POLITECNICO DI MILANO

School of Industrial and Information Engineering

Master’s Degree in Chemical Engineering

Tie Layers Development for Triple Bubble® Technology

In collaboration with: Dow™ – Tarragona, Spain

University advisor: Prof. Stefano Turri

Company advisors: Carolina Chirinos
Karlheinz Hausmann

Candidate: Alberta Detogni

Mat. 898825

Academic year 2018/2019

ABSTRACT

Nowadays, environment plastic pollution is a very discussed topic. No day passes
by without hearing at least a comment related to that in TV news or newspapers.
Concepts like circular economy and sustainability have gained importance in the
last years, of which the scope is to leave behind the “take-make-waste” economy
embracing sustainable solutions able to respond to human needs with renewable
energy sources, to provide environmental and societal benefits for current and
next generations.
Plastic producers need to be the pioneers of this society trend shift. Being active
part of the process, Dow™ is working on different solutions focused on
sustainability. In the field of food packaging, the idea is to progressively reduce
single-usage products that will be replaced by recyclable products able to show
the same mechanical, barrier and optical properties of previous products, or
even improved, besides reducing the material amount for the production. Dow™-
Kuhne™ collaboration agreement led to the generation of sustainable Triple
Bubble® films for different applications. These solutions are an optimal
alternative to other type of products, such as laminated films, showing ideal
mechanical and barrier properties, besides excellent transparency. Moreover,
thanks to the reduced thickness, together with the possibility of increasing the
amount of PE raw material constituting the film up to 95%, Triple Bubble®
solutions are an interesting player helping to move towards a circular economy.
In order to make them competitive in the food packaging market, some critical
aspects need to be faced and overcome. Between them, a huge decrease in
chemical bonding density leading to significant reduction in adhesion strength
due to orientation process represents a fundamental aspect to be considered.
Aligned to that, current work focused on experimental tie layer formulations
proposed by Dow™ for EVOH to polyolefins adhesion, to detect the best one
showing the widest adhesion range on one side, and to be extended to cook-in
applications, on the other.

I
Table of Contents

ABSTRACT……………………………………………………………………………………………. I
TABLE OF CONTENTS……………………………………………………………………………. II
LIST OF FIGURES…………………………………………………………………………………… IV
LIST OF TABLES……………………………………………………………………………………. VI

Chapter 1: INTRODUCTION & BACKGROUND………………………………………… 1
1.1) Food Packaging and basic requirements………………………………………… 1
1.1.1) Containment................................................................................................ 1
1.1.2) Protection..................................................................................................... 1
1.1.3) Convenience................................................................................................ 2
1.1.4) Communication.......................................................................................... 3
1.2) Circular economy and recyclability………………………………………………… 4
1.2.1) Plastics recycling....................................................................................... 6
1.3) Polymers in multilayer flexible food packaging……………………………….. 9
1.3.1) Polyethylene (PE) – Sealant and bulk material............................. 9
1.3.2) Polypropylene (PP) – Bulk material.................................................. 10
1.3.4) Ionomers – Bulk material....................................................................... 11
1.3.5) Polyethylene terephthalate (PET) – Structural material.......... 11
1.3.6) Ethylene Vinyl Alcohol (EVOH) – Barrier material..................... 12
1.3.7) Polyamide (PA) – Barrier material..................................................... 12

1.4) Film production technologies…………………………………………………………. 14
1.4.1) Extrusion....................................................................................................... 14
1.4.2) Cast technology.......................................................................................... 15
1.4.3) Blown technology...................................................................................... 17
1.4.4) Orientation processes.............................................................................. 19
1.4.4.1) Machine Direction Orientation (MDO).................... 19
1.4.4.2) Tenter Frame..................................................................... 19
1.4.4.3) Double Bubble................................................................... 20
1.4.5) Dow™ & Kuhne™ collaboration agreement.................................... 21
1.4.5.1) About Dow™....................................................................... 21
1.4.5.2) About Kuhne™................................................................... 21
1.4.6) Triple Bubble® technology................................................................... 23
1.4.6.1) General aspects................................................................. 23
1.4.6.2) Technology description................................................. 25
1.4.6.3) Basic components of a Triple Bubble® film.......... 27

II
 Chapter 2: TIE LAYERS ADHESION & PEEL STRENGTH TEST………………….. 29
2.1) Tie-layer basics and importance in Triple Bubble® structures................ 29
2.1.1) Film composition and materials properties................................... 33
2.1.1.1) Historical data analysis – Structures
configuration……………………………………………………………. 33
2.1.1.2) Test validation analysis – Structures
configuration……………………………………………………………. 35
2.1.1.3) Experimental tie layers formulation A –
Structures configuration.............................................................. 36
2.1.1.4) Experimental tie layers formulation B –
Structures configuration.......................................................……. 36
2.2) Design of Experiments (DOE)………………………………………………………….. 39
2.2.1) Peel strength – Test and equipment................................................... 39
2.2.1.1) Peel strength – Mechanical delamination............. 40
2.2.1.2) Peel strength – Chemical delamination.................. 41
2.2.1.2.1) Chloroform selective delamination….. 42
2.2.1.2.2) Formic acid selective delamination….. 43
2.2.2) Fourier Transform Infrared Spectrophotometer – Test and
equipment................................................................................................................. 44
2.2.3) Thickness distribution – Test and equipment............................... 45
2.2.4) Interferometer – Test and equipment.............................................. 46
2.2.5) Water-bath technology testing (cook-in applications)……….. 47
2.2.5.1) Laboratory test………………………………….. 48
2.2.6) Stand-Up Coffee Pouches………………………………………………….. 50

Chapter 3: RESULTS & DISCUSSION……………………………………………………….. 53
3.1) Peel strength test – Results……………………………………………………………... 53
3.1.1) Test validation analysis – Results....................................................... 53
3.1.2) Experimental tie layer formulations A – Results.......................... 54
3.1.3) Experimental tie layer formulations B – Results.......................... 57
3.1.3.1) Experimental tie layer formulations B – Fault
tree analysis........................................................................................ 59

Chapter 4: CONCLUSION REMARKS……………………………………………………….. 67

REFERENCES…………………………………………………………………………………………. 69

III
List of Figures
Figure 1.1: Average carbon footprint of food product production, processing and
packaging
Figure 1.2: Options for waste disposal according to “The Solid Waste Dilemma:
Agenda for Action”
Figure 1.3: Food waste sources in billion $
Figure 1.4: Ethylene polymerization reaction to polyethylene
Figure 1.5: Polypropylene isotactic
Figure 1.6: Commercialized ionomer
Figure 1.7: PET configuration
Figure 1.8: Single flight, single stage screw
Figure 1.9: Typical cast technology apparatus
Figure 1.10: Typical blown technology apparatus (single bubble)
Figure 1.11: Machine Direction Orientation (MDO)
Figure 1.12: Tenter frame orientation technology
Figure 1.13: Double bubble orientation technology
Figure 1.14: Dow™ trademark
Figure 1.15: Kuhne™ trademark
Figure 1.16: Triple Bubble® technology apparatus
Figure 1.17: Kuhne™ Triple Bubble® technology
Figure 1.18: Triple Bubble film construction

