAES ET AL.

be determined from the graph and is 55.27 and 49.84 kJ/(mol.K) for EVOH32 and EVOH44,
respectively.[21,45]

2.2.2. Relative humidity

The second environmental factor is the RH, which is also one of the most significant key fac-
tors when it comes to permeability of EVOH. Due to its hydrophilic character, EVOH
absorbs significant amounts of water from the environment when exposed to humid condi-
tions. The water uptake increases with an increasing RH to about 8–13% for a EVOH32 film
at 100% RH and 21
C. The water uptake also depends on the crystallinity, e.g., a non-ori-
ented EVOH32 film, with a crystallinity of approximately 58%, has a water uptake of 8.4%
in the above mentioned conditions, while the biaxial oriented film, with a crystallinity of
approximately 70%, has a water uptake of only 6.8%.[9,46] Lagaron et al. (2001) have shown
in different studies that the water uptake causes a decrease in the Tg to below freezing
point.[18,47]
The effect of moisture on the barrier properties of EVOH depends on the RH of the envi-
ronment. At lower RH the PO2 shows an initial decline, which increases after reaching a mini-
mum at about 20–40% RH (Fig. 6). This phenomenon is usually explained by the change in
free volume, where low RH has a positive effect on the barrier, because water molecules fill
up the free volume between the polymer chains. A small amount of water in EVOH also
induces an enthalpy relaxation, which could explain why the PO2 and the cavity size reach a
minimum around 20–40% RH. A further increase in RH coincides with a decrease in Tg, as
the additional water molecules will act as plasticizer and weaken the inter- and intramolecu-
lar hydrogen bonds between the chains, causing an increase in chain mobility and an
increase in free volume due to swelling of the polymer, which leads to a higher oxygen per-
meability. The moisture sensitivity of EVOH is often seen as a limitation. However it should
be noted that EVOH outperforms most barrier polymers even at 100% RH.[9,10,44,48]
As was mentioned previously, the same effect is known to occur with methanol and etha-
nol. Cava et al. (2007) were able to use the swelling behaviour of EVOH as an advantage.
Water, methanol and ethanol acted as swelling agents and led to a sorption-induced release

Figure 6. Oxygen permeability (20
C) of EVOH32 and EVOH44 as a function of the relative humidity.
Based on data from Kuraray co. Ltd. (2017).[7]
 POLYMER REVIEWS 217

of an antimicrobial component, which was added to the EVOH matrix, creating an active
packaging material.[49]

2.2.3. Pressure
Pressure can be seen as a third environmental factor. Here it is important to note the dif-
ference in total pressure and the partial pressure of one gas. In an ideal situation the total
pressure has no influence on the solubility and diffusion and therefore on the permeabil-
ity. However, plasticization and swelling effects may occur due to a change in pressure,
leading to either an increasing or decreasing effect on the permeability or like in most
cases with glassy polymers to an initial decrease followed by an increase upon increasing
upstream pressure.[21,50] This needs to be taken into consideration when working with
the differential pressure method, where a test specimen is mounted between two com-
partments of a cell, the test gas is introduced at the upstream compartment and the
downstream side is evacuated. The pressure increase is used to determine the permeabil-
ity.[51] Apart from the total pressure difference in the system the partial pressure differ-
ence of the test gas can also be used to measure the permeability. Opposed to the
differential pressure method, the total pressure on each side of the cell is at atmospheric
pressure in the equal pressure method, yet the partial pressure of the test gas is different,
creating a driving force from one side of the cell to the other. The gas molecules will per-
meate from the side with the highest partial pressure or concentration to the side with
the lowest partial pressure.[52]

2.3. Multilayer structures and blends

Due to the dependence of the PO2 on the RH (discussed in paragraph 2.3), EVOH is usually
applied in multilayer structures to reduce the effect of moisture on the EVOH layer. The
application of EVOH in multilayer structures also has other advantages as it improves the
processability, heat sealability, mechanical properties like tensile, impact and tear strength of
the overall structure.[53–56] These structures are a cost-effective and light-weight alternative
for traditional packaging materials such as glass and metal. Typical multilayer structures can
be produced by either coextrusion or lamination and often consist of 5 to 9 layers, including
the adhesive layers.[27]

2.3.1. Multilayers
There are two different approaches to effectively control the RH inside the EVOH using
multilayer structures. The first is the thickness of the layers protecting the EVOH. A thicker
layer should be used on the side with the highest RH and a thinner layer should be used on
the side with the lowest RH. A second approach is the choice of the materials protecting the
EVOH layer. The most efficient way is to use a material with a higher water vapor barrier or
lower PH2 O on the side with the highest RH and a material with a higher PH2 O on the side
with the lowest RH. In Table 3 the PO2 of different multilayer structures using EVOH32,
EVOH44 and PVDC as barrier layers sandwiched between different outer layers and PP
measured at 100% RH inside and either 65 or 75% RH outside are shown. PP, which is con-
sidered a good moisture barrier material (Fig. 7) is used on the side with the highest RH.
HDPE is a better moisture barrier than PP, but when used on the side with the lowest RH,
the PO2 of the film becomes worse than when PP is used on both sides. However, PET,
218 C. MAES ET AL.

Table 3. The impact of different inner and outer layers in multilayer structures on the oxygen permeability
(PO2 ) with different barrier materials (EVOH32, EVOH44 and PVDC) at 20
C and various relative humidity
settings. Based on data from Kuraray America Inc. (2007).[57]
PO2 [cm3.mm/(m3.day.atm)]

65% RH out/100% RH in 75% RH out/100% RH in

Multilayer structure (mm) outer/
barrier/inner (152/25/610) EVOH32 EVOH44 PVDC EVOH32 EVOH44 PVDC

PP/Barrier/PP 342 1184 1465 586 1587 1465

PET/Barrier/PP 183 1465 525 1465
PC/Barrier/PP 269 989 1465 427 1343 1465
PS/Barrier/PP 269 1465 427 1465
HDPE/Barrier/PP 427 1465 720 1465
PA/Barrier/PP 1013 1465 1343 1465
LDPE/Barrier/PP 1111 1465 1465 1465

polycarbonate (PC), PS, PA and LDPE are lesser moisture barrier materials than PP and
result in a more efficient protection of the EVOH against moisture and thus in a lower PO2 .
The increase in RH on the outside shows that even with the use of multilayer structures, the
PO2 of EVOH is still affected by the surrounding RH. PVDC is not affected by the RH, there-
fore different structures do not impact the barrier, but EVOH32 still easily outperforms
PVDC at both conditions. However, the choice of materials also depends on the desired
mechanical and physical properties.[57]
Jakobsen and Risbo (2008)[58] developed a model to calculate the total oxygen resis-
tance (Rt ) of multilayer structures containing EVOH in which Rt D O2 GTR
1
. The model was
based on a PE/tie/EVOH/tie/PE structure, but the tie layers were excluded from the model.
To determine the Rt , it is important to know the oxygen resistance of the EVOH barrier
layer (Rb ), which is dependent on the RH or water activity (aw ) inside the EVOH layer.
This in turn depends on the inner and outer water activity (ai and ao ) and the water vapor
resistance of the inner and outer layer (Rw;i and Rw;o ). Using eq. (2) the asymmetry a,
which can be interpreted as the fraction of water vapor resistance in the barrier layer

Figure 7. Oxygen permeability (EVOH at 20
C, 65% RH; PA 6 at 23
C, 0% RH and other materials at 23
C,
50% RH) and water vapor permeability (38
C, 0/90% RH according to ASTM E96-E) of EVOH and other bar-
rier materials. Based on data from Kuraray co. Ltd. (2017),[7] Lagaron et al. (2004),[24] Yam (2009),[27]
McKeen (2012)[21] and Lange and Wyser (2003).[54]
 POLYMER REVIEWS 219

mid-plane, can be calculated.

Rw;i C 1=2 Rw;b
aD (2)
Rw;t

Rw;t is the total water resistance of the multilayer. This value can be used in eq. (3) to cal-
culate the average water activity in the EVOH layer (ab ). Note that the water resistance of
EVOH (Rw;b ) is also dependent on ab , but a thin layer of EVOH contributes little to the total
water vapor resistance and therefore hardly influences a.

ab D aao C ð1 ¡ aÞai (3)

The Rb can now be calculated using eq. (4) by dividing the thickness of the EVOH layer
(xb ) by the PEVOH ðaw Þ, which is the PO2 of the used EVOH material at the calculated ab or
RH from experimental data as presented in Fig. 6.

xb
Rb D (4)
PEVOH ðaw Þ

Lastly the Rt is determined by taking the sum of all oxygen resistances using eq. (5).

Rt D Ro C Rb C Ri (5)

The study also concluded that it is not sufficient to sandwich the EVOH layer between
thick layers of polymers with a low water vapor permeability (PH2 O ). The key to an optimal
design lies in asymmetric multilayer structures, where a thin laminate can be more effective
than a thick laminate.

2.3.2. Microlayers
There is a lot of interest in microlayer extrusion technology. Microlayers are multilayer
structures consisting of very thin alternating layers of two or more materials, which are coex-
truded through multiplication extrusion by using multipliers. In each multiplier the melt
blend is split and recombined, multiplying the layers. There are claims that microlayer extru-
sion technology leads to improved physical and barrier properties of EVOH.[59,60]
Li et al. (2009) prepared a material with alternating layers of PP and PP/EVOH blend
through microlayer coextrusion. The morphology of the EVOH phase was changed from a
zero-dimensional sphere to a one-dimensional fiber, then to a two-dimensional sheet with the
increase of the layer number, which caused an improvement in the gas barrier properties when
compared to a conventional PP/EVOH blend. Alipour et al. (2015) found that the PO2 for a
5- and 19-layer structure of EVOH, LDPE and a PE adhesive was the same, however an
improvement in n-hexane uptake and improvement of mechanical strength were noted in the
19-layer structure compared to the 5-layer structure.[61] Su et al. (2015) prepared blends of
EVOH32 and linear low-density polyethylene with 5% LLDPE grafted with 1% maleic anhy-
dride (EVOH/LLDPE/LLDPE-g-MAH). These blends were coextruded with LLDPE using
microlayer extrusion technology. The microlayer structure decreased the barrier percolation
threshold from 50 wt% EVOH for a conventional EVOH/LLDPE/LLDPE-g-MAH blend to
220 C. MAES ET AL.

about 5.6 wt% in a 16 layer microstructure.[62] Microlayer technology can also help to main-
tain the barrier properties of films after flexing because of its improved flex crack resistance.[59]

2.3.3. Blends
The production of multilayer structures is a complex and expensive process; next to this the
end-material is often difficult to recycle. A good cost-reducing alternative for multilayer
structures is blending two or more polymers to attain the desired mechanical and barrier
properties depending on the application and the recycling process.[63] EVOH can be blended
with other polymers either to improve the other polymers properties or to improve EVOH’s
properties. Studies showed that the incorporation of 5–30 wt% of a barrier polymer into a
base polymer led to a 2- to 10-fold increase in barrier properties depending on the polymer.
However, unlike multilayer structures, the overall macroscopic property of a blended film is
not equal to that of a single material, as it is a combined system of several components. This
makes it more difficult to predict the barrier properties of a blended film. Ge and Popham
(2016) found that effective prediction of gas permeability depends on the morphology, per-
meability ratio of matrix-to-disperse phase and the selection of an appropriate model.[64] In
the following paragraph some examples of studies with EVOH blends are summarized.
Ait-Kadi et al. (2007) blended PP with 16.5 wt% EVOH32, which led to a decrease of PO2
of 24% as compared to PP. The effect of different compatibilizers in PP or styrene-ethylene-
butene-styrene copolymer (SEBS) grafted with maleic anhydride (polymer-g-MAH) and
grafted with diethyl maleate (polymer-g-DEM) was investigated. While the polymer-g-
MAH was a better compatibilizer it led to an increase of the PO2 when compared to the PP/
EVOH blend without compatibilizer, due to the domain size of the EVOH phase leading to
a fibrillar rather than lamellar morphology, the polymer-g-MAH on the other hand
decreased the PO2 further as compared to the blend.[63] Cerruti et al. (2007) found that for
the blends PA 6/EVOH and PA 6/EVOH/EVOH-COOH, the presence of EVOH reduced
the PO2 and the PH2 O as compared to PA 6. Small amounts of EVOH-COOH improved the
barrier properties even further especially the PO2 , due to stronger interfacial interactions
with PA 6.[65] Lopez-Rubio and Lagaron (2008) investigated the retort improvement, when
blending EVOH with amorphous PA (aPA) and a nylon-containing ionomer as blending
additives. Only the binary blend EVOH/aPA showed a real improvement in PO2 immediately
after retorting when compared to neat EVOH. The blends containing the ionomer per-
formed even worse than the pure EVOH.[66] Ares et al. (2009) developed a PP/EVOH blend
compatibilized with sodium ionomer. The PO2 of PP/EVOH blends containing more than 30
wt% decreased by 80% as compared to the pure PP. On the other hand the PH2 O was
increased more than 7 times upon addition of EVOH and less than 5 wt% sodium ionomer,
due to its hydrophilic character. However, when more than 5 wt% of the sodium ionomer
was added the PH2 O became even lower than pure PP, and the PO2 improved even further.[67]
EVOH29 was blended with poly(lactic acid) (PLA) by Sanchez-Garcia et al. (2011). The PO2
of the PLA was improved at 0% RH, but performed slightly poorer at 80% RH. The PH2 O
increased opposed to neat PLA.[68] A blend containing poly(ethylene-co-methacrylic acid)
(PEMA) and EVOH38 was produced by Seethamraju et al. (2014) for organic light emitting
diodes (OLED) application. When an EVOH content of 5, 10 and 20 wt% was added to the
blend, the PO2 , respectively, decreased 1.4, 2.0, and 3.3 times. For the PH2 O the decrease was,
respectively, 8 and 15 times for 5 and 10 wt% EVOH when compared to pure PEMA.
Addition of montmorillonite (MMT) to create a nano-composite blend of PEMA/EVOH led
 POLYMER REVIEWS 221

