Oxygen Barrier

Oxygen barrier plays a key role in food packaging, and it was found that NFC
contributed to the impermeability of films when they were prepared at a sufficient
thickness [24,148–150].

From: Green Composites for Automotive Applications, 2019

Related terms:

Chitosan, Nanocomposite, Polyamides, resin, Shelf-Life, Oxygen Permeability

View all Topics

Learn more about Oxygen Barrier

Barrier
Barry A. Morris, in The Science and Technology of Flexible Packaging, 2017

8.3.3 Grease and Oil Resistance

Most of the high oxygen barrier polymers such as EVOH, PA, PVDC, and even PET
have excellent oil and grease resistance due to their high level of crystallinity and
polarity. The oil and grease resistance of polyolefins vary with their crystallinity and
polarity. Based on an old chemistry adage of “like dissolves like” this is not surprising
since oils are simply low MW polyolefins and generally nonpolar. In the following
sections, the oil resistance of polyolefins is discussed based on work done at DuPont
[51–53].

8.3.3.1 Polyethylene
The oil resistance of polyethylene (PE) is strongly affected by its crystallinity. In
general, if the PE has lower crystallinity, the oil resistance is reduced. Crystallinity, in
turn, is influenced by the density of the resin and film fabrication conditions (partic-
ularly quench conditions). For polyolefins and ethylene alpha-olefin copolymers like
linear low-density polyethylene (LLDPE) the crystallinity increases with increasing
density. For polar ethylene copolymers like ethylene vinyl acetate (EVA) the opposite
is true due to the higher MW of the comonomer. One way to normalize the effect of
crystallinity is to plot the oil resistance versus the secant modulus of the film. Typical
data for the penetration of mineral oil in PE are given in Fig. 8.3. Here the time
to failure in a ground glass patch test (ASTM F-119-70) is plotted. In this method,
a longer time indicates greater oil resistance. A change in slope occurs at around
350 MPa (50 kpsi), equivalent to about 0.935 g/cc density for a PE. The oil resistance
levels off above this level of crystallinity. This suggests that an HDPE resin has about
the same oil resistance as a medium-density polyethylene resin.

Figure 8.3. Penetration of mineral oil through polyolefin films.

Reproduced with permission from E. I. du Pont de Nemours and Company.

Similar results are found for peanut oil and are plotted in Fig. 8.4. Here grades of
ionomer and a grade of PP are included for comparison.

Figure 8.4. Penetration of peanut oil through polyolefin films.

Reproduced with permission from E. I. du Pont de Nemours and Company.

EVA copolymer is expected to have comparable oil resistance to a PE with similar
crystallinity. Again, secant modulus can be used as a common parameter. One of the
data points in Figs. 8.3 and 8.4 is from a 5% VA copolymer (secant modulus equals
110 MPa or 16 kpsi); it fits on the same curves as the PE grades.

As the temperature is increased, the oil resistance decreases. The greater the density
of the PE, the less sensitive the oil resistance is to changes in temperature. This
may reflect the differences in melting points. Polyolefins melt over a temperature
range with HDPE having a peak melting point of 135°C and low-density polyethylene
(LDPE) 110°C. Some of the less perfect crystals melt at a temperature well below
the peak melting point. At 60°C, some of the crystals in LDPE have begun to melt
whereas very few crystals of HDPE have. It should be noted that this observation is
based on a study done before the introduction of metallocene PE, which have much
narrower melting point ranges.

8.3.3.2 Acid Copolymers

The oil resistance of acid copolymer resins (ACR) increases with increasing acid level.
As the acid level is increased, the crystallinity decreases. This contrasts with PE where
decreasing crystallinity reduces oil resistance. This suggests that hydrogen bonding
among the acid groups in the copolymer is important for oil resistance.