Figure 2.1: Mechanisms of adhesion in coextruded films
Figure 2.2: Chemical bonding density decrease during conventional 3x3 orientation
Figure 2.3: Qualitative adhesion strength trend in conventional Triple Bubble®
processes
Figure 2.4: PE/EVOH adhesion
Figure 2.5: PET/ionomer adhesion in shrink films – DuPont™ trials
Figure 2.6: PET/PP adhesion in shrink films – DuPont™ trials
Figure 2.7: PET/PP adhesion in non-shrink films – DuPont™ trials
Figure 2.8: Dynamometer testing the tie layer performance (peel strength test)
Figure 2.9: Theoretical peel strength approximate behavior – Peel strength vs
Specimen length
Figure 2.10: Samples immersed into the solvent for delamination activation
Figure 2.11: Samples hanging to be dried off
Figure 2.12: Expected film delamination for target structures due to chloroform
dissolution
Figure 2.13: Expected film delamination for target structures due to formic acid
dissolution, with EVOH/PP (a) or EVOH/PE (b) as weakest adhesion links

IV
Figure 2.14: FTIR spectrum
Figure 2.15: Gaugemeter
Figure 2.16: Beams constructive interference (left) vs beams destructive
interference (right)
Figure 2.17: Packaging after shrinkage during industrial trials
Figure 2.18: Water bath and metallic structure for cook-in applications
Figure 2.19: Sheets located onto the metallic structure
Figure 2.20: Original structure of PE//PET-based pouches
Figure 2.21: Laminated (a) and non-laminated (b) PE-based Dow™ pouches
solutions
Figure 2.22: Template for manual production of coffee SUPs
Figure 2.23: PE-rich Triple Bubble® coffee SUP

Figure 3.1: PET/PA adhesion results comparison – Meyrin vs Tarragona 1st trial vs
Tarragona 2nd trial
Figure 3.2: EVOH/PO adhesion for group A samples – Shrink films
Figure 3.3: EVOH adhesion for group A samples – Non-shrink films
Figure 3.4: EVOH/PO adhesion for group B samples – Shrink films
Figure 3.5: EVOH/PO adhesion for group B samples – Non-shrink films
Figure 3.6: Adhesion for group B tie layers – Chemical vs Mechanical delamination –
Shrink films Figure 3.7: Adhesion for group B tie layers – Chemical vs Mechanical
delamination– Non-shrink films
Figure 3.8: B #1 – LS FTIR analysis – Actual sample delamination
Figure 3.9: B #9 – LS FTIR analysis – Actual sample delamination

V
List of Tables
Table 1.1: Properties of PE films
Table 1.2: Advantages, limitations and applications of blown and cast technologies
Table 1.3: Functionalities related to different materials in Triple Bubble® films
Table 1.4: Properties of conventional orientation technologies vs Triple Bubble®

Table 2.1: EVOH/PO tie layer and annealing conditions for group A samples – Shrink
films
Table 2.2: EVOH/PO tie layer and annealing conditions for group A samples – Non-
shrink films
Table 2.3: EVOH/PO tie layer and annealing conditions for group B samples – Shrink
films
Table 2.4: EVOH/PO tie layer and annealing conditions for group B samples – Non-
shrink films

Table 3.1: Possible causes and hypothesis validation of failure
Table 3.2: Interferometer results for B #1 – LS
Table 3.3: B #1 – LS thickness measurements (average, highest and lowest)
Table 3.4: B #1 – LS thickness measurements

VI


CHAPTER 1: INTRODUCTION AND BACKGROUND

1.1) Food packaging and basic requirements

Nowadays, packaging is essential. As a matter of fact, no good is processed,
manufactured, handled and transported without the need of something to protect it.
Due to the increasing demand of materials able to withstand the needs, packaging
market has been tremendously expanded in the past 30 years, and this can be
obviously extended to the food market as well, since about 50% of the overall
packaging is dedicated to wrap, preserve and transport food. Moreover, modern
industrialization asks the food packaging market to respond to incredible changes
in society lifestyle, such as increasing single households and women working, with
a reduced time to cook fresh meals1.
The huge number of fields and the wide and deep knowledge required to meet the
food packaging market requirements make the choice and development of the
proper packaging an interdisciplinary and greatly challenging science.
Despite many consumers recognize in packaging somewhat superfluous and often
not fundamental, the socio-scientific community agrees in defining the discipline as
essential in safely delivering and protecting food in the best possible way after
processing2.
The tasks that packaging performs must be extended to a much wider group, other
than just protecting food from the external environment. The main roles it has in the
food field are listed as follows: containment, protection, convenience, and market
communication3. The next paragraphs will be dedicated to the deeper description of
such aspects.

1.1.1) Containment
This is the most obvious one, since to avoid product loss and contamination due to
the presence of an external environment, packaging is needed. Despite the
numerous studies dedicated to the development of adequate packaging and the
recognized environmental impact of the recurrent concept of over-packaging,
under-packaging is still an issue in some cases, and it often leads to food damage or
leaks3.

1.1.2) Protection
The main food spoilers are generally microorganisms, water vapors, gases, as
oxygen or carbon dioxide, but also many others. Most of the time, the protection
provided by packaging in terms of preservation of the energy spent during the
production process is underestimated. As demonstrated by previous practical
experiments, 1 kg of bread needs 15.8 MJ of energy, in different forms such as
1
transport fuel, heat, electrical energy and so on, to be processed from time zero
(production) to the storage, after being sold. Without proper protection, these 15.8
MJ would be completely lost, since the purchaser would not be able to consume the
final product, due to its spoilage. On the other hand, the production of a specific low-
density polyethylene bag able to protect such an amount of bread (1 kg) is estimated
in 1.4 MJ of energy, demonstrating that the packaging process is advantageous in
terms of energy savings3.
Furthermore, different works demonstrated the fundamental role of packaging in
protecting meat products. As a matter of fact, meat production process from the raw
material to the final product to be stored and consumed is one of the main
contributors to global environment damage4. As pointed out by the Food and
Agricultural Organization of the United Nations, it is estimated that 18% of global
greenhouse emissions come from meat treatments and production, overcoming the
worldwide impact of the transportation sector5. However, meat processing impact
would be even higher without proper packaging protection according to previous
studies6. Figure 1.17 reports an estimation of the average carbon footprint of major
food categories production, processing and packaging. It is of fundamental relevance
to highlight the huge environmental impact of meat production with respect to other
food types in general, but also when compared to its own packaging production.
Much lower emissions come from packaging production in general, for the reported
examples, confirming the importance of this specific role of packaging.

Figure 1.1: Average carbon footprint of food product production, processing and packaging7

1.1.3) Convenience
The extraordinary changes faced in the lifestyle of modern society, including the
growing trend towards “grazing” (snack-type meals), the increasing number of
people living alone, and often working extra-hours, result in the need of greater
convenience in household products, having an extended shelf life and long
expiration date3. Employing convenient packages, which allow, for instance, to
preferentially heat the food itself directly inside them or allow to easily spread the

2
sauces or dressings, can help the sales growing3. Moreover, packaging supports the
subdivision of industrial production into sale-like portions of the same product,
related to convenience of production on a large scale, which leads to the reduced
costs of the as-produced goods. As a matter of fact, if the apportionment would not
exist, the industrial-scale production would not be likely to occur, either. The
possibility of subdividing the products into single portions helps to keep the
freshness for as long as they are opened and consumed by the customer, as well3.
Finally, also the most convenient shape can be selected by making a careful package
choice. In this way, many much easier-to-handle products are available on the
market, even easier to be wrapped and packed into a second or third package for
delivery and storage, optimizing the space occupied3. Additionally, costumers’
categories of consumption are constantly monitored to adapt the packaging shape,
opening technique, color and other features to market requirements.