to a 25-fold reduction of the PO2 and a 12-fold reduction of the PH2 O .[69] A film of ethylene
vinyl acetate (EVA) copolymer was hydrolyzed on both surface sides by Puente et al. (2015),
creating the structure EVOH/EVA/EVOH. When the hydrolysis time increased, the thick-
ness of the generated EVOH layers was also increased, causing the PH2 O to decrease due to
the crystalline phase of the EVOH layers.[70]
More recent studies show the effect of multiplication extrusion, also used for microlayer
technology, on blends. Zhu et al. (2014) used an assembly of force-assembling elements
(FAEs), similar to multipliers, combined with one extruder. In a FAE the melt blend is first
sliced into a left and right part, then the melt is stretched biaxially, finally the two parts are com-
bined. When one FAE was applied on a blend with 25 wt% of EVOH32 the PO2 was decreased
with more than 1 order of magnitude compared with a non-FAE specimen. The PCO2 was
hardly effected by the application of FAE.[71] Zhang et al. (2015) on the other hand found that
a LLDPE/EVOH44 (50/50 wt%) blend extruded with up to 8 multipliers caused both the PO2
and PH2 O to increase when the number of multipliers increased, because the multipliers broke
the elongated and layer-like morphology of the blend. When no multiplier was used, the
LLDPE/EVOH blend had a PO2 , that was 1000 times lower than that of neat LLDPE.[60]

2.4. Additives and nano-composites

2.4.1. Additives
The addition of functional compounds can also change the barrier properties of EVOH,
resulting in either strengthening or weakening the barrier. Beta-cyclodextrin (bCD) was
incorporated into EVOH44 by L
opez-de-Dicastillo et al. (2010) as a scavenger for food
aroma compounds such as terpenes. Even though the Tg and crystallinity were slightly
increased, the barrier against O2, CO2, and H2O became worse due to an increase in free vol-
ume in the matrix.[72] This group also developed an antioxidant packaging film based on
EVOH44 and green tea extract (GTE). The addition of 5 wt% GTE led to a decrease of the
PO2 at 23
C and 50% RH and an increase at 90% RH. A similar effect was observed for the
PH2 O at 23
C, which decreased up to 50% at 50 and 75% RH, but increased at 90% RH as the
film appeared to be more sensitive to water than the regular film.[73] Lagaron et al. (2012)
found that 4 wt% of a nano-additive oxygen scavenger (O2BlockÒ ) decreased the PO2 of
EVOH29 by 29% at 21
C and 50% RH and by 42% at 90% RH. The PH2 O even decreased by
71%.[74] Peter et al. (2014) showed that the addition of low concentrations of N,N’-bis
(2,2,6,6-tetramethyl-4-piperidyl)-isophthalamide caused a decrease in PO2 of approximately
30% through molecular interactions, however once concentrations were over 1.5 wt%, the
PO2 increased again. It is interesting to note that the haze decreased at low additive concen-
trations and increased above 2 wt%, indicating that at low concentrations both the barrier
and optical properties improved due to the structural changes in EVOH.[13] Vannini et al.
(2016) added different low-molecular-weight additives to EVOH32 and EVOH44 in order
to improve the processability through a decrement in the crystallization temperature. How
this affects the barrier properties was not investigated, but it is known that the crystalline
phase notably influences the barrier so further research is needed.[75]

2.4.2. Nano-composites
Apart from additives, the addition of silicates can also influence the barrier properties of
EVOH. This can be achieved either through the creation of a tortuous path for gas diffusion
222 C. MAES ET AL.

or through structural changes to the polymer itself. In case of the tortuous path hypothesis
the silicate nano-platelets can be considered as impermeable inorganic crystals in the poly-
mer matrix, causing the gas molecules to diffuse around them thus resulting in a longer dif-
fusion path.[76,77] Liu et al. (2010) showed that by changing the blow film process, the
orientation of EVOH/nano-SiO2 composites can be improved so that the grain size of the
nano-composites becomes smaller and higher in number, which improves the crystallinity
and the degree of molecular chain order, thus improving the barrier properties. The addition
of 5 wt% SiO2 decreases thePO2 (23
C, 50% RH) by 64.4% and the PH2 O (38
C, 90% RH) by
54.2%. However, the optical properties (haze and transparency) became worse with
increased nano-SiO2 concentrations.[78] Nam and Kim (2010) used various contents of an
inorganic silicate precursor tetraethoxyorthosilicate (TEOS) and a silane coupling agent 3-
isocyanatopropyl triethoxysilane (IPTES) to prepare EVOH/SiO2 nano-composites, and
revealed that an optimum content of both was required to attain a high barrier material. In
the optimum range of TEOS and IPTES, the PO2 was respectively improved by approxi-
mately 70% and 50%.[79] Kim and Lee (2014) used graphene oxide (GO) and EVOH32 to
create EVOH/GO nano-composites and found that 0.3 wt% of GO can reduce the PO2
(25
C, 60% RH) to 63% compared to a pure EVOH32 film. However, the addition of GO
also decreased the transparency to 84% at a wavelength of 550 nm.[80] Kim and Cha (2014)
revealed that the incorporation of inorganic planar-structured nanoclay MMT can lead to a
dramatic decrease of both PO2 at 23
C, 50% RH and water vapor permeability (PH2 O ) at 40
C
90% RH: at 3 wt% the decrease was most prominent, respectively 59.4 and 90.1%. There was
also an improvement in transparency and mechanical properties. However tensile strength
deteriorated above 5 wt% due to stiffness of the nanoclay itself and the transparency became
worse at 7 wt%.[14] Kim et al. (2014) added small concentrations of exfoliated graphite
(EFG) to EVOH32 to create nanocomposites with improved barrier properties. At 23
C and
0% RH the PO2 was decreased by 97% and by 64% at 80% RH.[81] Cerisuelo et al. (2014)
coated EVOH29 nanocomposites containing 2 wt% bentonite on PP and PET, but found
that this did not significantly improve the barrier properties as opposed to the PP and PET
samples coated with regular EVOH29.[82] Sadeghi and Shahedi (2016) developed an EVOH/
chitosan polymer mixture film containing nano-ZnO. The incorporation led to a decrease in
both PO2 and PH2 O when the ZnO content was increased by filling pores in the film matrix
and the creation of a tortuous path.[83] The incorporation of MMT and phosphorylated soy-
bean isolate protein (PSPI) into EVOH32 led to nanocomposites with enhanced mechanical
and barrier properties. Wang et al. (2016) found that MMT-PSPI content of 3 wt% improved
the PO2 (23
C, 0% RH) by 73.5% and the PH2 O (25
C) by 61.3%. When the MMT-PSPI con-
tent became higher than 3 wt% the PO2 increased once more.[84]

2.5. Impact of processing conditions and technologies

The permeability can also be greatly influenced as a consequence of the polymer processing.
Parameters such as processing temperature and the time to cool down amongst others, often
have an effect on the material characteristics such as crystallinity. Processes like heat sterili-
zation, radiation and antibacterial treatments can also have an impact on the barrier proper-
ties. The most accurate way of determining the actual oxygen permeability for a certain
application is the measurement on the final item produced. In this paragraph the influence
of several process parameters on the gas barrier properties of EVOH are discussed.
 POLYMER REVIEWS 223

2.5.1. Processing temperature

Processing temperature has an important impact on the barrier properties. The data gener-
ated by Kuraray co. Ltd. were measured on samples that received a pre-heat treatment
according to the ISO 14663-2 norm of 10 minutes at 20
C below the Tm (e.g., approximately
160
C for EVOH32) to erase the thermal history of the films because samples often undergo
a different heat treatment during their processing.[85] The processing temperature has influ-
ence on the crystallinity. The non-heat treated EVOH32 film had a PO2 which was 4 times
higher than that of the EVOH32 film which received a heat treatment of 140
C. In case of
the uniaxially oriented EVOH32 film the heat treatment of 140
C improved the PO2 8 times
opposed to the non-heat treated film with uniaxial orientation (Fig. 3). This might explain
why some values of different studies measured under the same conditions may vary. How-
ever, more in-depth research is needed.

2.5.2. Stretching
Films can be stretched in one or even two directions resulting in uniaxially or biaxially ori-
ented films, respectively. The crystallinity of the film is on its turn directly related to the ori-
entation. In case of the heat treated films (140
C) the crystallinity of the uniaxially oriented
film was 68% as compared to 58% for a non-oriented film, the biaxially oriented film had a
crystallinity of 70%, which influences the oxygen permeability; the PO2 of the uniaxially ori-
ented film and the biaxially oriented film decreased respectively nearly 3 and 14 times
opposed to the non-oriented film, as shown in Fig. 3.[9,86]

2.5.3. Thermoforming
Thermoforming has a significant impact on the thickness distribution of the material. In this
process the sheet or film material is softened using heat and shaped in a mould by mechani-
cal stretching and/or pressure. The drawing depth and angle of the corners determine the
thickness distribution and surface area, and thus the barrier properties of the final packaging.
However, this effect can be partly counteracted as stretching of the film can affect the orien-
tation of the polymer chains, which are possibly drawn closer to each other. Because of this
the chain mobility in the amorphous zones can be restricted, making it more difficult for
oxygen molecules to pass through, and thus resulting in lower oxygen permeability. Addi-
tionally the cooling step to prevent shrinkage after production and the cooling rate affect the
crystallization of the polymer and therefore also the permeability. Buntinx et al. (2014) also
found that trays with straight corners performed better than round corners possibly due to
the stretching of the EVOH.[39]

2.5.4. Retort processing and similar treatments

Careful attention needs to be paid when multilayer structures containing EVOH are exposed
to a retort process (e.g., sterilization of ready meal and pet food). The combination of high
temperatures and steam can render the protective water barrier layer (e.g., PE, PP, etc.) in a
multilayer film ineffective for a limited time. The encapsulated EVOH layer will be exposed
to the steam and take up water. Once the water barrier of the surrounding layers has restored
itself the water is enclosed inside, resulting in a negative effect on the oxygen barrier of
EVOH. This phenomenon is called retort shock. Some studies even report an increase of
PO2 with a factor of 100. The barrier usually restores itself after a period of time (e.g., days to
224 C. MAES ET AL.