Fig. 8.5 shows the effect of acid level on the resistance to mineral oil penetration.
Most grades of acid copolymer have an acid level in the range between 4 and 12 wt%
methacrylic acid (MAA) or between 3% and 9.5% acrylic acid (AA). At 12 wt% MAA,
the oil resistance is substantially better than a standard LLDPE grade or metallocene
plastomer, but not as good as HDPE (see Fig. 8.2). Data for EAA are not generated in
this study, but EAA is expected to have similar performance as EMAA at equivalent
mole % acid. Because AA has a lower MW than MAA, the wt% AA must be multiplied
by 1.2 to convert from wt% AA to wt% MAA at the same mol%. Thus a 10 wt% AA
EAA resin has about the same amount of acid on a molar basis as a 12 wt% MAA
EMAA resin.
Figure 8.5. Mineral oil resistance of acid copolymers as a function of acid content
(methacrylic acid) and temperature.

Reproduced with permission from E. I. du Pont de Nemours and Company.

8.3.3.3 Ionomers
Partially neutralizing an acid copolymer typically improves its oil resistance. The
greater the acid level and percent neutralization, the better is the resistance. Sodium
ionomers typically give better resistance than equivalent zinc ionomers. In DuPont's
Surlyn ionomer product line, Surlyn 1707 (sodium, 0.9 MI) and 1605 (sodium, 2.8
MI) have the best oil resistance. Surlyn 1652 (zinc, 5 MI) has the least oil resistance,
but is still better than standard acid copolymers and LDPE.

Ionomers typically have better oil resistance than LDPE, LLDPE, and in many cases
HDPE. See Fig. 8.4 for a comparison of peanut oil penetration. DeGaravilla [52]
compares the corn oil penetration resistance of several polyolefins. His results,
shown in Fig. 8.6, show that ionomers have substantially better oil resistance than
other premium sealants such as very low-density polyethylene (VLDPE), metallocene
polyethylene plastomer (mPE), and EVA. The oil resistance of Surlyn ionomers is
sensitive to temperature; like PE, the higher the temperature, the poorer the oil
resistance. The temperature dependence of the penetration of vegetable oils is
illustrated in Fig. 8.7.

Figure 8.6. Oil resistance of several premium sealant resins. 50-μm film exposed to
40°C corn oil in ground glass test. Test terminated at 268 h (before ionomer samples
failed). EMAA, ethylene methacrylic acid; LLDPE, linear low-density polyethylene.

From deGaravilla J. Ionomer, acid copolymer, and metallocene polyethylene resins: a

comparative assessment of sealant performance. Tappi J 1995;78(6):192. Reproduced
with permission from E. I. du Pont de Nemours and Company.
Figure 8.7. Oil resistance of several grades of Surlyn ionomer as a function of
temperature. Samples from 25-μm extrusion coatings on paper. Tested in vegetable
oil using ground glass test. LDPE, low-density polyethylene.

Composite data taken from Ref. [53]. Reproduced with permission from E. I. du Pont
de Nemours and Company.

8.3.3.4 Polypropylene
One grade of PP is included in the DuPont study [51]. PP is found to have better oil
resistance than HDPE and is comparable to the best ionomer grades. The sensitivity
of the oil resistance of PP to temperature changes is greater than HDPE but about
the same as ionomers. See Fig. 8.4.

8.3.3.5 Film Thickness

The DuPont study finds that the oil resistance of polyolefin films is non-linear with
respect to film thickness. A doubling of the thickness results in a more than doubling
of the oil resistance. (No explanation was given at the time. Subsequent studies have
shown that the crystallinity at the surface of a blown film may be lower than the bulk.
Thus, one explanation is that the thicker the film, the less impact the surface regions
have on permeation.)

8.3.3.6 Oil Type

Most of the study by DuPont was done with mineral and vegetable (primarily peanut)
oils. For mineral oil, it was found that the MW of the oil can have a substantial
impact on oil resistance. A low MW oil, such as No. 2 fuel oil (similar to kerosene),
will permeate through the film much faster than a standard mineral oil.
Vegetable oils are composed mainly of triglycerides and these can normally be
expected to behave similarly regardless of the source. For example, it is found that
soy oil and peanut oil give similar permeation rates. Other studies show peanut oil,
corn oil, cottonseed oil, and olive oil give similar results. However, vegetable oil can
contain various levels of free fatty acid that can greatly alter the permeation rate and
even the comparison between ionomers and PE. In one such case, the permeation
rate of rice oil containing 18% free fatty acid is found to be considerably faster
through an ionomer than through LDPE. (For comparison, the peanut oil used in the
study has only 0.14% free fatty acid.) Consequently, the oil resistance of the ionomer
to rice oil is poorer than an LDPE with density 0.922 g/cc.