1.1.4) Communication
In a previous work developed by Judd et al., food packaging is defined as a “silent
salesman”8. As a matter of fact, while on one side the packaging must protect the
content inside, on the other hand many different studies recognized the importance
of the external aspect to rise customers attraction and, therefore, to increase sales.
Not only the shape of the final product at the supermarket has been demonstrated
to be of primary importance, but also labels are fundamental into providing
necessary information and convincing the purchaser that one product is better than
the other. Moreover, labels are not only convenient in terms of sales rise but, in fact,
they are required by legislation in developed countries, to show which the package
content and its formulation are3. Proper communication of the content is a main
concern during industrial production, too. As a matter of fact, warehouse storage
and product treatments could become messy and chaotic when the proper label is
not reported or not stated in an appropriate manner. More recently, barcodes have
been introduced to overcome the limitation of different languages used in different
countries, when international trade is performed for the production and shipping3.
In fact, traceability as essential subsystem of quality management9 needs to be
guaranteed at each production level, as well as during storage and selling, to
recognize the provenience of raw (and not) materials and to be able to address any
doubt or question quickly and correctly.

3
1.2) Circular economy and recyclability

The doubts and adverse general opinion against packaging, either made of plastic,
paper, aluminum, glass or others, significantly erased in the last two decades, with
polymeric containers being the main target of public protests and disappointment.
While, on one side, this theory could be related to personal attitudes and experience
coupled together with media awareness and information, most of the times the
subjective perception of unnecessity or environmental damage due to packaging use
is referred to the almost complete functions’ fulfillment of the package before
reaching the public, especially for food applications. Some of the myths globally
accepted by the common opinion rely, in fact, on the belief that food packaging is the
greatest and single cause of unrecoverable waste and that it consumes a
considerable amount of scarce materials and energy, as Levy et al. pointed out in
their work10. However, in the previous section of this work, the impact of food
production was already compared to packaging production for some food
categories, as reported in Figure 1.1, to highlight the fundamental protecting role
required to extend food shelf life to avoid over-waste and need of food over-
production.
Due to the actual recognized damages that waste generation and use-and-throw
packaging cause to the environment, concepts like sustainability and circular
economy have gained a fundamental relevance over scientific community, but also
public belief. As a matter of fact, despite ambiguous instrumentalization of the
concepts constantly takes place by different groups, sustainability has been proven
a “political concept as persistent as are democracy, justice and liberty”11. To sustain
that, the number of works focused on the concepts of sustainability and circular
economy is countless, as reported by Geissdoerfer et al.12, who also gave a proper
description of circular economy, reporting it as “a regenerative system in which
resource input and waste, emission, and energy leakage are minimized by slowing,
closing, and narrowing material and energy loops. This can be achieved through
long-lasting design, maintenance, repair, reuse, remanufacturing, refurbishing, and
recycling”.
A fundamental role in moving towards sustainability and circular economy is played
by municipal solid waste (MSW) tuning and management. Municipal solid waste is
considered as the left part of the product, which can be thrown away after its usage
because no longer needed. The highest percentage of MSW is constituted by different
products from country to country but, as general trend, paper has been recognized
as the most relevant group in high-income countries, while food waste guides the
trend in less developed regions13. Despite United States and Europe are
representative for less than the 17% of global population, it has been estimated that
the two are responsible for approximately one-fourth (25%) of the entire worldwide

4
waste production, significantly overcoming the year average production per person
on global assessment13.
According to “The Solid Waste Dilemma: Agenda for Action” essay, published by the
Environmental Protection Agency (EPA), the options for waste disposal can be
reported on a triangular-shaped representation following a specific hierarchy14. On
the left side of Figure 1.2, the differentiation is reported in terms of waste volume
production, with the landfill and waste-to-energy options clearly representing the
most important solutions for the waste treatment and disposal of high amount of
garbage, as located at the bottom of the “Traditional Waste Hierarchy”. On the other
hand, as highlighted on the right side of Figure 1.2, the most sustainable options rely
on waste reduction, by limiting the amount of material used, and, eventually, waste
reuse, completely aligned with a circular economy approach.

Figure 1.2: Options for waste disposal according to “The Solid Waste Dilemma: Agenda for Action”

A remarkable value is associated to recycling, with the aim of converting the waste
into a completely new product, that can be sold and used again. However, these
alternative solutions are still not competitive with respect to landfill and combustion
of disposed products in terms of volumetric capacity. As a matter of fact, the higher
waste treatment weight capacities and economic advantage of such technologies
keep them in pole position, even though the cost associated might vary significantly
from country to country, according to facilities’ availability and community
legislation and incentives. Today, the important role of all the disposal techniques,
joining together the positive aspects they bring, is widely recognized. Then, waste
management options are chosen depending upon local conditions, to optimize the
system as much as possible and, hence, to maximize sustainability14. Important
waste management efforts are spent to study and develop food recovering
techniques. In fact, it was previously mentioned that food waste represents the most
important waste source in lower-income countries, but a main player in developed

5
countries, too. It has been estimated that the 80% of food waste comes from homes
and consumer-facing businesses, as clear from Figure 1.3, and that if no efforts would
be spent for recovering the waste, potentially 89 million tons of food would be lost15.
This demonstrates that consumers education as well as an efficient improvement in
operational and supply chain management are fundamental aspects to be
considered to actively reduce food waste. According to ReFED™ economic value
analysis in 201615, the benefit-cost ratio associated to efficient education campaigns
could be of approximately 2.8/0.1.

Figure 1.3: Food waste sources in billion $

However, a primary role between prevention solutions is covered by food
protection, as discussed in Section 1.1 of the current work. Standardization of food
labels dates and instructions (benefit-cost ratio of approximately 1.8/0.0515),
optimization of food packaging design and sizing to favor complete food
consumption and avoid residuals (benefit-cost ratio of approximately 0.9/0.215),
improvement of food packaging properties to prolong products shelf life by slowing
down microorganisms’ spoilage without modifying products nature (benefit-cost
ratio of approximately 0.4/0.215) are some of the proposed solutions towards food
market sustainability goals in the field of food protection improvement15. Therefore,
constant work needs to be conducted in the field of food packaging to quickly
respond to needs’ change and sustainability requirements.