Figure 8. Schematic representation of the oxygen permeability of EVOH before, during and after a retort
process.

weeks) depending on the retort conditions and the structure of the multilayer.[9,11,87] In
Fig. 8 a schematic overview of the PO2 before, during and after retort is shown.
Mokwena et al. (2009) investigated the impact of microwave sterilization (MS) on the
barrier properties of 2 films in comparison to a regular retort process. Film A was a lami-
nated PET//EVOH32 (12 mm)//PP film and film B was a coextruded (represented by /) film
laminated (represented by //) to an outer PET layer: PET//PP/tie/Nylon 6/EVOH27
(15 mm)/Nylon 6/tie/PP. The retort procedure with a thermal treatment of F0 D 3 min led
to an 11- and 48-fold increase of the PO2 , as compared to the untreated film A and film B,
respectively. On the other hand, MS with F0 D 3 min led to a 5- and 17-fold increase of the
PO2 as compared to the controls of film A and B, respectively. Even a MS with F0 D 6 min
resulted in a lower PO2 than the retort samples, which was 10 and 24 times higher for respec-
tively film A and B. The higher values for retort heat treatment were attributed to the
increased plasticising effect from water absorption by the films. After 2 months of storage at
room temperature over 50% of the barrier was recovered, however beyond 2 months the bar-
rier slowly deteriorated.[88] Galotto et al. (2010) found that high pressure processing (HPP),
surprisingly slightly decreased the O2GTR of PE/EVOH/PE as compared to non-treated
samples. This is probably due to a more compact structure formed by the high temperature,
yet the changes were very small and the variation was large. It is also interesting to note that
the water vapor transmission rate (WVTR) increased due to swelling.[89] Juliano et al. (2010)
found that EVOH-based multilayer materials showed potential for HPP and are already
used for commercial production. The variation in PO2 for HPP at high temperature (HP-
HT) was lower than 12% compared to non-treated samples.[90] Dhawan et al. (2014) used
the same films as Mokwena et al. (2009) to evaluate the influence of Pressure-Assisted Ther-
mal Sterilization (PATS) also known as HP-HT of 680 MPa of 5 minutes at 100
C on the
PO2 at 23
C and 55% RH. For film A this led to a 5-fold increase and for film B this was
4 times higher. The PH2 O (38
C, 100% RH) also increased by, respectively, 74% and 16% for
films A and B. The difference between film A and B was explained by the overall change in
crystallinity and the free volume.[91] These studies show that the impact of either MS or
HPP on the barrier properties of the EVOH layer is less severe as compared to a regular
retort process.
 POLYMER REVIEWS 225

2.5.5. Irradiation
Lopez-Rubio et al. (2007) found that electron beam irradiation at doses of 30 and 90 kGy
caused oxygen scavenging activity in an EVOH29 film. Most likely free radicals formed dur-
ing the irradiation process react with oxygen, causing an oxygen blocking effect. However,
after exhaustion of this capacity the films showed a higher PO2 due to faster oxygen diffusion
caused by a reduction in crystallinity.[92]

2.5.6. Antimicrobial gases

Chlorine dioxide can be used as an antimicrobial gas in the headspace of fresh products like
meat, poultry and seafood. However, Rubino et al. (2010) showed that this gas also exerts an
effect on the material characteristics of polymers as it can change the chemical structure.
The PO2 of a multilayer EVA/EVOH/EVA film was increased by nearly 50% and the CO2
permeability (PCO2 ) even doubled, changing the permselectivity ratio (PCO2 6 PO2 ).[93]

3. Water vapor permeability of EVOH

Similar to the PO2 and O2GTR, in this paper the PH2 O is a thickness corrected value in g.mm/
(m2.day), while the WVTR is expressed in g/(m2.day). When compared to other polymers,
EVOH has medium to poor (for EVOH with lower mol% ethylene) water barrier proper-
ties.[94] Other medium water barriers are PET, LDPE and PVDC (Fig. 7). Materials like PP
and HDPE are preferred as moisture barriers whereas PS, polybutylene terephthalate (PBT),
PC and PA 6 have lesser water vapor barriers. The PH2 O of EVOH is also influenced by the
ethylene content (Fig. 2), showing a decreased PH2 O at higher mol% of ethylene.[10,26,95] The
PH2 O increases at higher temperatures and higher RH. At lower RH (30-60% RH) this pro-
cess is slow, but beyond 75% RH it becomes more pronounced.[10] Even though EVOH44
and EVOH48 show similar PH2 O like LDPE and PET, these last two polymers are still used
as outer barrier materials because they also provide good mechanical properties (e.g., heat
seal, strength) and can be more easily applied in thicker structures, whereas EVOH is usually
applied in thin structures.[9] Also, as was discussed previously the presence of water has a
negative impact on the barrier properties of EVOH due to its moisture sensitivity, thus
EVOH is not the best choice as water vapor barrier.[11]
There are several techniques like the addition of nano-platelets, which can be used to
increase the hydrophobicity and the water barrier of EVOH. This is especially interesting for
applications like encapsulating OLEDs, which require a very low O2GTR and WVTR.[96]
Several studies, which were already mentioned before, presented some effects of blending,
and the addition of additives and nano-particles on the PH2 O . Next to this, techniques like
surface treatments can also improve the PH2 O . Hong et al. (2009) treated EVOH32 with
plasma to modify the surface, which enhanced the hydrophobic properties due to the forma-
tion of fluorine-containing functional groups.[97] Tenn et al. (2012) also used plasma treat-
ment on EVOH29 and EVOH44 to generate hydrophobic surfaces. This reduced the PH2 O
up to 28% at 25
C.[98] Another study showed the use of hydrolysis reactions on an EVA
copolymer film. The surface of both sides of the film was hydrolyzed, creating the structure
EVOH/EVA/EVOH. When the hydrolysis time increased, the thickness of the generated
EVOH layers was also increased, causing the PH2 O to decrease due to the crystalline phase of
the EVOH layers.[70]
226 C. MAES ET AL.

Figure 9. Comparison of gas permeability between EVOH32 and HDPE at 23
C, 0% RH. Based on data
from Kuraray co. Ltd. (2017),[7] The Nippon Synthetic Chemical Industry co. Ltd. (2013),[136] Armstrong
(2011),[107] McKeen (2012)[21] and Maxwell and Roberts (2010).[137]

4. Permeation of other gases through EVOH

EVOH is not only an excellent barrier against oxygen, but also for a broad range of other
permanent gases such as carbon dioxide, nitrogen and hydrogen.[15,17] In Fig. 9, a compari-
son of the permeability of EVOH for several gases is made between EVOH32 and HDPE.
For the gases presented in Fig. 9, EVOH shows permeabilities for O2, N2, CO2, SO2, CH4
and Freon 12 between 0.4 and 12 cm3.mm/m2.day.atm at 23
C and 0% RH, which are 3 to 5
orders of magnitude lower than those of HDPE. He and H2 show higher permeabilities,
which are, respectively, 1–2 and 2–3 orders of magnitude lower for EVOH than HDPE. This
might be explained by their small molecule size.
However, the available data on these gases are usually limited to permeability measure-
ments at 0% RH, making it more difficult to estimate the permeability under different condi-
tions. Table 4 presents gas permeability data of EVOH32, EVOH38 and EVOH44.
When the ethylene content increases, the gas permeability increases as well. The influence
of temperature can be expressed by the Arrhenius equation for the other gas molecules in the
same manner as was previously discussed for oxygen, meaning that an increase in tempera-
ture leads to a higher gas permeability. The data also show that the permeability for other
gases is also influenced by the RH. In general the factors that influence oxygen permeability
also influence the permeability for other permeants, but the gas permeability is also strongly
dependent on the permeant itself. The permeability for nitrogen is lower than that of oxygen,
while the permeability for carbon dioxide and helium is higher when measured at the same
conditions. In general the gas permeability of polymers is lower for larger molecules. How-
ever, carbon dioxide is a larger molecule than oxygen, yet it has a higher permeation rate.
This phenomenon might be explained through the combination of the molecular size and
the affinity for the polymer matrix. Carbon dioxide has a lower diffusion rate than oxygen
through the same polymer due to its size, but it has a higher chemical affinity for the poly-
mer matrix leading to a much higher solubility than oxygen. The permeability P can be cal-
culated as the product of the diffusion coefficient D and the solubility coefficient S
(P D DS), and is higher for carbon dioxide than for oxygen resulting in a higher
 POLYMER REVIEWS 227

Table 4. Gas Permeability (P) through different types of EVOH at various conditions. Based on data from
Kuraray co. Ltd. (2017),[7] Yam (2009)[27] and Armstrong (2011).[107]
P [cm3.mm/(m2.day.atm)]

Gas Conditions EVOH32 EVOH38 EVOH44

N2 23
C, 0% RH 0.4 1.6 3.1

23
C, 65% RH 0.8 2 3.1
25
C, 0% RH 0.3 2.6
35
C, 0% RH 0.8 3.1 5.8
O2 5
C, 0% RH 1.1 2.3 6.5
23
C, 0% RH 5 10 23
23
C, 65% RH 7.9 12 31
35
C, 0% RH 12 24 48
Kr 50
C, 0% RH 8 36
Ar 35
C, 0% RH 32
50
C, 0% RH 10 140
CO2 5
C, 0% RH 3.9 6.6 22
23
C, 0% RH 12 26 83
23
C, 65% RH 24 59 91
25
C, 0% RH 16 142
35
C, 0% RH 26 83 193
H2 20
C, 0% RH 600 4000
He 5
C, 0% RH 1045 1783 2558
23
C, 0% RH 3603 6433 9223
23
C, 65% RH 7402 8661 9961
25
C, 0% RH 3200 8200
35
C, 0% RH 5308 9533 13795

permeability.[27] A more logical explanation for this is the kinetic diameter, which represents
the smallest effective dimension of a given molecule. The kinetic diameter is smaller for car-
bon dioxide than that of oxygen, respectively, 0.330 and 0.346 nm, making it easier for car-
bon dioxide to diffuse through the polymer matrix[21,99].
Next to helium there is only limited permeability data for other noble gases such as
krypton and argon at 35 and/or 50
C and 0% RH. Unlike helium, which permeates easily as
was mentioned before, the permeability of EVOH for krypton and argon is closer to that for
oxygen due to their larger molecular size.
Armstrong (2010) compared the radon diffusion coefficient (DRa ) of EVOH44 with other
materials typically used in the construction sector to prevent radon intrusion and improve
indoor air quality. The DRa of EVOH44 is several orders of magnitude lower than polyole-
fins, polyurethane (PU) coating and plasticized polyvinylchloride (PVC), and even lower
than bitumen coated aluminium foil as shown in Fig. 10. Therefore the use of EVOH in a
composite with commonly used materials such as HDPE, LLDPE and PP could dramatically
reduce the diffusion of radon.[17]

5. Permeability of EVOH for organic substances

5.1. Aromas and flavors barrier
Next to its outstanding gas barrier, EVOH is also extremely suitable to prevent aroma and
flavor scalping in food packaging.[15] In Fig. 11 the permeability of EVOH, PVDC and
LDPE for several aroma and flavor components is shown. The type of EVOH is not speci-
fied; however the barrier properties outperform both LDPE and PVDC for all components
228 C. MAES ET AL.

Figure 10. The radon diffusion coefficient of EVOH44 compared to other materials. Based on data from
Armstrong (2010)[17] and Jiranek et al. (2008).[138]

under dry conditions. PVDC has a permeability (P) for ethyl hexanoate, ethyl 2-methylbuty-
rate, hexanol, trans-2-hexanol, d-limonene and propyl butyrate of typically 1–3 orders of
magnitude greater than EVOH, whereas the permeability of LDPE for these compounds is
5–7 orders of magnitude higher than EVOH with the exception of the P for trans-2-hexenal
which is less than 1 order of magnitude higher for PVDC and about 4 orders of magnitude
higher for LDPE[27].
Over the past years various studies have been performed on the permeability of aromas
and flavors, yet no standard procedure is recommended similar to the permanent gases. The
simplest method is the gravimetric method similar to the ASTM E96 method used for
WVTR, in which the permeation is determined by weight loss.[100] Another method is the
sensory test, where trained panellists smell at different intervals until the aroma is detected.
It is also possible to detect the permeant aroma compounds through gas chromatography
(GC). There are many studies that focus on the sorption, which can be determined by the
gravimetric method or analytical techniques like GC and high performance liquid

Figure 11. Comparison of aroma permeability between EVOH, PVDC and LDPE at 25
C, 0% RH. Based on
data from Yam (2009).[27]
 POLYMER REVIEWS 229

Table 5. Permeability of ethyl butyrate and a-pinene through EVOH32 at 25
C and different RH. Based on
data from Lopez-Carballo et al. (2005).[15]
P [g.mm/(m2.day.atm)]

RH (%) Ethyl butyrate a-Pinene

0 <0.00011 <0.000021
11 <0.00011 <0.0000009
23 <0.000042 <0.0000088
54 0.0024 0.00021
75 0.22 0.017
100 1.5 0.096

chromatography (HPLC).[27] Fukamachi et al. (1996) used a GC-based method and found
that the sorption of flavors (ethyl hexanoate, n-octanal and n-octanol) from an ethanol solu-
tion into EVOH was influenced by the ethanol content in the solution. A maximum sorption
for the three components was detected at 10–20 v% ethanol and was, respectively, 6.2, 3.5
and 4.1 times higer for ethyl hexanoate, n-octanal and n-octanol than at 0 v% ethanol.[101]
Lopez-Carballo et al. (2005) determined the permeability, diffusion and sorption of ethyl
butyrate and a-pinene through an EVOH32 film at different RH. The organic compound
uptake was analysed by GC-flame ionization detector (FID) and Fourier transform infrared
spectroscopy (FT-IR) was used to determine the mass transport of the aromas. The results
are shown in Table 5. EVOH displays excellent barrier properties to both aroma compounds,
which were reported to be 1000 times lower than those measured in LDPE, even at 100%
RH. Remarkable is that the aroma permeability as a function of the RH shows a similar trend
as the oxygen permeability (Fig. 6), a slight improvement at low RH is noted compared to
dry conditions, which can be explained by the free volume theory.[15,102]
Aroma permeation can also be measured by solid-phase micro-extraction (SPME), where
a container filled with aroma compounds is placed in a glass container and a fused silica cap-
illary is used to trap the aroma compounds that permeated through the container to the out-
side. The compounds are desorbed and analyzed by GC. Berlinet et al. (2008) used this
method to investigate the permeation of orange juice aromas through a PET bottle and a
HDPE cap. It was discovered that the permeation mainly occurred through the cap. By using
a multilayer HDPE cap with an internal layer of LDPE/EVOH/LDPE, the permeation was
considerably limited. The permeation of ethyl butyrate was reduced by a factor 30.[103] Zhou
et al. (2004) developed an online measurement system to determine the permeation of aro-
mas through films by coupling a permeation system to a purge-and-trap/fast gas chro-
matographic system (P&T/fGC). With this method, the permeation of limonene and ethyl
butyrate was measured through three multilayer HDPE films, which contained respectively
EVOH, nylon and no barrier. The films containing EVOH and nylon had comparable aroma
barrier properties for both limonene and ethyl butyrate and were superior to the film with-
out barrier layer. This study also showed the effect of co-permeation, where one compo-
nent’s presence can influence the permeability of the other component. While there was no
effect on the permeability of limonene, the permeability of ethyl butyrate was more than
doubled when limonene was present as a co-permeant for both films.[104]
Just like the PO2 , different factors like RH influence the aroma and flavour permeability.
Apart from the factors mentioned in the section about PO2 , Leufven and Hermansson (1994)
found that the pH also has an impact on the permeation of aromas due to the changes in
230 C. MAES ET AL.