> Read full chapter

Packaging and Sterilization of UHMW-

PE
Steven M. Kurtz PhD, Matthew Zagorski MS, CPP, in UHMWPE Biomaterials Hand-
book (Third Edition), 2016

3.3 Gamma Sterilization in Oxygen Barrier Packaging

There are many types of oxygen barrier packaging currently in use by the orthopedic
industry (Table 3.2). The details about current packaging systems for orthopedic
components are proprietary, but basically consist of multiple evacuations of the
air from the packaging and multiple backflushing with an inert gas (e.g., nitrogen,
carbon dioxide, or even noble gases such as argon or helium) prior to sealing.
The “barrier” in the package consists of a metallic foil laminate, silica-coated PET
laminates or ethyl-vinyl-alcohol-based polymer laminates to block gas diffusion (see
the photo of barrier-packaged tibial components in Figure 3.4, provided in Jan. 2003,
courtesy of David Schroeder, Biomet, Inc). Three further examples of contemporary
barrier packaging for UHMWPE components from different manufacturers are
shown in Figures 3.5–3.7. Additionally, oxygen scavengers using materials such as
purified and modified layered clay may be incorporated as packaging elements.

Table 3.2. Summary of Contemporary Barrier Packaging Techniques Used for Gam-
ma Sterilization of UHMWPE Among Major Orthopedic Manufacturers (as of Oc-
tober 2008)

Company Package Environment Sterilization/Packaging Trade

Name
Biomet Argon flushed, near-vacuum ArCom
sealed
DePuy, Inc. Near vacuum GVF® (Gamma Vacuum Foil)
Stryker Howmedica Osteonics Nitrogen N2-Vac™; Duration™
Synthes USA Vacuum, nitrogen, vaccum N/A
Zimmer, Inc. Nitrogen

Figure 3.4. Contemporary barrier packaging used with the fabrication of ArCom™
(Biomet, Inc., Warsaw, IN). ArCom packaging currently uses a glass film interposed
between polymer sheets for an oxygen barrier. The packaging is argon-flushed and
then vacuum-sealed.

Figure 3.5. Contemporary nitrogen-filled barrier packaging for gamma sterilization

of UHMWPE components used by Zimmer, Inc. (Warsaw, IN).
Figure 3.6. Contemporary N2-Vac barrier packaging for gamma sterilization of
UHMWPE components used by Stryker Howmedica Osteonics (Mahwah, NJ).

Figure 3.7. Contemporary GVF barrier packaging for gamma sterilization of

UHMWPE components, used by DePuy Orthopedics (Warsaw, IN).

As shown in Table 3.2, many major orthopedic manufacturers continue to distribute

UHMWPE components that are barrier packaged and gamma sterilized in an inert
environment. The goal of barrier packaging is to minimize oxidative degradation
during long-term shelf-life storage. Because gamma-sterilized UHMWPE in a
low-oxygen environment still contains macroradicals, the successful mitigation of
oxidation during shelf storage depends upon its ability to limit access of oxygen to
the polymer. At present, the ideal residual level of oxygen is considered proprietary
and has not been published as a consensus standard. As highlighted in a recent
survey [1], and covered in a subsequent section of this chapter, polymeric barriers
may not be successful at preventing UHMWPE oxidation during shelf aging if they
do not incorporate an impermeable glass or metallic layer into the laminate.