1.2.1) Plastics recycling
Food plastic packaging has been replacing traditional solutions in the last decades,
such as metal- and glass-based packages, thanks to exceptional lightweight and
functionality, with the possibility of meeting the different requirements of the
market, in terms of low density, strength, robustness and fabrication capabilities16.
Due to the important role of plastic recycling in approaching sustainability goals for
the coming future, this section will be dedicated to some considerations regarding
the procedure, to understand its opportunities and limitations. As a matter of fact,
plastic recycling has clearly to be considered a main player in sustainable
manufacturing, due to the exploitation of recovered plastic wastes for the

6
production of brand-new products, which would have otherwise been produced
with virgin materials.
Despite the recognized developments and widespread use of polymeric films as
reported above, recycling, which has been employed since the years 1970s, is mostly
limited to some classes of flexible products, such as polyolefin-based films, and rigid
materials, such as PET-based and HDPE-based products, since issues are erased by
low processability and purity of the products to be disposed17. Two different waste
streams are generally considered, which are post-consumer, coming from
households, and post-industrial, which is related to industrial processes waste.
Recycling procedures must be differentiated in the two cases, since the two streams
have a very different composition18. Homogeneity generally characterizes post-
industrial scraps, while, on the other hand, the post-consumer stream is composed
by many different polymers and it is highly contaminated. Contamination derives
from the presence of additives, labels, inks and similar, which are not an integral
part of the polymeric structure18. Particularly for inks, which represents a main
concern for post-consumer stream purification, many companies developed
technologies for removal. Cationic surfactants have been proven effective for water-
based ink removal from polyethylene flexible films19. More recently, University of
Alicante researchers developed a plant process to favor ink removal without the
harm deriving from chemicals usage, as previously reported, due to the exploitation
of water-based solvents to obtain a recycled plastic having similar properties to the
original one20.
Disregarding the composition, a general recycling procedure to be followed for
waste stream purification can be described. Waste collection and sorting are the first
steps of the cycle. Difficulties in sorting are related to the variable nature of the
disposed products, as already discussed, which causes variability in properties
distribution, often requiring human supervision to obtain a subdivided mixed
fraction from which the energy spent for its initial production might be recovered21.
However, machineries implementation has been introduced to perform the sorting
step in a growing number of fields. Automatization of the process requires huge
investments from the machine production side, since the detection of differences in
shape or optical properties between different polymers and contaminants is
mandatory for further steps21.
Once sorting is completed, materials are washed and dried. Following treatments of
the so-obtained compounds allow to remove volatile substances, damaged particles
and particulate solids through filtration, and extrusion and pellets cutting give the
final product. Chemical solvents might be used as well to interact with specific
components and modify the structure to favor the recycling process21, as discussed
for ink removal.

7
To conclude, post-consumer packaging recycle can provide wide opportunities for
the reduction of virgin materials usage, as well as carbon dioxide emissions and
landfilling disposal. Sustainability is improved due to exploitation of wasted
materials for the manufacturing of brand-new products, which can eventually show
mechanical and optical properties close to the original product. However, limitations
in waste volumes disposal and improvable mechanical and optical properties of the
recycled package need to be faced in order to build a fully competitive process
against traditional disposal techniques such as landfill and waste-to-energy
disposal14.

8
1.3) Polymers in multilayer flexible food packaging

1.3.1) Polyethylene (PE) – Sealant and bulk material
Polyethylene ((𝐶# 𝐻% )' ), produced by ethylene polymerization starting from 1930s,
represents the most important polymer in food packaging, mainly due to its
advantageous quality-price ratio. Polyethylene belongs to partially crystalline,
hydrophobic, light weight thermoplastics group22. Besides showing a good
resistance to many different chemicals, such as acids and inorganic solvents, its
application as bulk material in multilayer food packaging films favors a significant
decrease of the water vapor structure permeability, but not relevant reductions in
oxygen transmission, even though this directly depends on density.

Figure 1.4: Ethylene polymerization reaction to polyethylene

Its synthesis technique is the addition polymerization of ethylene gas, but depending
upon the reaction conditions, which can vary in a wide range of temperatures (100-
350ºC) and, mostly, pressures, three main different products, having dissimilar
properties, can be obtained: low-density (LDPE) produced according to a high-
pressure process (1000 to 3000 atm), linear low-density (LLDPE) synthesized at low
to medium pressure (200 up to 1000 atm), eventually with a metallocene catalyst,
and high-density (HDPE) polyethylene, obtained with a low-pressure process and a
Ziegler-Natta catalyst guiding the synthesis22. Some of the most relevant Dow™
polyethylene commercial grades are Attane®, Dowlex®, Elite®, Affinity® and many
others37.
Basic properties of the three polyethylene classes are reported in Table 1.1 below.

9
 H2O Vapor O2 CO2
Tensile Softening
Polyethylene Transmission Transmission Transmission
Strength Point
type (g/100 in2/24 (cc/100 in2/24 (cc/100 in2/24
(MPa) (°C)
h) h) h)

Low density
(0.91-0.94 1.4 500 1350 9-15 120-180
g/cm3)

Linear Low
density (0.915- 0.6 225 500 21 120-180
0.925 g/cm3)

High density
(0.94-0.975 0.3 125 350 28 135-180
g/cm3)
Table 1.1: Properties of PE films22

1.3.2) Polypropylene (PP) – Bulk material
Polypropylene ((𝐶( 𝐻) )' ) synthesis is performed at
approximately 100 atm and 60°C, and operative conditions
together with the catalyst type (Ziegler-Natta, metallocene)
define the nature of the product, according to different
stereo-configurations: isotactic, syndiotactic or atactic23. The Figure 1.5:
Polypropylene
most regular isotactic configuration is reported in Figure 1.5
isotactic
as a reference. Polypropylene is extensively used in configuration
manufacturing fibers, packaging films, molded and extruded articles. Like
polyethylene (and, eventually, polyolefins in general), it is used as interior liming in
box-type containers for beverages. In recent years, the demand and use of oriented
(OPP) and biaxially oriented (BOPP) polypropylene for food packaging applications
has dramatically increased, fueling the market of orientation technology
development for multilayer films properties improvement23, as will be discussed
later.

10
1.3.3) Ionomers – Bulk material
Market name reference for this class of materials, obtained
by copolymerization of ethylene with a small percentage
(7 to 30%) of unsaturated carboxylic acid24, was first
introduced in 1960s by DuPont™ as Surlyn®, which is also
the current identification. As reported by Brown25 in one Figure 1.6:
Commercialized
of his works, formability, toughness and visual appearance
ionomer
are improved by joining Surlyn® with polyamides or PET
in coextruded films, which is a direct application in the Triple Bubble® technology
market. Additionally, ionomers show exceptional puncture and impact resistance
which allow to exploit Surlyn®-based multilayer structures in food applications
where sharp products need to be wrapped and protected, such, for instance, in meat
with bones packaging by exploitation of Triple Bubble® shrink bags. Despite the
further positive tendency of heating very fast during the shrink process, poor oxygen
barrier properties are one of the worst aspects concerning ionomers exploitation,
which could be overcome by coupling them with traditional barrier materials, such
as EVOH or polyamides25.

1.3.4) Polyethylene terephthalate (PET) – Structural material
Polyethylene terephthalate (known as PET), of which
the structure is shown in Figure 1.7, is the most
important polyester that belongs to the class of linear, Figure 1.7: PET configuration
transparent thermoplastics. Its application as
structural material in Triple Bubble® films is related to its good stiffness, due to its
crystallinity and the presence of a benzene ring in its structure, but also to its
excellent mechanical properties and stability. Its outstanding capacities are related
to tensile strength, chemical resistance, light weight, elasticity and stability over a
wide temperature range, which brings to its exploitation not just in the development
of “boil-in-the-bag” packaging and oven trays, but also frozen food bags26.
Orientation eventually increases the already good tensile strength of PET films and
reduces the elongation at break by 4-5 times. Oxygen and carbon dioxide barrier
properties, and gases in general, are improved with respect to polyolefins, but still
worse than EVOH resins. Moreover, PET films are glossy and transparent, fulfilling
the food market requirements for good optical properties of the packaging, when
the food needs to be visualized by the consumer. In fact, PET is mostly employed in
the market in biaxially oriented and heat stabilized forms. This is because, when in
the crystalline form, it is brittle but opaque, while, on contrary, it shows excellent
transparency but low toughness after orientation and heat stabilization26.