polarity and structure of the molecules. The sorption of trans-2-hexenol, 2-heptanone,

6-methyl-5-hepten-2-one, 6-methyl-5-hepten-2-ol and limonene increased when the pH
increased from 4 to 7.[105,106]

5.2. Fuels and chemicals barrier

EVOH can also be used as a barrier against fuels and other chemicals like liquid solutions of
benzene, toluene, ethylbenzene and xylene isomers (BTEX). EVOH is already widely used as
a barrier material in automotive applications like fuel tanks.
EVOH also offers good chemical resistance to volatile organic compounds, hydrocarbons
and organic solvents. The exposure to certain solvents can cause softening, swelling or envi-
ronmental stress cracking in many polymers. However, EVOH retains its key physical prop-
erties in the presence of most organic solvents, acid and alkali solutions, and non-ionic
surfactants. This is attributed to the combination of a highly ordered crystalline structure
dispersed in disordered amorphous regions which give EVOH desirable properties of high
resistance to the diffusion of gases and solvents.[107]

5.2.1. Fuels and alcohols

Lagaron et al. (2001) determined the permeability of fuel using the gravimetric method and
found that EVOH has outstanding barrier properties to fuel C (toluene and iso-octane 50/50
v/v) compared to PA 6 and HDPE (Table 6). However when methanol is added to create oxy-
genated fuel as a clean alternative to standard fuels, the barrier deteriorates drastically, due to
methanol’s plasticizing effect on EVOH, the same phenomenon can be observed in PA 6.
HDPE is more resistant to methanol permeation than EVOH and PA 6, although EVOH still
easily outperforms HDPE as a barrier against fuel CM15 (fuel C with 15 v% methanol). The
plasticizing effect is less pronounced when 10 v% ethanol is added to fuel C (i.e., CE10).[18]
Zhao et al. (2015) developed an automated permeameter using a GC-FID to measure the
permeation of the different fuel components as low as 1 mg/m2.day. These results showed
that the permeated flux of fuel C mainly contained toluene, which was confirmed with per-
meation experiments with pure toluene and iso-octane (no results were shown due to no
detectable loss), whereas mixtures with ethanol mainly contained ethanol. This means that
the higher permeability of fuel CE10 compared to fuel C is due to the high permeation of
ethanol. This also corresponds to the permeability of EVOH32 for CM15, which is about 3

Table 6. Fuel permeability through EVOH, PA 6 and HDPE. Fuel C: toluene/iso-octane (50/50 v/v); Fuel
CM15: Fuel C C 15% methanol; Fuel CE10: Fuel C C 10% ethanol. Based on data from Lagaron et al.
(2001)[18] and Nulman et al. (1998).[135]
P [g.mm/(m2.day)]

40
C, 12% RH 21
C, 12% RH

Fuel/ Permeant EVOH32 PA 6 HDPE EVOH32

Fuel C 5 5,060 62,600 9

Fuel CM15 4,500–5,500 205,000 71,000 700
Fuel CE10 20 40
Methanol 24,000–61,700 360,000 1,400 7,300
Toluene 4 6
 POLYMER REVIEWS 231

orders of magnitude higher than for fuel C at 40
C and 12% RH due to the high permeability
of EVOH32 for methanol, which is 4–5 orders of magnitude than fuel C. At 21
C and 12%
RH, this effect is less pronounced, yet the permeability for CM15 is still nearly 2 orders of
magnitude higher than fuel C.[108] Gagnard et al. (2004) observed the co-permeation of tolu-
ene and methanol using a GC-FID. EVOH has a low permeability to toluene, but this is
increased by the presence of methanol, which has a higher permeation. This makes struc-
tures with EVOH sandwiched between HDPE interesting in the automotive sector, since
HDPE has a lower permeability to methanol (Table 6).[109,110] Inverse GC (IGC) was used
by Cava et al. (2007) to measure the influence of RH on alcohol transport through EVOH38.
Three alcohols, methanol, ethanol and 1-butanol were used. The methanol diffusion was
most influenced by RH and 1-butanol the least, however for all three alcohols a sharp incre-
ment could be noticed between 35 and 47% RH owing to the plasticization of the
copolymer.[111]

5.2.2. BTEX
In several studies the barrier properties of EVOH against BTEX have been investigated. BTEX
contamination is especially important in groundwater and soils from where they can evapo-
rate into building constructions and thus affect the indoor air quality.[17] Geomembranes
with an EVOH barrier layer offer protection against these toxic vapors.[112,113] McWatters
and Rowe (2015) found that the permeability coefficients for BTEX and chlorinated hydro-
carbons of HDPE and LLDPE monolayer geomembranes can be reduced by 2 to over 4
orders of magnitude by inclusion of an EVOH barrier layer in a LLDPE geomembrane.[114]

5.2.3. Other applications

Sensor nodes in ubiquitous sensor networks (USN) require autonomous replacement of
deteriorated sensors with reserve sensors. Lee et al. (2012) developed an encapsulation tech-
nique to avoid poisoning of the reserve sensors and an autonomous activation method to
replace the sensor through thermal decomposition of the encapsulation material. EVOH27
was found to be a suitable barrier material to protect the sensor against formaldehyde gas
and also did not have a negative impact on the sensor during its thermal decomposition.[115]
The permeation of flammable liquids through intermediate bulk containers (IBC), jerricans
and drums during transport can lead to the creation of an explosive atmosphere. Bethke
et al. (2013) found that when no barrier like EVOH was present, the lower explosive limit
(LEL) for trichloroethylene, toluene and n-hexane was reached within a few hours at 40
C.
Whereas the incorporation of EVOH reduced the permeation with more than 1 order of
magnitude.[116] Agricultural films containing a barrier like PA are used for three reasons: to
decrease the dose of fumigants in soil disinfestations, to decrease the emission of fumigants
into the atmosphere and to decrease the operator exposure. Fouillet et al. (2014) compared a
new film containing EVOH to an existing film with PA as a barrier to dimethyl disulfide
(DMDS) fumigant and found that EVOH is an alternative for PA.[117]
The effect of blending EVOH with modified PA (mPA) on the permeation of turpentine
(white spirit) was investigated by Yeh et al. (2006). Three different EVOH types (EVOH32,
EVOH44 and EVOH48) were blended with mPA and bottles were prepared from these res-
ins. The white spirit permeation decreased when the mol% ethylene in EVOH was lower
and increased with an increasing mPA content in the EVOH/mPA blend. The white spirit
permeation of neat EVOH32, EVOH44 and EVOH48 was, respectively, 882, 254 and
232 C. MAES ET AL.

208 times lower than PE.[43] Yeh et al. (2006) also investigated the permeation of gasoline. It
was found that 22% of a gasoline mixture permeated through a PP bottle within one month.
When 10 wt% EVOH32 was blended with PP, the permeation was reduced by a factor 8.6. A
PP and 10 wt% mPA blend led to a decrease of a factor 10.1, which is better than the PP/
EVOH blend. Although EVOH is intrinsically a better barrier, this can be explained by the
fracture of the lamina structure of the EVOH. When EVOH/mPA blend was added to PP
the barrier improved as the mPA content increased, reaching a minimum permeation, which
was 113 times better than neat PP, at 83.3 wt% mPA in the EVOH/mPA blend.[118]

5.3. Functional barrier

Packaging materials intended for food contact, commonly referred to as food contact mate-
rials (FCM) must comply with Regulation (EC) N
1935/2004 and plastic materials addi-
tionally must meet with Regulation (EU) N
10/2011. These regulations state that FCM
may not transfer their constituents to food in quantities that may endanger human health
or bring about unacceptable changes in the composition of the food or bring about a dete-
rioration of the organoleptic characteristics thereof; and contain a union list of authorized
substances and their specific migration limit (SML) into food. However, non-authorised
substances may be used, provided they are separated from the food by a functional barrier,
which meets the criteria and limits the migration of these substances to below a given
detection limit.[27,119]

5.3.1. Mineral oils

In 2012 the European Food Safety Authority (EFSA) published a scientific report on the
occurrence of mineral oil hydrocarbons in food,[120] in which possible health risks caused by
exposure to mineral oil in food are brought to attention. One of the main causes for mineral
oil contamination in food is recycled cardboard. Lorenzini et al. (2010) found that mineral
oil compounds migrated from printing inks and recycled fibers in paperboard to dry food in
concentrations far exceeding the acceptable daily intake (ADI). The highest measured con-
centrations were 1000 times higher than the ADI value. It was also found that higher molec-
ular weight compounds (>C24) seem negligible with regards to migration for both mineral
oil saturated hydrocarbons (MOSH) and mineral oil aromatic hydrocarbons (MOAH).
About 60–80% of the <C24 fraction might be transferred into the packaged food when no
functional barrier is present.[121] Vollmer et al. (2011) observed similar findings. The con-
centration of MOSH surpassed the ADI of 0.6 mg/kg bodyweight (using generally applied
conventions of 60 kg bodyweight and the consumption of 1 kg contaminated food) with a
factor of 10 to 100 and about 10–20% of the migrated compounds were MOAH of which
the safety is still uncertain based on the available toxicological data. These results are quite
alarming, especially because the samples were only 2–3 months old.[122]
The 3rd draft document for the regulation of mineral oils from recycled fibres in paper-
board was presented in 2014 by the German Federal Ministry of Food and Agriculture, in
this document the limits were set on 2 mg/kg and 0.5 mg/kg for MOSH and MOAH, respec-
tively.[123] In 2017 the 4th draft was published, which only mentions the migration limit for
MOAH and obligates the use of a functional barrier.[124] This upcoming regulation makes
the need for inclusion of functional barriers in paper-based packaging for food more urgent.
Several studies have investigated functional barriers against the migration of mineral oils
 POLYMER REVIEWS 233

from paperboard packaging. A few studies mention EVOH as a possible functional barrier,
but only limited data on permeation or migration rates have been published so far. One of
the main reasons is that no standard method has been established yet, also the detection
limit is challenging. Diehl and Welle (2015) summarized three different methods, which are
currently used by different research institutes: migration experiments, permeation experi-
ments and lag time experiments.
Migration experiments are performed according to standard testing procedure DIN EN
14338, in which the concentration of migrants in the food or food stimulants is deter-
mined.[125] Pastorelli et al. (2008) performed migration experiments on benzophenone,
which is commonly used as a photo-initiator in UV-cured inks. The migration was mea-
sured in cake at two different conditions. Cake packaged in PP contained over 30 times
more benzophenone than when a structure of PP/EVOH/PP was used at 40
C for 10 days.
At 70
C and 48 h the migration was twice as high for PP than for PP/EVOH/PP, the exact
structures were not specified.[126]
Permeation experiments are kinetic studies in which the permeation rate is derived by
measuring the concentration of the permeated migrants at different time points. In most
cases the migrants are spiked in much higher or the worst case concentrations either using
real mineral oil mixtures or model compounds. Fiselier and Grob (2012) spiked a donor
pack with real mineral oil mixtures at worst case concentrations on one side of the barrier
material and a PE film was used on the other side as an acceptor material. At different time
points a piece of the PE film was extracted with hexane for 2 hours at ambient temperature
and analyzed for presence mineral oils by on-line HPLC-GC-FID to determine the break-
through time of 1% of the initial concentration of the mineral oil at 60
C. This could be
recalculated to a time at 22
C (ambient temperature) by the Arrhenius equation. Because
mineral oil mixtures are complex and difficult to separate into single compounds only
the total amount of migrants could be determined when using a real mineral oil mixture.
The results are presented in Table 7. Whereas polyolefins such as PE and PP showed poor
barrier properties towards the mineral oil, PA and PET did not show breakthrough of 1% up
to 84 days at 60
C, which translates to a shelf life of more than 3910 days or 10.7 year at
22
C.[127] The same test was performed on two multilayer films containing only a few mm of
either EVOH32 or EVOH44 (Table 7). EVOH32 can easily compete with PA and PET.
There might have been a slight breakthrough of 2% at 84 days at 60
C, this was close to the
detection limit, however, after 56 days no breakthrough was detected, which still results in a
shelf life of over 2576 days or 7.1 year at 22
C. Considering that the initial spiked

Table 7. Comparison of breakthrough time of mineral oils through EVOH with other materials. Based on
data from Fiselier and Grob (2012)[127] and Maes et al. (2017).[128]
Time to reach 1% breakthrough of MOH

Film sample Test at 60
C [days] Recalculated to 22
C [days]