Concerns about oxidative degradation during shelf life prompted some orthopedic
manufacturers in the 1990s to adopt sterilization of conventional UHMWPE using
chemical sterilization methods such as gas plasma or EtO. These sterilization meth-
ods admittedly generate minimal to no free radicals that can subsequently oxidize
during shelf storage. However, UHMWPE sterilized in this manner does not receive
a tribological benefit associated with radiation-induced cross-linking. McKellop et al.
[18] reported on the wear performance of UHMWPE in a contemporary hip simula-
tor following gamma irradiation in air, gamma irradiation in an inert gas, EtO, or gas
plasma. Between 2 and 5 million cycles (each million of cycles corresponds to about
a year of use in vivo for an average patient), the wear rate of the gamma-sterilized
UHMWPE was significantly lower than UHMWPE sterilized by either gas plasma
or EtO. For example, the wear rate from 3.5 to 5 million cycles for EtO-sterilized
UHMWPE was reported as 40 ± 0.6 mm3/million cycles; in contrast, the wear rate
for UHMWPE that was gamma irradiated in an air-permeable package was found
to be 18.5 ± 0.9 mm3/million cycles [18]. A similar trend has been reported by Wang
et al. [19], who observed over a 50% drop in the hip simulator wear rate following
a single 25 kGy dose of gamma sterilization. When oxygen is excluded from the
package during sterilization, further cross-linking, and additional improvement in
wear performance, may be achieved in a hip simulator relative to gamma sterilization
in air [18].

The effect of gamma inert sterilization on wear has been evaluated in clinical studies.
The clinical wear rate for both gamma air and gamma inert sterilized components
is comparable. However, gas-plasma-sterilized implants have a clinical wear rate
that is approximately two times greater than gamma-air sterilized liners [20]. This is
because wear processes in hip replacements are dominated by cross-linking. Even
following gamma sterilization in air, the beneficial effects of cross-linking dominate
over the deleterious effects of oxidative degradation, helping to explain the decades
of successful use of gamma-air sterilized components starting in the 1960s:

“Perhaps surprisingly, the mean true wear rate for the conventional polyethylene
liners that had been sterilized with gamma radiation in air was not significantly
different from that for the liners that had been sterilized with gamma radiation in
vacuum-barrier packaging.”– Sychterz et al. [21]

Because gamma sterilization, whether in air, or in a low-oxygen environment,

produces a comparable extent of radiation cross-linking, one would not expect a
substantial difference between gamma-air and gamma-inert sterilized polyethylene
in a hip replacement. To achieve a clinically meaningful reduction in wear for total hip
replacements, a higher level of radiation treatment is necessary than can be achieved
using a standard sterilization dose (25–40 kGy).

> Read full chapter

Barrier Resins
Thomas Dunn, in Flexible Packaging, 2015

This chapter presents the ability of oxygen barrier resins, polyvinylidene chloride
(PVDC), ethylene vinyl alcohol (EVOH), and nylon (PA), to retard the movement of
oxygen across layer made of them when different oxygen partial pressures exist on
either side of the layer. Polyolefins, especially highly crystalline ones, have a similar
ability to retard the movement of water vapor when the partial pressure differences
represent relative humidity. The process is quantitatively described at the molecular
level and can be quantified in relative terms for flexible packaging materials. Similar
molecular interactions are recognized in such effects as slip additive migration,
flavor scalping, and extractables from packaging into packaged foods. Coextrusion
of barrier resins with olefin polymer and copolymers provides an effective and
economical means of incorporating this functionality into a packaging material.

> Read full chapter

Commonly Used Resins and Substrates

in Flexible Packaging
Barry A. Morris, in The Science and Technology of Flexible Packaging, 2017

4.2.7 Ethylene Vinyl Alcohol

EVOH is one of the high oxygen barrier resins used in flexible packaging. It is
derived from EVA copolymers where the vinyl acetate is completely hydrolyzed to
hydroxyl (OH) groups. Unlike EVA copolymers described in Section 4.2.2.4, these
EVA copolymers have much higher levels of vinyl acetate in the range of 56–73 mol%
(EVA used as sealants typically contain about 5 mol% vinyl acetate). EVOH is a
random copolymer with a chemical structure that is a combination of ethylene and
vinyl alcohol units as shown in Fig. 4.16.

Figure 4.16. Chemical structure of EVOH.

EVOH is characterized by its mole percent ethylene and melt flow. Grades with
ethylene contents ranging from 27 to 48 mol% are available commercially. The
ethylene content represents a trade-off between ease of processing and barrier
performance. As the mole% ethylene is decreased, the oxygen transmission rate
(at low RH) decreases but processing becomes more difficult. An easy way to
remember these effects is that the higher the ethylene content, the more like
polyethylene and less like PVOH the molecule is.