11
1.3.5) Ethylene-vinyl alcohol (EVOH) – Barrier material
Ethylene-vinyl alcohol (EVOH) is a crystalline copolymer synthesized from ethylene
and vinyl alcohol. Extensive hydrogen bonding increases its crystallinity, to which
EVOH relates its exceptionally high barrier characteristics. As a matter of fact, the
barrier capacity against gases such as oxygen, carbon dioxide and many other polar
chemicals is extremely high. Then, food flavor and quality retention are significantly
improved27.
The presence of EVOH layers in multilayer food packaging has practically allowed
the substitution of many metal and glass containers with polymeric structures.
Indeed, while EVOH gas barrier performance has clearly been shown superior with
respect to most of the other synthetic materials at low humidity, a sharp decline of
the barrier properties has been reported at humidity higher than 70%. The reason
is related to hydroxyl groups presence in the structure and, hence, material
hydrophilicity27. However, EVOH in Triple Bubble® multilayer films is eventually
surrounded by additional water-resistant layers, such as polyolefins or ionomers, to
overcome the issue in performance decline due to environmental humidity. Despite
EVOH copolymers are generally characterized by high crystallinity, the property
results to be affected by the percentage between different monomers. As a matter of
fact, the higher the amount of ethylene monomer, the lower the crystallinity and the
lower the barrier properties. On the other hand, processability increases and water
moisture transmission decreases. Experimental evidence demonstrated a ten-time
increase in oxygen barrier properties with a shift from 42% to 27% w/w of ethylene
content27.

1.3.6) Polyamide (PA) – Barrier material
Synthetic polyamides, known in the market as nylon, were developed starting from
the 1930s by DuPont™, with nylon-6,6 as first attempt28. Nowadays, based on
manufacture techniques, two different groups of polyamide resins are available: the
first identified by the number of carbon atoms in the diamine and in the acid (for
instance, nylon-6,6) exploited for the synthesis, the second one identified uniquely
by the number of carbon atoms constituting the amino acid chain from which it is
obtained (for instance, nylon-6).
Polyamide films are generally modified by using fillers, plasticizers, antioxidants and
stabilizers, resulting in a huge availability of different formulations. Furthermore,
the performance is strongly affected by the distance between repeating units in the
main chain of the structure, and the overall length of the structure, too28.
Due to the polarity of amide groups, a common feature is related to permeability to
water vapor, which affects the barrier performance of polyamide films. As a matter
of fact, wet polyamide layers show a worse performance as gas barriers due to water
plasticizing effect, and this is the reason why their application as barrier layers

12
requires them to be dried before exploitation28. Other fundamental properties of
polyamide films are odor retention, thermoformability, flex-crack resistance and
mechanical strength, which can then be further improved by orientation or biaxial
orientation, as in Triple Bubble® films.

13
1.4) Film production technologies

1.4.1) Extrusion
Nowadays, extrusion process is recognized to be one of the most used plastics
processing methods. It employs a screw rotating in a heated barrel to create finish-
shaped products with a constant cross section (sheet, film, coatings, tubes, pipes,
profiles). The feed is made of pellets, which are then transformed, homogeneously,
into a molten state by a continuous process29. The molten plastic is then passed
through a die (circular for blown technology, flat for cast technology) and collected
at the exit of the extruder. With the aim of joining polymeric layers to other types of
materials, to include labels or include additional performance properties to the
package, extrusion-coating or lamination are the traditional techniques for the
application of a continuous polymer layer of uniform thickness to a substrate, such
as paper, board or metal29. Extrusion-coating requires as first step the application of
an adhesion promoter (primer) to the unwound substrate. The coated web is dried
and pressurized into a nip to be then wounded up30. Lamination is performed to
support plastic films and prevent wrinkling and tearing of foils for packaging
purposes. Polyurethane- or polyethylene-based adhesives or waxes are applied to
the underside of the foil so that combination with the substrate occurs on a
subsequent nip. Drying in a heated oven followed by a cooling step by means of
cooling rolls complete the lamination process30.

Figure 1.8: Single flight, single stage screw37

Figure 1.8 shows the simplest extruder configuration. Three regions are
distinguished, from right to left according to the picture: feed, transition and
metering section. Plastic is preheated in the feed zone to be supplied to the other
sections of the extruder. Screw movement compacts the plastic and removes
eventual trapped air in the transition section and plastic is finally homogenized in
the metering zone, in order to provide a material uniform in temperature and
pressure to the subsequent circular or flat die31.

14
A further development of the conventional extrusion technology is the so-called
coextrusion process, in which, as the name suggests, more extruders are exploited
to obtain two or more molten polymer layers coming out from the same line
(multilayer structure). Coextrusion meets a wide range of application needs and is
very useful when the requirements of the final product cannot be fulfilled by
exploitation of a single polymeric material, solution which is anyways very unlikely
to be exploited nowadays, allowing the possible combination of different
compounds in adjacent layers, providing specific functions, and optimizing the cost.
Downgauging is then achieved without losing in performance, but even improving
it, and without modifying material key properties, by employing compounds
characterized by very high performance, but higher cost, as well31.

1.4.2) Cast technology

Figure 1.9: Typical cast technology apparatus37

Cast technology employs a flat die for the extrusion. An accurate and constant die
body temperature is important to avoid gauging variances, since a cold area results
in a thin-gauge band, while a hot in a heavier band. Insulation jackets are then
available to maintain a uniform temperature condition, exploiting heating media as
oil, steam or electrical resistance heaters. Thermocouples or resistance temperature
detectors are used for the measurements32. The die feeding port is generally placed
in the system with the aim of giving an equal distribution of the flowing material on
both sides of the die itself, with the melt web cast directly onto a chill roll afterward,
having an internal cooling shell for temperature control by means of a cooling fluid.
At this point, the choice of adding supplementary cooling devices, such as air
blowers, might help to quench down the system after passing through the flat die, as
well as pinning the web securely to the chill rolls, providing good contact. The
cooling device guarantees a proper regulation of the final temperature and film

15
behavior, representing one of the main advantages that the current technique has
when compared to other solutions available on the market32. Furthermore, the film
thickness is exceptionally controlled, and the polymer melt strength required is not
as high as in the blown technique. However, when a viscosity mismatch is present
between polymers constituting the different layers of the plastic film, the resulting
thickness of the single layers can significantly differ, bringing the lower viscosity
material to flow towards the edges of the die. On contrary, in some other and more
peculiar cases, viscosities are required to be different to avoid flow instabilities32.
Since cast dies show a constant width, and the process of die changing is time-
consuming and expensive, the final process obviously results being more sensitive
to the desired width of the final product, on contrary to the blown film technology,
in which the blow-up ratio can be easily varied32. The role of the subsequent nip
arrangement is mainly to control the tension in the generated web, which is then
treated, slit and wounded into rolls, to be finally stored32.
Obviously, the cast methodology can be extended to coextrusion applications,
introducing a combining adapter, so-called feed block, able to join the layers exiting
from the single dies. A second and alternative possibility relies on a multimanifold
die, which is more flexible in terms of thickness of the skin layer, resins viscosity
range and melt temperature differentials between adjacent layers. As a matter of
fact, adapters combination forces to exploit a skin layer thickness not overcoming
the 10% of the core layers total thickness, a resin viscosity differential between
layers of at least 2:1, then up to 4:1, and a temperature as homogeneous as possible,
to avoid negative effects on the final product quality and characteristics. On the other
hand, the construction of multimanifold dies is much more complicated compared
to the conventional solution, being made of more parts joint together32.