50 mm LDPE/LLDPE 0.0033 0.15

60 mm LLPE/HDPE 0.010 0.44
50 mm OPP 0.13 5.9
20 mm PA cast > 85.0 > 3910.0
12 mm PET > 85.0 > 3910.0
PE/tie/EVOH32/tie/PE film (16/5/4.4/5/18 mm) > 84.0 > 3864.0
PE/tie/EVOH44/tie/PE film (16/6/5.2/6/18 mm) > 56.0 > 2576.0
234 C. MAES ET AL.

concentration is far above the normal concentration present in cardboard, both EVOH films
can be considered effective functional barriers.[128]
Biedermann-Brem and Grob (2014) used a similar method, but instead of real mineral
oil mixtures, the donor paper was spiked with four surrogate substances: dipropyl
phthalate (DPP), 4-methyl benzophenone (MBP), triethyl citrate (TEC) and n-heptade-
cane (C17). Also a silicone paper was used as acceptor material instead of a PE film.[129]
Richter et al. (2014) used this method to evaluate the barrier of different samples from
the German and Swiss market, but added n-octadecane (C18) as a fifth surrogate sub-
stance. The barrier efficiency was classified in five classes, where class 1 had no signifi-
cant barrier, class 4 was a virtually tight barrier and class 5 included aluminum foil in
the barrier. Multilayer structures with EVOH were classified in class 4 as being virtually
tight barriers.[130] An automated permeation method was developed by Ewender et al.
(2013). No acceptor material was used, instead the downstream of a permeation cell was
flushed constantly with a permanent gas flow which led to a cryogenic sample trap cou-
pled to a GC-FID. At certain time intervals the trapped permeants in the sample trap
were desorbed by fast heating into the GC, allowing the permeation rate to be deter-
mined quite accurately by using 15 model substances (see Table 8) like n-alkanes (n-C12
to n-C24), substituted naphthalenes, substituted benzophenones, 2,7-diisopropyl naphtha-
lene (DIPN) and 2,2,4-trimethyl-1,3-pentanediol-di-isobutyrate (TXIB) representing
mineral oil chemistry. The paperboard was spiked with 750 mg/kg per substance, which
can be considered as worst case scenario. The study also showed that there is a linear
correlation between the logarithm of the experimental determined permeation rate at
40
C and logarithm of the vapor pressure calculated at 25
C, making it possible to pre-
dict other permeants. The study concluded that oriented PA (OPA) and oriented PET
(OPET) are good functional barrier materials against mineral oil migration, whereas pol-
yolefins provide insufficient barrier (see Table 8). It was also mentioned that a PP/
EVOH/PP multilayer structure reduced the permeation of benzophenone for about a fac-
tor of 2 compared to a PP monolayer film, however, no thickness or type of the EVOH
were specified.[131] Ewender et al. (2015) performed the same experiment on different
commercially available barrier films to find possible alternatives for OPA and OPET. A
biaxially oriented PP (BOPP) multilayer film containing EVOH and a biaxally oriented
PET film were found to be suitable alternatives for OPA and OPET. Unfortunately the
thickness of the EVOH layer in the BOPP film was not mentioned.[132] According to the
migration limits set in the draft document for the regulation of mineral oils from
recycled fibres in paperboard the time to reach the SML can be calculated according to
Eq. (6), where mfood is the mass in kg of the packed food, PR is the permeation rate in mg/
dm2.day which can be found in Table 8 for the different films, and A is the area of the
packaging in dm2 which is in contact with the food.[132]

SML : mfood
tSML D (6)
PR : A

Ewender and Welle (2014) adapted the previously described method by replacing the
spiked donor material by a spiked gas stream. This enabled the possibility of preconditioning
the cell with a non-spiked stream. Using this method the lag times at 70–120
C could be
experimentally determined, and allow a prediction of the lag times at ambient temperature
 POLYMER REVIEWS 235

Table 8. Permeation rate at 40
C of model compounds for MOSH/MOAH through different types of films.
Based on data from Ewender et al. (2013)[131] and Ewender et al. (2015).[132]
Permeation rate [mg/dm2.day]

Boiling point 20 mm 14.9 mm 12.4 mm 12 mm 20 mm BOPP multilayer

Substance [
C] BOPP OPA OPET BOPET with EVOH

Dodecane (C12) 216 4900 <0.01 <0.01 0.01 0.02

Tetradecane (C14) 254 1390 <0.01 <0.01 0.008 0.014
Hexadecane (C16) 287 238 <0.01 <0.01 <0.006 0.008
Octadecane (C18) 317 33 <0.01 <0.01 0.009 0.01
Eicosane (C20) 343 5.51 <0.01 <0.01 <0.006 <0.006
Docosane (C22) 369 1.02 <0.01 <0.01 <0.007 <0.007
Tetracosane (C24) 391 <0.03 <0.01 <0.01 <0.007 <0.007
Naphthalene 218 693 <0.01 <0.01 0.01 0.009

1-Methyl naphthalene 243 1590 <0.01 <0.01 <0.006 <0.006

1-Ethyl naphthalene 260 1000 <0.01 <0.01 <0.006 <0.006

DIPN 279 88 <0.01 <0.01 <0.006 <0.006

TXIB 280 244 <0.01 <0.01 0.015 <0.009

Benzophenone 305 68 <0.01 <0.01 <0.007 0.008

4-Methyl-benzophenone 326 22 <0.01 <0.01 0.017 0.017

Phenanthrene 336 32 <0.01 <0.01 <0.006 <0.006

236 C. MAES ET AL.

through the use of diffusion modelling. A functional barrier is sufficient if the lag time is
much higher than the shelf life of the packaged food. But so far no results on EVOH have
been published using this method.[133]

5.3.2. Non-intentionally-added substances

Several recent studies also investigated EVOH as a barrier against non-intentionally-added
substances (NIAS) migrants coming from PU adhesives used in laminated multilayer films.
F
elix et al. (2012) found more than 63 volatile and semi-volatile compounds as potential
migrants in the PU adhesives by using headspace solid-phase micro-extraction and gas chro-
matography coupled to mass spectrometry (HS-SPME-GC-MS). Two of these compounds
were NIAS: 1,6-dioxacyclododecane-7,12-dione and 1,4,7-trioxacyclotridecane-8,13-dione.
EVOH was shown to act as a barrier for polar migrants like caprolactam, triphenyl phos-
phate, an unknown adipate and 1,4,7-trioxacyclotridecane-8,13-dione. Although the migra-
tion of 1,6-dioxacyclododecane-7,12-dione was not quantified, it was not found in
the multilayer film containing EVOH between the PU adhesive and the food simulant, indi-
cating that EVOH acted as a functional barrier[134] Isella et al. (2013) used ultra-performance
liquid chromatography quadrupole-time-of-flight mass spectrometry to demonstrate the
efficiency of EVOH as a functional barrier against non-volatile NIAS from PU adhesives.
PE, even at higher thickness than normally used, showed no barrier for migration. Films
containing EVOH, on the other hand, showed good properties to retain these NIAS, only
one component migrated: N,N-dimethyllauramide[22] Carrizo et al. (2015) also found that
1,4,7-trioxacyclotridecane-8,13-dione easily migrated through PE, at even higher concentra-
tion than the 10 ppb limit (Regulation (EU) N
10/2011). EVOH successfully decreased the
migration, but did not inhibit it completely[119] Further research in this field is necessary to
confirm the usefulness of EVOH as a functional barrier.

6. Conclusion
EVOH copolymer has excellent barrier properties to gases, aromas, fuels, chemicals and even
offers a good functional barrier for mineral oils and NIAS, making it useful in a wide range
of applications. Its barrier properties are influenced by various parameters that are either
intrinsic material properties or extrinsic factors like environmental conditions or permeant
properties. The combination of these factors determines the barrier of EVOH.
A higher ethylene content in EVOH causes an increase in the PO2 and a decrease in the
PH2 O , additionally it also improves the processability. EVOH also has a high degree of crys-
tallinity and the barrier improves when the crystallinity is increased. The high Tg and low
free volume lead to low chain mobility, which inhibits the permeation of molecules through
the polymer. Addition of additives and nano-particles can either strengthen or weaken the
barrier of EVOH. In addition, material processing can change the material properties and
therefore have an impact on the barrier as well.
The temperature, RH and pressure of the environment also influence the barrier proper-
ties of EVOH. Generally a higher temperature will increase the permeability coefficient. Plas-
ticization and swelling effects may occur due to a change in pressure, which also affect the
barrier. The most important environmental parameter is RH due to water sensitivity of
EVOH. At low RH the permeability is initially reduced compared to dry conditions, which
reaches a minimum at about 20–40% RH. But at higher RH the barrier becomes worse owing
 POLYMER REVIEWS 237

to the plasticization effect of water molecules. The same effect is also caused by alcohols and
other molecules containing polar groups. EVOH also offers less resistance to permeation of
these molecules. Because of this, EVOH is usually applied in multilayer structures or blended
with other materials to protect the EVOH layer from moisture and alcohols and it also
improves the processability of the final material.
However, there is still a lot of demand for in-depth research concerning the permeability
of other gases than oxygen, volatile organic compounds and the effect of different compo-
nents (e.g., in co-permeation) at different conditions. This will lead to deeper understanding
of the EVOH barrier mechanisms and create new possibilities and markets for EVOH as a
barrier layer material. Online permeation measurement coupled to a GC is a powerful tool
to determine the permeability for different kinds of organic substances like aromas, flavours,
fuel, mineral oils and other chemicals.

List of abbreviations
ADI acceptable daily intake
aPA amorphous polyamide
BOPP biaxially oriented polypropylene
BTEX benzene, toluene, ethylbenzene and xylene isomers
CE10 fuel C with 10 v% ethanol
CM15 fuel C with 15 v% methanol
DIPN 2,7-diisopropyl naphthalene
DRa radon diffusion coefficient
EFSA European Food Safety Authority
EVA ethylene vinyl acetate
EVOH ethylene vinyl alcohol copolymer
EVOHxx EVOH containing xx mol% ethylene
FAE force-assembling element
FCM food contact material
FID flame ionization detector
GC gas chromatography
g-MAH grafted with maleic anhydride
GO graphene oxide
GTE green tea extract
HDPE high-density polyethylene
HP-HT high pressure high temperature processing
HPLC high performance liquid chromatography
HPP high pressure processing
IPTES 3-isocyanatopropyl triethoxysilane
LDPE low-density polyethylene
LLDPE linear low-density polyethylene
MMT montmorillonite
MOAH mineral oil aromatic hydrocarbons
MOSH mineral oil saturated hydrocarbons
mPA modified polyamide
238 C. MAES ET AL.

MS microwave sterilization
NIAS non-intentionally-added substances
O2GTR oxygen gas transmission rate
OLED organic light emitting diodes
OPA oriented polyamide
OPET oriented poly(ethylene terephthalate)
P permeability (coefficient)
PA polyamide
PA 6 polyamide nylon 6
PBT polybutylene terephthalate
PC polycarbonate
PCO2 carbon dioxide permeability (coefficient)
PE polyethylene
PEMA poly(ethylene-co-methacrylic acid)
PET poly(ethylene terephthalate)
PH 2 O water vapor permeability (coefficient)
PLA poly(lactic acid)
PO2 oxygen permeability (coefficient)
PP polypropylene
PS polystyrene
PSPI phosphorylated soybean isolate protein
PU polyurethane
PVC polyvinylchloride
PVDC poly(vinylidene dichloride)
PVOH poly(vinyl alcohol)
RH relative humidity
SML specific migration limit
TEOS tetraethoxyorthosilicate
Tg glass transition temperature
Tm melting point
TXIB 2,2,4-trimethyl-1,3-pentanediol-di-isobutyrate
WVTR water vapor transmission rate

Acknowledgments
The authors acknowledge support from the agency Flanders Innovation & Entrepreneurship via the
VLAIO Baekeland mandate of Caroline Maes. The authors also acknowledge Cynthia Teniers, Didier
Houssier and Bruno Steenssens of EVAL Europe nv for their valuable input.