The barrier performance of EVOH is highly influenced by the RH of the environ-

ment. This is explored in more detail in Chapter 8. Fig. 4.17 shows the relationship
between oxygen transmission and RH. Above an RH of about 70%, the transmission
rate increases rapidly. The lower ethylene content grades are more susceptible to
changes in transmission rate with increasing RH.

Figure 4.17. Oxygen transmission rate of EVOH as a function of relative humidity.

Data from Kuraray. Technical bulletin no. 110: gas barrier properties of resins.
http://www.eval-americas.com/media/36916/tb_no_110.pdf.

EVOH comes in a variety of flow rates for processing on blown and cast film and
extrusion coating processes. EVOH is transparent, stiff, and highly crystalline, and is
an excellent oxygen barrier, but has a relatively high MVTR. EVOH is used primarily
in coextruded structures for both rigid and flexible packaging. Because of its high
crystallinity it can be difficult to thermoform or orient. A number of technologies
have been developed to overcome these deficiencies, including

• sandwiching the EVOH layer between layers of PA6;

• blending in amorphous nylon [49–51] or ionomer [52–54];

• development of specialty grades by EVOH resin producers [55–57];

• splitting the EVOH layer into two or more thinner layers [58]. New microlayer
technology reduces the crystallinity of EVOH, making the film more flexible
and orientable [59,60] (see Section 8.5.2);
•
 using a rapid quench cast film or water quench blown film process, which
suppresses crystallinity [61,62].

EVOH has become a ubiquitous barrier resin in transparent coextruded flexible

packaging. It can be found in many applications where long shelf life is needed.
Examples include processed meat and cheese packaging, instant coffee machine
cups, lidding films, high barrier formable films for fresh pasta, barrier cereal liners,
thermoformed cups and trays, extrusion-coated paper for soups, coffee and tea, and
toothpaste tubes.

> Read full chapter

Compatibilization
Johannes Karl Fink, in Reactive Polymers Fundamentals and Applications (Second
Edition), 2013

16.5.20 PE and EVA

Saponified ethylene-vinyl acetate copolymers in general have good oxygen barrier
properties, mechanical strength, etc. and, as such, have found application in many
uses such as film, sheet, container material, and textile fiber. However, this saponi-
fied copolymer gives rise to a variation in product thickness in the molding process
for manufacture of film or sheet, with the consequent decrease in the marketability
of the product. Because of the deficiency in stretchability and flexibility, it gives rise
to uneven stretching in deep-drawing and other processes involving a stretching
force or pinholes in use of the product, thus imposing serious limitations on its
application as a packaging raw material.

Blends of saponified ethylene-vinyl acetate copolymer and an ethylene copolymer,

such as low-density poly(ethylene), linear low-density poly(ethylene), ethylene-vinyl
acetate copolymer, or an ethylene acrylic ester copolymer show improved proper-
ties; however, they need a compatibilizer. The compatibilizer can consist of a graft
polymer, obtainable by grafting an ethylenically unsaturated carboxylic acid such as
acrylic acid or methacrylic acid to a polyolefin resin, and reacting this carboxylic acid
or derivative thereof with a polyamide oligomer or polyamide. The compatibilizer is
added in amounts of 0.5 to 10% [144].

The compatibility of the blend is markedly improved and the material shows an
excellent oxygen barrier property and improvements in stretchability, film thickness,
and flexibility which are deficient in the saponified ethylene-vinyl acetate copolymer
alone.
> Read full chapter

Nylon-MXD6 resins for food packaging

A. Ammala, in Multifunctional and Nanoreinforced Polymers for Food Packaging,
2011

9.3.1 Oxygen transmission rate

One of the most notable properties of Nylon-MXD6 is its excellent oxygen barrier
properties. Table 9.2 compares the oxygen transmission rates to those of various
other polymer films at different relative humidity. The oxygen barrier properties
of Nylon-MXD6 exceed that of many other polymers used in packaging. It is
particularly useful that Nylon-MXD6 can retain its excellent gas barrier properties
at high humidity. In contrast, ethylene vinylalcohol copolymer (EVOH) films do not
perform as well under a high humidity environment. Figure. 9.2 shows the oxygen
permeability dependence on relative humidity for Nylon-MXD6. This behaviour at
both low and high relative humidity makes Nylon-MXD6 a very practical polymer
for both dry and wet food packaging applications.