16
1.4.3) Blown technology

Figure 1.10: Typical blown technology apparatus (single bubble)37

Blown film dies are typically characterized by a circular shape, which allows the
molten material to be uniformly distributed, obtaining a homogeneous bubble to be
inflated by a certain and controlled amount of air depending upon the desired
diameter. The bubble-to-die diameter ratio (BDR) is, in fact, a critical parameter for
the process control and final product characterization. The die design must be
related to the viscosity and melt index of the different layers involved in the
formation of the final polymeric film33. Randomization of film thickness variations
guarantees an improvement of the final product flatness and quality, on contrary to
what happens when flat dies are exploited. However, purging and polymer
degradation might occur due to a characteristic higher residence time of the
polymeric material in the system33. Additional advantages shown by the blown
technique are a good film orientation control, which could be further increased
introducing a proper orientation step, and high range of viscosity tolerance of the
treated material. Two orientation directions are considered: machine and cross. A
machine-oriented film is uniquely stretched in machine direction (MD). On the other
hand, biaxial orientation requires the film to be stretched in both machine (MD) and
transversal, or cross, direction (TD) 34.
In coextrusion blown applications, the die design is more complicated. The spiral
mandrels or rings constituting the core of the feeding structure are fed by a certain
number of holes, and some junctions are then available to combine the flows into a
single, but multicomponent, one. Geometry and space limitations due to the
presence of a multilayer molten material represent a challenge for blown
coextrusion technology development. However, thanks to the simulation models
developed for non-Newtonian fluids, the capability of predicting and controlling the

17
system behavior when the melt viscosity significantly varies has dramatically
improved33.
Another fundamental factor to be tuned is the residence time of the multicomponent
material into the spiral system. An increase of such parameter leads to a much better
uniformity of temperature between layers, but higher pressure drops and
temperature values, as well. A cooling system is then required to quickly decrease
the temperature below the melting point following extrusion, by means of an air ring
which encircles the die exit, forming the so-called “die lips”33. Inflation and an
additional cooling step are performed afterwards, to stabilize the structure, so that
the bubble can be finally closed by a series of nip rolls. Two winders are required for
winding up the film and controlling the film tension-to-diameter ratio, by
monitoring the difference in speed between nip and winding rolls. Alternatively, a
pneumatically activated idler roll that applies pressure to the web can be used. After
production, in most cases, blown films are post-treated by lamination, metallization
and orientation to obtain the structure suitable for packaging33.
The next section of this work will be dedicated to the description of advantages and
challenges associated to the orientation process, and the technologies currently
available for performing it.

18
1.4.4) Orientation processes
Orientation techniques, for which material molecules are forced to line up in a
specific direction, are extensively employed in the packaging market. Different
processor manufacturers employ orientation for improving products properties34.
As a matter of fact, orientation provides the enhancement of different properties of
a plastic film, creating new opportunities for reducing the amount of material used
(downgauging) or obtaining much better performance of the employed film with the
same material amount due to a concrete increase in product yield. Some of the
properties positively affected by orientation are, for instance, moisture barriers,
tensile strength and stiffness, optical properties and many others34. As pointed out
in the previous section, orientation is performed in two directions: machine,
generally by means of some rolls, and transversal, for instance by exploitation of a
tenter frame or by air blowing. Different orientation processes are available in the
market to improve certain properties of plastic films and will be described next:
Machine Direction Orientation (MDO), Tenter Frame and Double Bubble are the
most commercially used34.

1.4.4.1) Machine Direction Orientation (MDO)
Films MD oriented are suitable for achieving high stiffness,
low machine direction tear, and high transparency. The film is
oriented by rotating rolls placed at the exit of the bubble, as
Figure 1.11 shows. The process is organized into four
separated steps36:
1. Preheating, for a uniform temperature distribution in the
film, to have no wrinkles;
2. Drawing, for molecules orientation and film stretching,
reducing the thickness and increasing the length;
3. Annealing, to freeze the structure configuration and control Figure 1.11:
shrinkage percentage; Machine Direction
4. Cooling. Orientation (MDO)

1.4.4.2) Tenter Frame
Extrusion and casting are performed to obtain the initial thick sheet for subsequent
orientation. The typical thickness ranges between 300 and 3000 μm after the flat
die, depending on the target final thickness and the stretch ratio37. Following the
casting roll, a machine direction stretcher provides the orientation of the semi-
molten film web in machine direction (generally of 4-5 times) by means of three
groups of rollers for the pre-heating (first), stretching (second) and annealing
(third). In the last step, the orientation in transversal direction (TDO) takes place by
means of clips, in three subsequent steps as reported for the machine direction

19
orientation. The orientation ratio is of 8-9 times, and the film is kept in the semi-
molten state to achieve the typical final target thickness of 10-60 μm. Temperature
is higher during transversal orientation with respect to machine orientation, and it
is controlled by inflating air in the chamber37. The film is collected by a final winder
placed at the exit of the transverse direction stretcher.

Figure 1.12: Tenter frame orientation technology

Tenter Frame process provides huge potential for lightweight structures
simplification, and many new opportunities are open in the field concerning possible
polymer improvement/substitution, full recyclability and better protection37.

1.4.4.3) Double Bubble
The technology could be slightly different depending upon the final product. For
instance, in PVdC production the first bubble is formed using traditional blown film
technique and hot water is used to pre-heat the system, while infra-red rays are
exploited with the same aim for polyolefin shrink films production. After film
formation in the first bubble, the second bubble is dedicated to orientation, as it
happens in three-bubble processes37. As it will be deeply described later in this
work, orientation in machine direction takes place due to the presence of some rolls
at the exit of the bubble itself, while transversal orientation is guaranteed by air
blowing. The difference between double and three-bubble technologies is related to
the annealing step. As a matter of fact, in the current case annealing is performed
using a combination of hot and cold rolls right before the final wrapping winder, and
not in a dedicated bubble like in Kuhne™ Triple Bubble® characteristic process,
belonging to the class of three-bubble processes, as will be explained next37.
Additionally, a cross linking unit is available after the first bubble in current lines.

Figure 1.13: Double bubble orientation technology

20
1.4.5) Dow™ & Kuhne™ collaboration agreement

1.4.5.1) About Dow™
Dow™ was founded in 1897 by H.H. Dow, an
industry and electrochemical pioneer, but the
first commercial-scale production of bleach
began only in 1898. During the first years of the
previous century, Dow™ pursued research in
calcium chloride, magnesium metal and
Figure 1.14: Dow™ trademark
acetylsalicylic acid fields, before expanding to
the new area of organic chemistry.
However, it was not until World War II that the research towards plastics was
accelerated, fueling the production of different products, belonging to various fields
such as automotive industry or high-value product lines.
At the very beginning of the years 2000, Dow™ began to restructure its portfolio by
going deeper into targeted high-value markets and to rebuild the company’s R&D
infrastructure. Over the past 10 years, Dow™ has strengthened its innovation and
integration, making long-term investments in R&D and low-cost feedstocks.
In 2015 Dow™ and DuPont™ announced that their boards of directors unanimously
approved a definitive agreement under which the companies would merge, then
subsequently spin off into three independent companies. The merger was
successfully completed in 2017 with the aim of separating into industry-leading,
publicly traded companies in Agriculture, Materials Science and Specialty Products.
Then, the spin off officially occurred on April 1st, 201938.