ORCID
Caroline Maes http://orcid.org/0000-0001-7226-7933

References
[1] Wagner, J. R. Multilayer Flexible Packaging; Elsevier Science: Oxford, United Kingdom and
Cambridge, MA, USA, 2016.
 POLYMER REVIEWS 239

[2] Kable. EVAL Production Expansion, Antwerp, Belgium:http://www.chemicals-technology.

com/projects/eval-expansion/(last accessed 6 June 2016)
[3] Kuraray co. Ltd. The Story of the Birth of New Products (EVAL):http://www.kuraray.co.jp/en/
company/history/story/eval.html (last accessed 9 June 2016)
[4] Finch, C. A. Polyvinyl Alchol Developments; John Wiley & Sons Ltd.: Hoboken, NJ, USA, 1992.
[5] ICIS Chemical Business. Eval to Build EVOH Plant to Meet Global Demand:https://www.icis.
com/resources/news/2001/06/25/141585/eval-to-build-evoh-plant-to-meet-global-demand/
(last accessed 13 March 2017)
[6] Kuraray America Inc. Kuraray Americas EVAL Plant to Increase Production by More than 17
Million Pounds:http://www.kuraray.us.com/kuraray-americas-eval-plant-to-increase-produc
tion-by-more-than-17-million-pounds/ (last accessed 13 March 2017)
[7] Kuraray Co. Ltd. Kuraray – EVALTM :http://www.evalevoh.com (last accessed 28 February
2017)
[8] Iwanami, T.; Hirai, Y. Ethylene vinyl alcohol Resins for Gas-Barrier Material. Tappi J. 1983, 66,
85–90.
[9] Mokwena, K. K.; Tang, J. Ethylene vinyl alcohol: A Review of Barrier Properties for Packaging
Shelf Stable Foods. Crit. Rev. Food Sci. Nutr. 2012, 52, 640–650. doi: 10.1080/
10408398.2010.504903.
[10] Zhang, Z. B.; Britt, I. J.; Tung, M. A. Permeation of Oxygen and Water Vapor Through EVOH
Films as Influenced by Relative Humidity. J. Appl. Polym. Sci. 2001, 82, 1866–1872. doi:
10.1002/app.2030.
[11] Mokwena, K. K.; Tang, J.; Laborie, M. P. Water Absorption and Oxygen Barrier Characteristics
of ethylene vinyl alcohol Films. J. Food Eng. 2011, 105, 436–443. doi: 10.1016/j.
jfoodeng.2011.02.040.
[12] L
opez-Rubio, A.; Lagaron, J. M.; Gim
enez, E.; Cava, D.; Hernandez-Mu~ noz, P.; Yamamoto, T.;
Gavara, R. Morphological Alterations Induced by Temperature and Humidity in ethyle-
ne¡vinyl alcohol Copolymers. Macromolecules 2003, 36, 9467–9476. doi: 10.1021/ma035346j.
[13] Peter, Z.; Kenyo, C.; Renner, K.; Krohnke, C.; Pukanszky, B. Decreased Oxygen Permeability of
EVOH Through Molecular Interactions. Express Polym. Lett. 2014, 8, 756–766. doi: 10.3144/
expresspolymlett.2014.78.
[14] Kim, S. W.; Cha, S. H. Thermal, Mechanical, and Gas Barrier Properties of ethylene- vinyl alco-
hol Copolymer- Based Nanocomposites for Food Packaging Films: Effects of Nanoclay Load-
ing. J. Appl. Polym. Sci. 2014, 131, 8. doi: 10.1002/app.40289.
[15] Lopez-Carballo, G.; Cava, D.; Lagaron, J. M.; Catala, R.; Gavara, R. Characterization of the
Interaction Between Two Food Aroma Components, Alpha-Pinene and Ethyl Butyrate, and
ethylene-vinyl alcohol Copolymer (EVOH) Packaging Films as a Function Of Environmental
Humidity. J. Agric. Food Chem. 2005, 53, 7212–6. doi: 10.1021/jf051041n.
[16] Shimo, H.; Yamashita, T. Pipe For Hot-Water Circulation. Google Patents. U.S. 6447858 B1,
2002.
[17] Armstrong, R. B.; Asme, M.; Spe, M.; Ig, M. Improving Indoor Air Quality by Reducing Radon
and Vapor Intrusion Through the Use of ethylene vinyl alcohol (EVOH). International Radon
Symposium, Columbus Ohio, 2010.
[18] Lagaron, J. M.; Powell, A. K.; Bonner, G. Permeation of Water, Methanol, Fuel and Alcohol-
Containing Fuels in High-Barrier ethylene–vinyl alcohol Copolymer. Polym. Test. 2001, 20,
569–577. doi: 10.1016/S0142-9418(00)00077-5.
[19] Armstrong, R. Reduction in Landfill Emissions of Hydrocarbons and Greenhouse Gasses
Through the use of EVOH. Global Waste Management Symposium: Arizone Grand Resort –
Phoenix, AZ, USA, 2012.
[20] Armstrong, R. B. Improving Performance of Geosynthetics for Containment of Volatile
Organic Compounds Through the use of ethylene vinyl alcohol (EVOH). Geo-Frontiers: Shera-
ton Dallas Hotel; Dallas, Texas USA, 2011.
[21] Mckeen, L. W. Permeability Properties of Plastics and Elastomers; William Andrew: Waltham,
USA and Oxford, UK, 2012.
240 C. MAES ET AL.

[22] Isella, F.; Canellas, E.; Bosetti, O.; Nerin, C. Migration of Non Intentionally Added Sub-
stances from Adhesives by UPLC–QTOF/MS and the Role of EVOH to Avoid Migration
in Multilayer Packaging Materials. J. Mass Spectrom. 2013, 48, 430–437. doi: 10.1002/
jms.3165.
[23] Stevens, M. Permeation Basics. 14th International MOCONÒ Conference: Permeation Mea-
surement Today: Montabour, Germany, 2015.
[24] Lagaron, J. M.; Catala, R.; Gavara, R. Structural Characteristics Defining High Barrier Properties
in Polymeric Materials. Mater. Sci. Technol. 2004, 20, 1–7. doi: 10.1179/026708304225010442.
[25] Holland, B. J.; Hay, J. N. The Thermal Degradation of Poly(vinyl alcohol). Polymer 2001, 42,
6775–6783. doi: 10.1016/S0032-3861(01)00166-5.
[26] Zhang, Z. B.; Britt, I. J.; Tung, M. A. Water Absorption in EVOH Films and its Influence on
Glass Transition Temperature. J. Polym. Sci. Part B-Polym. Phys. 1999, 37, 691–699. doi:
10.1002/(SICI)1099-0488(19990401)37:7%3c691::AID-POLB20%3e3.0.CO;2-V.
[27] Yam, K. L. The Wiley Encyclopedia of Packaging Technology; John Wiley & Sons Ltd: Hoboken,
NJ, USA, 2009.
[28] Robertson, G. L. Food Packaging: Principles and Practice; Taylor & Francis Group: Boca Raton,
FL, USA, 2012.
[29] Ito, K.; Saito, Y.; Yamamoto, T.; Ujihira, Y.; Nomura, K. Correlation Study Between Oxygen
Permeability and Free Volume of ethylene-vinyl alcohol Copolymer Through Positronium Life-
time Measurement. Macromolecules 2001, 34, 6153–6155. doi: 10.1021/ma001813a.
[30] Artzi, N.; Narkis, M.; Siegmann, A. Review of Melt-Processed Nanocomposites Based on
EVOH/Organoclay. Journal of Polymer Science Part B-Polymer Physics 2005, 43, 1931–1943.
doi: 10.1002/polb.20481.
[31] Ezquerra, T. A.; Sics, I.; Nogales, A.; Denchev, Z.; Balta-Calleja, F. J. Simultaneous Crystalline-
Amorphous Phase Evolution During Crystallization of Polymer Systems. Europhys. Lett. 2002,
59, 417–422. doi: 10.1209/epl/i2002-00211-3.
[32] Artzi, N. Why Nano-Composites are in? A Glimpse into Polymer Based Nanocomposites. Rev.
Chem. Eng. 2005, 21, 307–345. doi: 10.1515/REVCE.2005.21.5.307.
[33] Cabedo, L.; Lagar
on, J. M.; Cava, D.; Saura, J. J.; Gim
enez, E. The Effect of Ethylene Content on
the Interaction Between ethylene-vinyl alcohol Copolymers and Water—II: Influence of Water
Sorption on the Mechanical Properties of EVOH Copolymers. Polym. Test. 2006, 25, 860–867.
doi: 10.1016/j.polymertesting.2006.04.012.
[34] Armstrong, R. B. Crystallization Kinetics of Semi-Crystalline Thermoplastic: Ethylene Vinyl
Alcohol; Topcon; 2008.
[35] Alvarez, V. A.; Kenny, J. M.; Vazquez, A. Isothermal Crystallization of Poly(vinyl alcohol-co-
ethylene). J. Appl. Polym. Sci. 2003, 89, 1071–1077. doi: 10.1002/app.12255.
[36] Rwei, S.-P.; Jue, Z.-F.; Chiang, W.-Y.; Chen, J.-H.; Chen, Y.-H. Characterization of melt spinn-
ability of ethylene vinyl alcohol copolymers. Text. Res. J. 2015, 86, 1191–1201. doi: 10.1177/
0040517515603805.
[37] Ketels, H. H. T. M. Synthesis, Characterization and Applications of ethylene vinylalcohol
Copolymers. Technische Universiteit Eindhoven Eindhoven, 1989.
[38] Michaels, A. S.; Barrie, J. A.; Vieth, W. R. Diffusion of Gases in Polyethylene Terphthalate. J.
Appl. Phys. 1963, 34, 13–&. doi: 10.1063/1.1729054.
[39] Buntinx, M.; Willems, G.; Knockaert, G.; Adons, D.; Yperman, J.; Carleer, R.; Peeters, R. Evalua-
tion of the Thickness and Oxygen Transmission Rate before and after Thermoforming Mono-
and Multi-layer Sheets into Trays with Variable Depth. Polymers 2014, 6, 3019–3043. doi:
10.3390/polym6123019.
[40] Aharoni, S. M. Increased Glass Transition Temperature in Motionally Constrained Semicrystal-
line Polymers. Polym. Adv. Technol. 1998, 9, 169–201. doi: 10.1002/(SICI)1099-1581(199803)
9:3%3c169::AID-PAT740%3e3.0.CO;2-Z.
[41] Adam, G.; Gibbs, J. H. On Temperature Dependence of Cooperative Relaxation Properties in
Glass-Forming Liquids. J. Chem. Phys. 1965, 43, 139–146. doi: 10.1063/1.1696442.
[42] Eyring, H. Viscosity, Plasticity, and Diffusion as Examples of Absolute Reaction Rates. J. Chem.
Phys. 1936, 4, 283–291. doi: 10.1063/1.1749836.
 POLYMER REVIEWS 241

[43] Yeh, J.-T.; Chen, H.-Y.; Tsai, F.-C. Blending and White Spirit Permeation Properties of the
Blends of Modified Polyamide and ethylene vinyl alcohol with Varying vinyl alcohol contents.
J. Appl. Polym. Sci. 2006, 102, 1224–1233. doi: 10.1002/app.24425.
[44] Muramatsu, M.; Okura, M.; Kuboyama, K.; Ougizawa, T.; Yamamoto, T.; Nishihara, Y.; Saito,
Y.; Ito, K.; Hirata, K.; Kobayashi, Y. Oxygen Permeability and Free Volume Hole Size in Ethyl-
ene-Vinyl Alcohol Copolymer Film: Temperature and Humidity Dependence. Radiat. Phys.
Chem. 2003, 68, 561–564. doi: 10.1016/S0969-806X(03)00231-7.
[45] Botos, J.; Muller, K.; Heidemeyer, P.; Kretschmer, K.; Bastian, M.; Hochrein, T. Rapid Perme-
ation Measurement System for the Production Control of Monolayer and Multilayer Films.
Proceedings of Pps-29: The 29th International Conference of the Polymer – Conference Papers
2014, 1593, 64–67.
[46] Aucejo, S.; Marco, C.; Gavara, R. Water Effect on the Morphology of EVOH copolymers. J.
Appl. Polym. Sci. 1999, 74, 1201–1206. doi: 10.1002/(SICI)1097-4628(19991031)74:5%3c1201::
AID-APP17%3e3.0.CO;2-8.
[47] Lagar
on, J. M.; Gim
enez, E.; Gavara, R.; Saura, J. J. Study of the Influence of Water Sorption in
Pure Components and Binary Blends of High Barrier Ethylene–Vinyl Alcohol Copolymer and
Amorphous Polyamide and Nylon-Containing Ionomer. Polymer 2001, 42, 9531–9540. doi:
10.1016/S0032-3861(01)00496-7.
[48] Yamamoto, T.; Kanda, T.; Nishihara, Y.; Ooshima, T.; Saito, Y. Correlation Study among Oxy-
gen Permeability, Molecular Mobility, and Amorphous Structure Change of Poly(ethylene-
vinylalcohol copolymers) by Moisture. Journal of Polymer Science Part B-Polymer Physics 2009,
47, 1181–1191. doi: 10.1002/polb.21723.
[49] Cava, D.; Sammon, C.; Lagaron, J. M. Sorption-Induced Release of Antimicrobial Isopropanol
in EVOH Copolymers as Determined by ATR-FTIR Spectroscopy. J. Appl. Polym. Sci. 2007,
103, 3431–3437. doi: 10.1002/app.25532.
[50] Minelli, M.; Sarti, G. C. Permeability and Diffusivity of CO2 in Glassy Polymers with and With-
out Plasticization. J. Membr. Sci. 2013, 435, 176–185. doi: 10.1016/j.memsci.2013.02.013.
[51] ISO “ISO 15105-1”, In Plastics – Film and sheeting – Determination of gas-transmission rate –
Part 1: Differential-pressure methods, 2007.
[52] ISO “ISO 15105-2”, In Plastics – Film and sheeting – Determination of gas-transmission rate –
Part 2: Equal-pressure method, 2003.
[53] Lee, S. Y.; Kim, S. C. Morphology and Oxygen Barrier Properties of LDPE/EVOH Blends. Int.
Polym. Process. 1996, 11, 238–247. doi: 10.3139/217.960238.
[54] Lange, J.; Wyser, Y. Recent Innovations in Barrier Technologies for Plastic Packaging—A
Review. Packag. Technol. Sci. 2003, 16, 149–158. doi: 10.1002/pts.621.
[55] Gaucher-Miri, V.; Jones, G. K.; Kaas, R.; Hiltner, A.; Baer, E. Plastic Deformation of EVA, EVOH
and Their Multilayers. J. Mater. Sci. 2002, 37, 2635–2644. doi: 10.1023/A:1015872129472.
[56] Ebnesajjad, S. Plastic Films in Food Packaging: Materials, Technology, and Applications;
William Andrew: Waltham, MA, USA, 2013.
[57] Kuraray America Inc. Gas Barrier Properties of EVAL resins – Technical Bulletin no. 110. Supplier
technical report.:http://evalevoh.com/media/36916/tb_no_110.pdf (last accessed 1 August 2016)
[58] Jakobsen, M.; Risbo, J. A Simple Model for the Interaction Between Water Vapor and Oxygen
Transmission in Multilayer Barrier Materials Intended for Food Packaging Applications.
Packag. Technol. Sci. 2008, 21, 207–216. doi: 10.1002/pts.799.
[59] Lee, P. C.; Dooley, J.; Robacki, J.; Jenkins, S.; Wrisley, R. Flex Barrier Property Enhancement in
Film Structures Using Microlayer Coextrusion Technology. ANTEC: Duke Energy Convention
Center; Cincinnati, Ohio, 2013.
[60] Zhang, G. J.; Xu, H.; MacInnis, K.; Baer, E. The Structure-Property Relationships of LLDPE-
EVOH Blend Films Fabricated by Multiplication Extrusion. Polymer 2015, 57, 117–124. doi:
10.1016/j.polymer.2014.12.025.
[61] Alipour, N.; Gedde, U. W.; Hedenqvist, M. S.; Yu, S.; Roth, S.; Br€ uning, K.; Vieyres, A.;
Schneider, K. Structure and properties of polyethylene-based and EVOH-based multilayered
films with layer thicknesses of 150 nm and greater. Eur. Polym. J. 2015, 64, 36–51. doi: 10.1016/
j.eurpolymj.2014.12.011.
242 C. MAES ET AL.