Table 9.2. Oxygen transmission rates of various polymer films

Film Oxygen transmission rate (cm3/m2.day.atm), 20

µm, 23 °C
60% RH 80% RH 90% RH
Nylon-MXD6 (oriented: 2.8 3.5 5.5
4 x 4)
Nylon-MXD6 (non-ori- 4.3 7.5 20
ented)
EVOH (32 mol% ethyl- 0.5 4.5 50
ene)
EVOH (44 mol% ethyl- 2.0 8.5 42.5
ene)
PAN copolymer 17 19 22
Nylon-6 (oriented) 40 52 90
Nylon-6 (oriented, 10 10 10
PVDC coated)
PET (oriented) 80 80 80
PP (oriented) 2500 2500 2500
PP (PVDC coated) 14 14 14

Source: http://www.mgc.co.jp/eng/products/nop/nmxd6/barrier.html
9.2. Humidity dependence of oxygen permeability at 23 °C.

Source: http://www.mgc.co.jp/eng/products/nop/nmxd6/barrier.html

Oxygen scavenging systems

In the late 1980s the UK packaging company Carnaud MetalBox (CMB) found that
the incorporation of small amounts of cobalt produced an oxygen scavenging system
that enhanced the oxygen barrier performance of Nylon-MXD6/PET systems.9 The
cobalt salt catalyses the reaction of Nylon-MXD6 with oxygen passing through the
package wall and prevents oxygen reacting with the food product. Bottles made
using this technology were successful in demonstrating the inhibition of oxygen
reacting with oxygen-sensitive products like orange juice, beer and wine.

In today's market, there are two major producers of Nylon-MXD6/PET bottles that
use the oxygen scavenging technology. Constar International market a product
under the name Oxbar™ for multilayer bottles and in addition they have mono-
layer systems, Monoxbar™ and the high clarity DiamondClear™ Amcor market the
system called Bind-Ox™, where the oxygen scavenger is incorporated in the middle
layer of a three-layer multilayer bottle. In this system, the rate at which oxygen is
bound is faster than the rate of oxygen permeation, so the Bind-Ox™ layer acts like
a sponge, capturing oxygen which has virtually no chance of reaching the product.

Although oxygen scavenging systems are highly effective, they do have a limited
lifetime and will only stay active until there is sufficient catalyst present to sustain
the oxidation reaction. The barrier properties are usually a function of scavenging
capacity and rate of consumption.10 The composition (MXD6 and cobalt content) as
well as the container wall thickness are factors that can affect the scavenging capacity.
Similarly, the barrier performance is dependent on package surface area/volume
ratio.11 Large surface/volume ratios limit cost-effective performance and for this
reason oxygen scavengers have primarily been used for bottled products.

An example of the oxygen barrier improvement observed with the use of Oxbar™ has
been reported by Brody et al. (2001).10 A 1-litre PET-only bottle showed an oxygen
transmission rate of 3.5 cm3/m2/day (22 °C), while the equivalent Oxbar™ bottle
(PET/MXD6/Co) had a transmission value of less than 0.04 cm3/m2/day. This low
level persisted for a period approaching two years.

> Read full chapter

Corona Treatment
Joanna Izdebska, in Printing on Polymers, 2016

8.3.7 Polylactide
PLA is a biodegradable polymer, which is characterized by perfect transparency, high
gloss, and thermoplasticity and it provides the same oxygen barrier as PP used for
production of packages. Due to the mechanical properties, it may be compared with
PA or polyester (Nampoothiri, Nair, & John, 2010). Surface free energy of this plastic
is relatively high but, like in the case of PET, it may require treatment before the
printing and gluing processes.

Moraczewski et al. (2014) noticed the growth of the value of PLA surface free energy
and the improvement of wettability (reduction of contact angle with water and
diiodomethane) resulting from the modification of the upper layer with corona
discharges in air and nitrogen atmosphere. The improvement of parameters was
visible for processes with unit activating energy which did not exceed 7 kJ/m2. Further
increase in Ej did not cause significant changes in the value of surface energy of
the material. This results from maximum saturation of layers with polar groups.
The growth of Ej during modification in nitrogen atmosphere is accompanied by a
constant increase in the value of PLA surface free energy. It is a sign of longer time
of the layers' saturation with polar groups in such conditions.