1.4.5.2) About Kuhne™
Kuhne™ was founded in 1934, but Kuhne™ Anlagenbau GmbH,
currently specialized in the production of individual blown film
lines, became an official independent subsidiary division in 1979,
four years after headquarters were moved to Sankt Augustin. Core
competence is related to the manufacture of multilayer systems of
up to 13 layers, which can process virtually all thermoplastic resins.
Systems are divided into the following segments: Cool Bubble®,
Figure 1.15:
producing water-quenched blown films, Triple Bubble®, for Kuhne™
biaxially oriented blown films production, and SmartBubble®, trademark
synthesizing air-cooled blown films. As will be recalled in the next
section, Triple Bubble® lines guarantee exceptional barrier and optical properties,
as well as mechanical strength, for products to be exploited in the food packaging
market for high-barrier packaging, sausage casings and shrink bags production39.

21
In the last five years, Dow™ and Kuhne™ have been collaborating in some projects
for the development of materials for Triple Bubble® lines, where Kuhne™ provides
the machines and Dow™ provides the resins. Current project is a result of such
agreement.

22
1.4.6) Triple Bubble® technology

1.4.6.1) General aspects
Triple Bubble® technology is a tradename of Kuhne™ Anlagenbau GmbH, which
allows the production of multilayer films, up to 13 to 17 layers, in one single and
continuous pass, mainly for food packaging applications, according to a three-bubble
process. A wide variety of different materials can be exploited, such as PE, PP, EVOH
and PET, each of them providing a specific functionality to the structure, as reported
in Table 1.2 below. Flexibility in properties control allows to exploit Triple Bubble®
films in different fields, such as in the production of sausage casings, shrink bags and
lidding films, with great importance associated to meat packaging market37.

Layer Functions Resins examples

Mechanical & Thermal

Structural material PET
protection, thermoforming

Barrier Gas protection PA, EVOH (PVDC)

Affinity®, Surlyn®, Appeel®,

Sealant Sealing and secondary sealing
Dowlex®

Dowlex®, Attane®, Elite®,

Bulk layer Shrinking, puncture resistance
Innate®

Tie layer To keep all layers together Bynel®, Elvax®

Table 1.2: Functionalities related to different materials in Triple Bubble® films

The resulting film shows a consistent 3 to 6 times increase of the gas barrier
performance thanks to the presence of a high barrier material such as EVOH or PA
in the core of the structure, related to a significant improvement of food protection
and, hence, shelf life extension37. Furthermore, a high stiffness, tensile strength,
puncture resistance, but lower tear resistance have been reported by films produced
in Triple Bubble® processes.
The orientation in the second step of the process in both machine and cross direction
leads to an exceptionally uniform performance along the whole width, while the
third bubble step increases the dimensional stability of the product thanks to the
annealing relaxation of the structure occurring in it, providing the chance to exploit
the product in both shrinkable and non-shrinkable applications37. Triple Bubble®
technology allows the replacement of conventional lamination techniques by a
procedure able to decrease the multilayer thickness up to 50% and eventually down
to 20-30 μm, guaranteeing the cut in packaging waste, besides condensing the

23
process into a three-step continuous method, with no need of batch or manual
operations37. Moreover, actual work is focused on film recyclability intensification
by increasing the percentage of same-type materials to approach the market
demand for enhanced sustainability.
Table 1.3 below shows a comparison in advantages and limitations of the main
orientation techniques described in the previous section and Triple Bubble®
technology37.

Machine Direction
Orientation Tenter Frame Double Bubble Triple Bubble®
(MDO)

• Output depends • Huge output • Crosslinking • Medium to high

on line • Single material equipment output
(blown/cast) film (PET, PP) included • Multi-material
• Can be single or • Multi-material • No annealing in film
multilayer film (PP and rd
the form of a 3 • Homogeneity of
EVOH, PP and bubble properties
amorphous PA • • Low waste
and others) • Highest cooling
• High cooling rate rate
• Light weighting
(thin films)
• High stiffness,
tensile strength,
puncture
resistance
• Low tear
resistance
Table 1.3: Properties of conventional orientation technologies vs Triple Bubble®

24
1.4.6.2) Technology description
As highlighted, Triple Bubble® technology belongs to blown film methods, since
three in-series bubbles are formed between the extruder and the final wind up to
produce the multilayer highly performing film.

Figure 1.16: Triple Bubble® technology apparatus37

Coextrusion, by means of up to 13 extruders equipped with melt pumps, occurs as
very first step in the process, before entering the first bubble, in which film
generation takes place. A water bath unit is fundamental for a fast quenching
afterwards, maintaining an amorphous or just slightly crystalline structure, to
guarantee the consequent ease of bubble stretching and orientation in the second
stage37. The quenching is performed quickly by means of cooling water at a variable
temperature of 5 to 40°C, with a fast cooling rate, bringing the raw material
temperature from 260/270°C down to 15/20°C.
Starch powder might be added at this point by a dedicated spray system, to prevent
blocking during pre-heating process when the film is closed, as well as to favor the
further bubble re-opening.
Infrared heaters at the very beginning of the second-bubble step allow a
temperature increase favoring the melting of compounds to be oriented. The second
bubble provides film stretching, with a conventional orientation ratio of 3x3 (three
times increase in length in both machine and cross direction). Machine orientation
is controlled by differential roller speeds at bubble end, while transversal
orientation is performed by blowing up the air37. Double orientation enhances
barrier to gases and water, besides improving mechanical properties, stiffness,
puncture resistance and transparency. Refer to previous section for more details
about orientation effect.
These positive aspects concerning performances of Triple Bubble® films help
understanding how they can efficiently replace laminated films, as previously

25
defined, by easier to recycle, coextruded, multilayer films. One of the driving forces
in the process development is related to an actual packaging waste reduction up to
50%, but also to improved perforated resistance and consequent consumer
satisfaction, especially for those applications in which sharp and harsh products
need to be wrapped and packed, such as, for instance, meat with bones or dried
spaghetti37.
The last step, taking place in the third bubble, is the film annealing for shrinkage
control. Shrinkable films are obtained at lower annealing temperatures (60°C to
80°C depending upon the film), while non-shrinkable films at higher annealing
temperatures (80-100°C), even though the shrinkage percentages and the
temperature to be selected depend on the nature of the material itself. Typical
shrinkage levels vary according to the application of the produced Triple Bubble®
film: approximately 0-5% for lidding films (no shrinkage required), 2-40% for
sausage casings (low shrinkage required), 20-70% for shrink bags (shrinkage is
required)39. Again, also in this step, the desired process temperature is reached by
using infra-red heaters, which could also be substituted by hot air injection. At the
exit of the third bubble, the film is collected into rolls by winding it up.
The line output and speed for the conventional Triple Bubble® process are in the
range of 20-250 kg/h and 30-300 m/min, respectively39.

Figure 1.17: Kuhne™ Triple Bubble® technology

Sustainability goals for the coming future are not just focused on a concrete food
waste reduction by the exploitation of very light packaging to favor downgauging,
but also on the production of a 100% thermoplastic structure, and on the
achievement of a higher waste stream purity. Research & Development target is
driven towards material combinations using same family-type raw materials, with
only 5 to 10% amount of dissimilar resins, so that the materials compatibility will be
dramatically improved. Avoiding the use of different packaging substrates and by
introducing compatibilizers in the form of thermoplastic-based tie layers, the
expected recyclability capacity of multilayer films will be vividly enhanced, as well.