[62] Su, H. J.; Xue, J.; Cai, P. L.; Li, J.; Guo, S. Y. Structure and Oxygen-Barrier Properties of (linear
low-density polyethylene/ethylene-vinyl alcohol copolymer)/linear low-density polyethylene
Composite Films Prepared by Microlayer Coextrusion. J. Appl. Polym. Sci. 2015, 132, 7. doi:
10.1002/app.42211.
[63] Ait-Kadi, A.; Bousmina, M.; Yousefi, A. A.; Mighri, F. High Performance Structured Polymer
Barrier Films Obtained from Compatibilized polypropylene/ethylene vinyl alcohol Blends.
Polym. Eng. Sci. 2007, 47, 1114–1121. doi: 10.1002/pen.20794.
[64] Ge, C. F.; Popham, J. A Review and Evaluation of Prediction Models of Gas Permeation for a
Blended Flexible Packaging Film. Packag. Technol. Sci. 2016, 29, 247–262. doi: 10.1002/
pts.2200.
[65] Cerruti, P.; Laurienzo, P.; Malinconico, M.; Carfagna, C. Thermal Oxidative Stability and Effect
of Water on Gas Transport and Mechanical Properties in PA6-EVOH films. J. Polym. Sci. Part
B-Polym. Phys. 2007, 45, 840–849. doi: 10.1002/polb.21095.
[66] Lopez-Rubio, A.; Lagaron, J. M. Improving the Resistance to Humid Heat Sterilization of
EVOH Copolymers Through Blending. J. Appl. Polym. Sci. 2008, 109, 174–181. doi: 10.1002/
app.27991.
[67] Ares, A.; Silva, J.; Maia, J. M.; Barral, L.; Abad, M. J. Rheomechanical and Morphological Study
of Compatibilized PP/EVOH blends. Rheol. Acta 2009, 48, 993–1004. doi: 10.1007/s00397-009-
0381-9.
[68] Sanchez-Garcia, M. D.; Nordqvist, D.; Hedenqvist, M.; Lagaron, J. M. Incorporating Amylopectin
in Poly(lactic acid) by Melt Blending Using Poly(ethylene-co-vinyl alcohol) as a Thermoplastic
Carrier. II. Physical Properties. J. Appl. Polym. Sci. 2011, 119, 3708–3716. doi: 10.1002/app.32891.
[69] Seethamraju, S.; Ramamurthy, P. C.; Madras, G. Performance of an Ionomer Blend-nanocom-
posite as an Effective gas Barrier Material for Organic Devices. Rsc Adv. 2014, 4, 11176–11187.
doi: 10.1039/c3ra47442a.
[70] Puente, J. A. S.; Fatyeyeya, K.; Marais, S.; Dargent, E. Multifunctional Hydrolyzed EVA Mem-
branes with Tunable Microstructure and Water Barrier Properties. J. Membr. Sci. 2015, 480,
93–103. doi: 10.1016/j.memsci.2015.01.008.
[71] Zhu, J. M.; Shen, J. B.; Guo, S. Y. In Situ Biaxial Stretching for the Platelet Formation of an Eth-
ylene-Vinyl Alcohol Copolymer Through Multistage Stretching Extrusion and Its Effect on the
Gas-Barrier Properties of Polyethylene. J. Appl. Polym. Sci. 2014, 131, 7. doi: 10.1002/app.40221.
[72] Lopez-de-Dicastillo, C.; Gallur, M.; Catala, R.; Gavara, R.; Hernandez-Munoz, P. Immobiliza-
tion of Beta-Cyclodextrin in Ethylene-Vinyl Alcohol Copolymer for Active Food Packaging
Applications. J. Membr. Sci. 2010, 353, 184–191. doi: 10.1016/j.memsci.2010.02.049.
[73] de Dicastillo, C. L.; Nerin, C.; Alfaro, P.; Catala, R.; Gavara, R.; Hernandez-Munoz, P. Develop-
ment of New Antioxidant Active Packaging Films Based on Ethylene Vinyl Alcohol Copolymer
(EVOH) and Green Tea Extract. J. Agric. Food Chem. 2011, 59, 7832–7840. doi: 10.1021/
jf201246g.
[74] Lagaron, J. M.; Nunez, E.; Onishi, H. Novel EVOH Compound with Enhanced Moisture Resis-
tance for High Oxygen Barrier Packaging. 18th Iapri World Packaging Conference 2012, 225–
228.
[75] Vannini, M.; Marchese, P.; Celli, A.; Lorenzetti, C. Strategy To Modify the Crystallization
Behavior of EVOH32 through Interactions with Low-Molecular-Weight Molecules. Ind. Eng.
Chem. Res. 2016, 55, 3517–3524. doi: 10.1021/acs.iecr.5b04191.
[76] Duncan, T. V. Applications of Nanotechnology in Food Packaging and Food Safety: Barrier
Materials, Antimicrobials And Sensors. J. Colloid Interface Sci. 2011, 363, 1–24. doi: 10.1016/j.
jcis.2011.07.017.
[77] Nielsen, L. E. Models for the Permeability of Filled Polymer Systems. J. Macromol. Sci.—Chem.
1967, 1, 929–942. doi: 10.1080/10601326708053745.
[78] Liu, Y. W.; Liu, Y. J.; Wei, S. S. Processing Technologies of EVOH/Nano-SiO2 High-Barrier
Packaging Composites. Sci Res Publ, Inc-Srp: Irvin, 2010.
[79] Nam, J.-D.; Kim, S. W. Phase Compatibility and Barrier Properties of Ethylene/Vinyl Alcohol
Copolymer Based Hybrid Materials. J. Appl. Polym. Sci. 2010, 115, 1663–1670. doi: 10.1002/
app.31159.
 POLYMER REVIEWS 243

[80] Kim, H. M.; Lee, H. S. Water and Oxygen Permeation Through Transparent ethylene vinyl
alcohol/(graphene oxide) Membranes. Carbon Lett. 2014, 15, 50–56. doi: 10.5714/
CL.2014.15.1.050.
[81] Kim, D.; Kwon, H.; Seo, J. EVOH Nanocomposite Films with Enhanced Barrier Properties
under High Humidity Conditions. Polym. Compos. 2014, 35, 644–654. doi: 10.1002/pc.22707.
[82] Cerisuelo, J. P.; Gavara, R.; Hernandez-Munoz, P. Natural Antimicrobial – Containing EVOH
Coatings on PP and PET Films: Functional and Active Property Characterization. Packag.
Technol. Sci. 2014, 27, 901–920. doi: 10.1002/pts.2078.
[83] Sadeghi, K.; Shahedi, M. Physical, Mechanical, and Antimicrobial Properties of ethylene vinyl
alcohol copolymer/chitosan/nano-ZnO (ECNZn) Nanocomposite Films Incorporating Glyc-
erol Plasticizer. J. Food Meas. Charact. 2016, 10, 137–147. doi: 10.1007/s11694-015-9287-7.
[84] Wang, H. L.; Zhang, H.; Niu, B. C.; Jiang, S. W.; Cheng, J. F.; Jiang, S. T. Structure and Proper-
ties of the poly(vinyl alcohol-co-ethylene)/montmorillonite-phosphorylated Soybean Protein
Isolate Barrier Film. Rsc Adv. 2016, 6, 29294–29302. doi: 10.1039/C6RA03158G.
[85] ISO “ISO 14663-2”, In Plastics — Ethylene/vinyl alcohol (EVOH) copolymer moulding and
extrusion materials – Part 2: Preparation of test specimens and determination of properties,
2006.
[86] Armstrong, R. B. Effects of Polymer Structure on Gas Barrier of ethylene vinyl alcohol (EVOH)
and Considerations for Package Development. PLACE; TAPPI, 2002.
[87] Fraunhofer IVV Oxygen-scavengers combat retort-shock.
[88] Mokwena, K. K.; Tang, J.; Dunne, C. P.; Yang, T. C. S.; Chow, E. Oxygen Transmission of Mul-
tilayer EVOH Films after Microwave Sterilization. J. Food Eng. 2009, 92, 291–296. doi: 10.1016/
j.jfoodeng.2008.11.011.
[89] Galotto, M. J.; Ulloa, P.; Escobar, R.; Guarda, A.; Gavara, R.; Miltz, J. Effect of High-Pressure
Food Processing on the Mass Transfer Properties of Selected Packaging Materials. Packag.
Technol. Sci. 2010, 23, 253–266.
[90] Juliano, P.; Koutchma, T.; Sui, Q.; Barbosa-Canovas, G. V.; Sadler, G. Polymeric-Based Food
Packaging for High-Pressure Processing. Food Eng. Rev. 2010, 2, 274–297. doi: 10.1007/s12393-
010-9026-0.
[91] Dhawan, S.; Varney, C.; Barbosa-Canovas, G. V.; Tang, J.; Selim, F.; Sablani, S. S. Pressure-
Assisted Thermal Sterilization Effects on Gas Barrier, Morphological, and Free Volume Proper-
ties of Multilayer EVOH films. J. Food Eng. 2014, 128, 40–45. doi: 10.1016/j.
jfoodeng.2013.12.012.
[92] Lopez-Rubio, A.; Lagaron, J. M.; Yamamoto, T.; Gavara, R. “Radiation-Induced Oxygen Scav-
enging Activity in EVOH Copolymers. J. Appl. Polym. Sci. 2007, 105, 2676–2682. doi: 10.1002/
app.26502.
[93] Rubino, M.; Netramai, S.; Auras, R.; Annous, B. A. Effect of Chlorine Dioxide Gas on Physical,
Thermal, Mechanical, and Barrier Properties of Polymeric Packaging Materials. J. Appl. Polym.
Sci. 2010, 115, 1742–1750. doi: 10.1002/app.31244.
[94] Aucejo, S.; Catala, R.; Gavara, R. Interactions Between Water and EVOH Food packaging films.
Food Sci. Technol. Int. 2000, 6, 159–164. doi: 10.1177/108201320000600211.
[95] Cava, D.; Cabedo, L.; Gimenez, E.; Gavara, R.; Lagaron, J. M. The Effect Of Ethylene Content
On The Interaction Between Ethylene–Vinyl Alcohol Copolymers And Water: (I) Application
of FT-IR Spectroscopy to Determine Transport Properties and Interactions in Food Packaging
Films. Polym. Test. 2006, 25, 254–261. doi: 10.1016/j.polymertesting.2005.09.018.
[96] Seethamraju, S.; Ramamurthy, P. C.; Madras, G. “Flexible poly(vinyl alcohol-co-ethylene)/mod-
ified MMT Moisture Barrier Composite for Encapsulating Organic Devices. Rsc Adv. 2013, 3,
12831–12838. doi: 10.1039/c3ra41557k.
[97] Hong, S. I.; Kim, K. B.; Lee, Y.; Cho, S. Y.; Ko, J. A.; Hong, S. K.; Park, H. J. Surface Modification
of Ethylene-Vinyl Alcohol Copolymer Treated with Plasma Source Ion Implantation. J. Appl.
Polym. Sci. 2009, 113, 2988–2996. doi: 10.1002/app.30383.
[98] Tenn, N.; Follain, N.; Fatyeyeva, K.; Valleton, J.-M.; Poncin-Epaillard, F.; Delpouve, N.; Marais,
S. Improvement of Water Barrier Properties of Poly(ethylene-co-vinyl alcohol) Films by
244 C. MAES ET AL.