In another study, Stepczyńska and Żenkiewicz (2014) examined an impact of corona

treatment on PLA film in air and helium atmosphere. Application of the second gas
improves the uniformity of activation. Helium is a neutral gas that is ionized more
easily than air. Contact angles of modified PLA films were declining along with the
growth of Ej, regardless of the used gas. Greater roughness of the samples occurred
during treatment in air atmosphere. In the case of these films, it was noticed that the
level of oxidation was lower than in the case of the material activated with helium.

> Read full chapter

Gas Transport, Mechanical, Interphase,

and Interdiffusion Properties in Coex-
truded-Multilayered Films
Deepak Langhe, Michael Ponting, in Manufacturing and Novel Applications of
Multilayer Polymer Films, 2016

3.2.7.1 Nanobiaxially Oriented Polypropylene (Nano-BOPP)

Biaxially oriented PP (BOPP) film is widely used in flexible packaging applications
due to its improved toughness, transparency, and oxygen barrier properties over
unoriented PP [17]. Various fillers with high aspect ratio have also been investigated
to improve the oxygen barrier in BOPP films at the expense of optical properties [18].
Using PEO or PCL nanolayers in BOPP film at thicknesses lower than the quarter
wavelength of light allows barrier improvement without sacrificing the mechanical
and optical properties. Multilayered sheets with 33-layered PP/PEO structure were
produced by layer multiplication process followed by addition of thick PP skin layers
in the coextrusion process [19]. The final composite structure was produced in
PP[(PEO/PP)n]PP form with significantly thick PEO layers (2.5 μm). To improve the
barrier properties, it was necessary to reduce PEO layer thickness down to a few
tens of nanometer. Biaxial stretching of the composites produced oriented PP film
and achieved simultaneous reduction in the PEO layer thickness to nanoscale by its
melting and recrystallization into in-plane lamellae. The schematic of this process
transforming micro- to nanolayers is shown in Figure 3.11a. Multiple processes –
coextrusion followed by biaxial stretching and melt recrystallization– created novel
BOPP films with PEO nanolayers (nano-BOPP).
Figure 3.11. (a) Schematic showing the biaxial stretching of microlayers to nanolayers
to produce nano-BOPP film, cross-section AFM images of PP/PEO-90/10 showing
the layer morphology; (b) before stretching (1 × 1); and (c) after biaxial stretching (7
× 7) at 145°C.

Biaxial stretching of the composites was carried out in 135–150°C temperature range
to draw ratios of 5 × 5, 6 × 6, and 7 × 7. An example of cross-section image of the
composite sheet with PP/PEO (90/10, vol./vol.) as a core structure is shown in Figure
3.11b. A thick PEO layer visible in the image shows randomly oriented PEO lamellae.
Biaxial stretching to 7 × 7 draw ratio produced nano-BOPP films with 16 PEO layers
in 33-layered PEO/PP core. Individual PEO layers down to 38 nm were successfully
produced with in-plane lamellar structures. The oxygen permeability 0.703 ± 0.041
barrer in BOPP control films reduced to 0.029 ± 0.007 barrer in nano-BOPP film with
10% PEO after stretching to 7 × 7 draw ratio. The effective PEO permeability decrease
was similar to earlier work. The multilayered films also showed a CO2/O2 selectivity
of 10, when PEO layers were present in the core. Transparency properties did not
show any significant changes in presence of PEO as the PEO layer thicknesses
were significantly below the quarter wavelength of light. An improvement of
10% in tear energy was measured in nano-BOPP films. Because the properties of
PEO are significantly affected in presence of water, measurement of permeability
properties in presence of high humidity was performed. The oxygen permeability
of nano-BOPP films showed a factor of two increment in effective permeability in
presence of 85% relative humidity. However, the overall film performance was still
significantly better than the neat BOPP films.

This approach was further extended to using PCL as a barrier layer in the multilayered
BOPP composite. Multilayered films with a layered core structure of PCL/PP and
outside thick layers of PP were produced in PP[(PCL/PP)n]PP format. The PCL volume
fraction range varied from 3% to 10% [20]. The multilayered films were biaxially
oriented at 155°C, which was sufficient to melt PCL nanolayers (Tm = 57°C).
Subsequent cooling of multilayered films to room temperature, however, resulted
into formation of on-edge lamellae in presence of PP due to transcrystallization
at the interface. The film structure was modified to incorporate PS layers as a
substrate layer in the film structure to produce PP[(PP/PS/PCL/PS/PP)n]PP film,
where PCL layers were confined against PS layers. Biaxially stretched BOPP and melt
recrystallized PCL nanolayers improved the gas transport properties by at least one
order of magnitude, from 0.635 ± 0.018 barrer in BOPP to 0.063 ± 0.002 barrer in
nano-BOPP with 15% PCL. Processing conditions were optimized to isothermally
quench the films between 33 °C and 41°C for improved barrier, as the air-quenched
samples did not show significant improvement. Further analysis of the films for
mechanical properties (tear energy and puncture strength) did not show significant
changes with the addition of PCL and PS components in the layered structure.

> Read full chapter

Biobricks
Michel Biron, in Industrial Applications of Renewable Plastics, 2017

5.4.2 Polyethylene Furanoate

Avantium’s researchers claim that PEF bottles outperform PET bottles in some areas,
particularly, as follows:

•
Barrier properties•PEF oxygen barrier could be 10 times better than PET.•PEF
carbon dioxide barrier could be four times better than PET.•PEF water barrier
could be two times better than PET.

That results in longer-lasting carbonated drinks and extended shelf life.

• Heat behavior•The Tg of PEF is 86°C compared to 61–79°C for PET.•The

melting temperature is about 235°C compared to 240–265°C for PET.

PEF could replace PET in typical applications like films; fibers; and in particular
bottles for the packaging of soft drinks, water, alcoholic beverages, fruit juices,
sauces, dressings, baby foods and edible oils, personal and home care applications,
cosmetics, detergents, food and nonfood products.

> Read full chapter

Ethylene–norbornene copolymers and

advanced single-site polyolefins
T.J. Dunn, in Multifunctional and Nanoreinforced Polymers for Food Packaging,
2011

7.6 Future trends

The future role for single-site polymers in nanofilled food packaging materials is
promising. Nanocomposites are already finding a place in food packaging. They
offer the promise of key benefits, oxygen barrier improvement and moisture barrier
improvement, and they work with generally low-cost materials that process well in
existing processing equipment for film extrusion. They also bring along necessary
food contact compliance in most cases.

The needs are relatively simple: compounding low-cost masterbatch materials and
assuring reliable performance levels independent of processing equipment. And so,
the opportunities are attractive. Ideally, families of compatibilizers appropriate to the
performance expectations of various primary polymers will be offered. These would
seem to be needed in relatively small percentages in a given functional packaging
material, so the cost of managing and maintaining such a broad product line can
be accommodated in the market prices.

Compatibilizers may also provide other functions that enhance value to the pack-
aging material. Better adhesion, stiffness, heat resistance, strength, and surface
properties are well within reach. By way of example, the maleic anhydride mod-
ification of single-site polymers for increasing their compati-bilizing function for
 nanocomposites is chemically identical to the modification of ethylene or propylene
copolymers that act as ‘tie’ resins. Coextruded films require such products to adhere
disparate resins (e.g. Nylon-6 and LDPE) in their multilayer construction. Separate
extruders and die channels direct the tie resins required to their designated position
in the coextrusion. A compatibilizer that can enhance the barrier performance of a
nanolayer while it binds it to an adjacent layer in a coextrusion not only eliminates a
costly structural component, but also simplifies the manufacturing equipment and
process needed to produce functional packaging material.

Importantly, the main principles for using modified single-site polymers to en-
hance nano-composite performance are understood. The challenge becomes one
of combining single-site polymer design latitude with an appreciation of working
knowledge of the principles that control successful and repeatable compatibilization
of nanoclays into target polymers.

> Read full chapter

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