Hydrophobic Plasma Surface Treatments. J. Phys. Chem. C 2012, 116, 12599–12612. doi:
10.1021/jp302223j.
[99] Vandewijngaarden, J.; Murariu, M.; Dubois, P.; Carleer, R.; Yperman, J.; Adriaensens, P.; Schreurs,
S.; Lepot, N.; Peeters, R.; Buntinx, M. Gas Permeability Properties of Poly(3-hydroxybutyrate-co-
3-hydroxyhexanoate). J. Polym. Environ. 2014, 22, 501–507. doi: 10.1007/s10924-014-0688-1.
[100] MOCON Inc. Permeation Measurement of Organic and Volatile Compounds. Minneapolis,
MN 55428 USA, 2015.
[101] Fukamachi, M.; Matsui, T.; Hwang, Y. H.; Shimoda, M.; Osajima, Y. Sorption Behavior of Fla-
vor Compounds into Packaging Films from Ethanol Solution. J. Agric. Food Chem. 1996, 44,
2810–2813. doi: 10.1021/jf950707i.
[102] Brody, A. L. Flavor Scalping: Quality Loss Due to Packaging. Food Technol. 2002, 56, 124–125.
[103] Berlinet, C.; Brat, P.; Ducruet, V. Quality of Orange Juice in Barrier Packaging Material. Packag.
Technol. Sci. 2008, 21, 279–286. doi: 10.1002/pts.802.
[104] Zhou, Q. X.; Guthrie, B.; Cadwallader, K. R. Development of a System for Measurement of Cou-
pling Dynamic Vapor Sorption with Purge-And-Trap/Fast Gas Chromatography. Packag.
Technol. Sci. 2004, 17, 175–185. doi: 10.1002/pts.648.
[105] Sajilata, M. G.; Savitha, K.; Singhal, R. S.; Kanetkar, V. R. Scalping of Flavors in Packaged Foods.
Comprehensive Rev. Food Sci. Food Saf. 2007, 6, 17–35. doi: 10.1111/j.1541-4337.2007.00014.x.
[106] Leufven, A.; Hermansson, C. The Sorption of Aroma Components From Tomato Juice by
Food-Contact Polymers. J. Sci. Food Agric. 1994, 64, 101–105. doi: 10.1002/jsfa.2740640115.
[107] Armstrong, R. B. Improving Performance of Geosynthetics for Containment of Volatile
Organic Compounds through the Use of Ethylene Vinyl Alcohol (EVOH). Geo-Frontiers 2011:
Advances in Geotechnical Engineering, Dallas, Texas, 2011. ISBN: 978-1-61782-594-1.
[108] Zhao, J.; Kanaan, C.; Clement, R.; Brule, B.; Lenda, H.; Jonquieres, A. Permeability of EVOH
Barrier Material Used in Automotive Applications: Metrology Development for Model Fuel
Mixtures. Oil Gas Sci. Technol.-Revue D Ifp Energies Nouvelles 2015, 70, 353–366. doi: 10.2516/
ogst/2013167.
[109] Gagnard, C.; Germain, Y.; Keraudren, P.; Barriere, B. Permeability of Semicrystalline Polymers
to Toluene/Methanol Mixture. J. Appl. Polym. Sci. 2004, 92, 676–682. doi: 10.1002/app.20184.
[110] Clement, R.; Kanaan, C.; Brule, B.; Lenda, H.; Lochon, P.; Jonquieres, A. An Original Auto-
mated Desorption Apparatus for Measuring Multi-Component Sorption Properties of Barrier
Polymer Films. J. Membr. Sci. 2007, 302, 95–101. doi: 10.1016/j.memsci.2007.06.031.
[111] Cava, D.; Lagaron, J. M.; Martinez-Gimenez, F.; Gavara, R. Inverse Gas Chromatography Study
on the Effect of Humidity on the Mass Transport of Alcohols in an Ethylene-Vinyl Alcohol
Copolymer Near the Glass Transition Temperature. J. Chromatogr. A 2007, 1175, 267–274. doi:
10.1016/j.chroma.2007.10.050.
[112] Armstrong, R. Performance of Model Geosynthetics for Containment of Volatile Organic Com-
pounds in Landfill Applications. Global Waste Management Symposium: Arizona Grand
Resort – Phoenix, AZ, USA, 2012.
[113] McWatters, R. S.; Rowe, R. K.; Wilkins, D.; Spedding, T.; Jones, D.; Wise, L.; Mets, J.; Terry, D.;
Hince, G.; Gates, W. P.; Di Battista, V.; Shoaib, M.; Bouazza, A.; Snape, I. Geosynthetics in Ant-
arctica: Performance of a Composite Barrier System to Contain Hydrocarbon-Contaminated
Soil After Three Years in The Field. Geotext. Geomembr. 2016, 44, 673–685. doi: 10.1016/j.
geotexmem.2016.06.001.
[114] McWatters, R. S.; Rowe, R. K. Permeation of Volatile Organic Compounds through EVOH
Thin Film Membranes and Coextruded LLDPE/EVOH/LLDPE Geomembranes. J. Geotech.
Geoenviron. Eng. 2015, 141, 14. doi: 10.1061/(ASCE)GT.1943-5606.0001209.
[115] Lee, H.-K.; Yang, W. S.; Choi, N.-J.; Moon, S. E. Encapsulation of Semiconductor Gas Sensors with
Gas Barrier Films for USN Application. Etri J. 2012, 34, 713–718. doi: 10.4218/etrij.12.0112.0266.
[116] Bethke, J.; Goedecke, T.; Jahnke, W. Permeation Through Plastic Dangerous Goods Packaging
During Transport in Freight Containers – Detection of Potentially Explosive Mixtures in Con-
tainers Under Normal Conditions of Carriage. Packag. Technol. Sci. 2013, 26, 1–15. doi:
10.1002/pts.994.
 POLYMER REVIEWS 245

[117] Fouillet, T.; Rebizak, R.; Descamps, S.; Ciesla, Y.; Guery, B. Development of a New Gastight
Film Containing EVOH. Viii International Symposium on Chemical and Non-Chemical Soil
and Substrate Disinfestation 2014, 1044, 301–305.
[118] Yeh, J.-T.; Chen, H.-Y.; Tsai, F.-C. Gasoline Permeation Resistance of Polypropylene, Polypro-
pylene/Ethylene Vinyl Alcohol, Polypropylene/Modified Polyamide, and Polypropylene/Blends
of Modified Polyamide and Ethylene Vinyl Alcohol Containers. J. Polym. Res. 2006, 13, 451–
460. doi: 10.1007/s10965-006-9066-6.
[119] Carrizo, D.; Maccagnan, A.; Felix, J. S.; Nerin, C.; Bosetti, O. The Barrier Effect of EVOH versus
1,4,7-Triaxocyclotridecane-8,13-Dione, a Non-intentionally Added Compound from Polyure-
thane Adhesives in Multilayer Food Packaging. Packag. Technol. Sci. 2015, 28, 1039–1046. doi:
10.1002/pts.2182.
[120] EFSA “EFSA Panel on Contaminants in the Food Chain (CONTAM). Scientific Opinion on
Mineral Oil Hydrocarbons in Food. EFSA Journal 2012, 10, 185.
[121] Lorenzini, R.; Fiselier, K.; Biedermann, M.; Barbanera, M.; Braschi, I.; Grob, K. Saturated and
Aromatic Mineral Oil Hydrocarbons from Paperboard Food Packaging: Estimation of Long-
Term Migration From Contents in the Paperboard and Data on Boxes from the Market. Food
Additives Contaminants: Part A 2010, 27, 1765–1774. doi: 10.1080/19440049.2010.517568.
[122] Vollmer, A.; Biedermann, M.; Grundb€ock, F.; Ingenhoff, J.-E.; Biedermann-Brem, S.; Altkofer,
W.; Grob, K. Migration of Mineral Oil From Printed Paperboard Into Dry Foods: Survey of the
German Market. Eur. Food Res. Technol. 2010, 232, 175–182. doi: 10.1007/s00217-010-1376-6.
[123] Bundesministerium f€ ur Ern€ahrung und Landwirtshaft: Entwurf – Stand: 24.07.2014 –
Zweiundzwanzigste Verordnung zur Anderung € der Bedarfsgegenst€andeverordnung. 2014.
[124] Bundesministerium f€ ur Ern€ahrung und Landwirtshaft: Entwurf – Stand: 24.02.2017 –
Zweiundzwanzigste Verordnung zur Anderung € der Bedarfsgegenst€andeverordnung. 2017.
[125] Diehl, H.; Welle, F. How to Determine Functional Barrier Performance Towards Mineral Oil
Contaminants from Recycled Cardboard. Food Packag. Shelf Life 2015, 5, 41–49. doi: 10.1016/j.
fpsl.2015.05.003.
[126] Pastorelli, S.; Sanches-Silva, A.; Manuel Cruz, J.; Simoneau, C.; Paseiro Losada, P. Study of the
Migration of Benzophenone from Printed Paperboard Packages to Cakes Through Different
Plastic Films. Eur. Food Res. Technol. 2008, 227, 1585–1590. doi: 10.1007/s00217-008-0882-2.
[127] Fiselier, K.; Grob, K. Barriers Against the Migration of Mineral oil from Paperboard Food Pack-
aging: Experimental Determination of Breakthrough Periods. Packag. Technol. Sci. 2012, 25,
285–301. doi:10.1002/pts.982.
[128] Maes, C.; Teniers, C.; Luyten, W.; Herremans, G.; Peeters, R.; Carleer, R.; Buntinx, M. Card-
board Packaging with Ethylene Vinyl Alcohol Copolymer (EVOH) as a Functional Barrier
Against Mineral Oil Migration. In 28th IAPRI Symposium on Packaging 2017: Unlocking the
full potential of packaging across the value-chain: The Olympic Museum in Lausanne, Switzer-
land, 2017.
[129] BiedermannBrem, S.; Grob, K. Barriers Against the Migration from Recycled Paperboard Into
Food: Measuring Efficiency by Surrogate Components. Packag. Technol. Sci. 2014, 27, 713–726.
doi: 10.1002/pts.2062.
[130] Richter, L.; Biedermann-Brem, S.; Simat, T. J.; Grob, K. Internal Bags with Barrier Layers for
Foods Packed in Recycled Paperboard: Recent Progress. Eur. Food Res. Technol. 2014, 239,
215–225. doi: 10.1007/s00217-014-2208-x.
[131] Ewender, J.; Franz, R.; Welle, F. Permeation of Mineral Oil Components from Cardboard Pack-
aging Materials Through Polymer Films. Packag. Technol. Sci. 2013, 26, 423–434. doi: 10.1002/
pts.1990.
[132] Ewender, J.; Langowski, H.-C.; Welle, F. Functional Barriers Towards Mineral Oil Contami-
nants. Verpackungs-Rundschau 2015, 50–51.
[133] Ewender, J.; Welle, F. Determination and Prediction of the Lag Times of Hydrocarbons through
a Polyethylene Terephthalate Film. Packag. Technol. Sci. 2014, 27, 963–974. doi: 10.1002/
pts.2085.
[134] F
elix, J.; Isella, F.; Bosetti, O.; Ner
ın, C. Analytical Tools for Identification of Non-Intentionally
Added Substances (NIAS) Coming from Polyurethane Adhesives in Multilayer Packaging
246 C. MAES ET AL.

Materials and their Migration into Food Simulants. Anal. Bioanal. Chem. 2012, 403, 2869–2882.
doi: 10.1007/s00216-012-5965-z.
[135] Nulman, M.; Olejnik, A.; Samus, M.; Fead, E.; Rossi, G. State of Alternative Fuel Technologies.
In Paper 981360; Society of Automotive Engineers, Inc Warrendale, PA, 1998.
[136] The Nippon Synthetic Chemical Industry Co. Ltd. High gas-barrier resin SoarnolTM:www.soar
nol.com/ (last accessed 27 July 2016)
[137] Maxwell, A. S.; Roberts, S. J. Review of Data on Gas Migration through Polymer Encapsulants:
Report to NDA – Radioactive Waste Management Directorate; Serco, 2010.
[138] Jiranek, M.; Rovensk
a, K.; Fronka, A. Radon Diffusion Coefficient – A Material Property Deter-
mining the Applicability of Waterproof Membranes as Radon Barriers. In American Associa-
tion of Radon Scientists and Technologists 2008 International Symposium: Las Vegas NV,
September 14–17, 2008.