26
The prerequisites for this to happen are the elimination of non-thermoplastic
adhesives, extensively used in laminated structures, the absence of entrapped ink,
which cannot be washed away, favored by surface printing, and crosslinking
elimination, which can cause environmental issues and make structure recycling
difficult37. As a matter of fact, the “take-make-waste” system that characterizes a
linear economy in which resources are taken from the ground to be transformed into
products and then thrown away once used must be substituted by a circular
economy focused on recyclability and waste recovery and reuse. Only making the
circular economy a priority it will be possible to benefit everyone’s needs within the
limits of the planet40.
Trible Bubble® technology, coupled with the use of high performance resins, clearly
represents an excellent solution to produce valuable food packaging products, since
it can fulfill the requirements for laminated films in terms of barrier and mechanical
properties, therefore being able to extend food shelf life and, hence, to reduce food
waste. Furthermore, a decrease in the amount of material needed for the production
(downgauging) is in-line with plastic market sustainability requirements, together
with the removal of non-recyclable adhesives and cross-linking elimination37. As a
matter of fact, Ellen MacArthur Foundation stated the must-have of the new plastic
economy, which needs to be focused on plastic never becoming waste or pollution
through elimination of unnecessary items, innovation to ensure plastic to be
reusable, and circulation to guarantee that every plastic product can be part of a
continuous cycle and not an harm for the environment40.

1.4.6.3) Basic components of a Triple Bubble® film
The structure of a Triple Bubble® film can vary, according to the number of layers
and type of materials constituting them. The most general assembly in terms of
materials role and nature can be reported as shown in Figure 1.18.

Figure 1.18: Triple Bubble film construction

The most external PET layer, so-called structural, provides mechanical and thermal
protection to the overall film. However, novel developments aligned to sustainability
goals will consider the possible substitution of such compounds with a polyolefin
layer, to increase the amount of same family-type raw materials, as anticipated in
the previous section of this work37. As a matter of fact, the following bulk multilayer,
visible in the above list, is generally constituted either by an ionomer or polyolefin.
The bulk compound must provide a good shrinking capacity, puncture resistance
and low water vapor permeation. Barrier layers limiting gas diffusion through the

27
structure, especially oxygen, are mostly made of EVOH, PA and PVDC, while the
sealant is generally a polyolefin-based plastomer, providing sealing and secondary-
sealing resistance and which can vary depending upon the requirements and testing
conditions. Finally, tie layers, that repetitively appear in the structure, are
compounds providing adhesion between layers of different nature37. In fact, their
importance will be stressed and highlighted in a dedicated section of this work.
Chapter 2 will give a complete overview about their fundamental role and the
importance of developing new formulations to improve the performance of the
overall Triple Bubble® film37.
Stability to temperature, light, water and solvents is of extreme importance in the
definition of the final properties of the film, and it is directly related to the chemical
nature of polymers37.

28
CHAPTER 2: TIE LAYERS ADHESION & PEEL STRENGTH TEST

2.1) Tie-layer basics and importance in Triple Bubble® structures

Tie layers have been employed for bonding dissimilar layers in multilayer
coextruded and laminated structures starting from 1970s41, especially in multilayer
films applied in food packaging. Improved flexibility in their application and affinity
towards the huge variety of materials that need to be joint together are provided
thanks to the peculiar wide adhesion range generally shown by this class of
products. Depending upon the material they must be compatible with, their
composition might differ significantly, moving from PE-based to acrylate-based
compounds, modified by acid or anhydride grafting, even though these are just some
examples37. Being tie layers an integral and challenging component of the overall
structure, film properties and final performance can be tuned by careful tie layer
choice, control and eventual modification. In fact, to satisfy the extremely
demanding requirements of the barrier packaging market, the selected tie layer
must respond to the specific type of barrier layer employed (EVOH, nylon or others),
the required adhesion level, the employed processing technique (cast, blown), the
equipment constraints and expected final properties of the film. Therefore, the
choice of a proper tie layer is extremely significant, especially where the number of
layers to be joint belong to more than two different classes of materials, as it happens
in Triple Bubble® films37. Additionally, depending upon the layers’ nature, adhesion
mechanisms involved in the structure bonding might differ. Diffusion/compatibility
to polyolefins and chemical reaction with polar materials are recognized as the two
most relevant processes involved in keeping coextruded structures together, as
Figure 2.1 shows for a conventional multilayer coextruded film. Chemical
interactions are always promoted by the presence of reactive sites, which are more
likely to exist in polar polymers, such as EVOH (hydroxyl groups) or polyamide
(amine-end groups). Yet, hydrogen bonds, induced dipoles and covalent bonds are
important sources of interaction, as well41.

29

Figure 2.1: Mechanisms of adhesion in coextruded films37

Due to all the challenges tie layers need to respond to, the understanding of the
importance of their constant formulation developments in Triple Bubble®
structures is straightforward. In fact, tie layers must be functional under the
demanding mechanical and thermal conditions of the film synthesis process,
additionally showing a good viscosity matching and adhesion to the materials in
contact on the two opposite sides37. Particularly in the case of Triple Bubble®
processes, extensive orientation in both machine and cross direction, performed in
correspondence of the second bubble, results in an additional demanding step for
tie layers, due to dramatic decrease of chemical bonding density, as shown in Figure
2.237. As a matter of fact, previous studies on tie layers behavior demonstrated a
consistent decrease in adhesion strength passing from the first (film formation) to
the second bubble (film orientation), which is recovered only in a small extent
during annealing (third bubble), as reported in Figure 2.3 where indicative peel
strength values are recalled42.

Figure 2.2: Chemical bonding density decrease during conventional 3x3 orientation37

30

Figure 2.3: Qualitative adhesion strength trend in conventional Triple Bubble® processes42

As already pointed out, tie layer composition is tremendously important due to the
need of bonding materials of different nature. As an example, Figure 2.4 shows the
adhering interface between a PE-based resin and an EVOH barrier. Due to materials
types, tie layer formulation in the current case must include a PE-based copolymer
(polyolefin matrix or base copolymer) to promote diffusion at PE/tie layer interface,
but also an anhydride (grafting of maleic anhydride) or acid group (functional
group) to favor the chemical interaction at tie layer/EVOH interface37. In fact,
PE/EVOH adhesion strength evaluation was the target of the current study.

Figure 2.4: PE/EVOH adhesion

Frequently, polyolefin-based matrixes are selected as fundamental constituents of
tie layers to provide the optimal combination between polarity, compatibility,
reactivity and bulk physical properties. In fact, the choice is related to some of their
characteristic features43. As a matter of fact, most of the structures in which tie layers
are employed are partly constituted by polyolefin or polyolefin-based materials,
showing a great compatibility with the polyolefin-based tie layer matrixes. The
reactivity of polyolefin-based compounds is another great and important aspect,

31
since they can be easily modified and functionalized by either grafting or
copolymerization. Finally, the combination of toughness and flexibility drives
polyolefin-based matrixes applications towards the minimization of delamination,
critical for the integrity of multilayer structures, and the improvement of mechanical
properties of the final product. Furthermore, toughening components can be added
to the matrix to favor the adhesion, while processability can be improved by
antioxidants addition, to prevent melt fractures43.
Before moving to films description, some of the many factors affecting adhesion
performance in multilayers structures will be reported and commented. Clearly,
many factors can enhance adhesion. Between them, high polymers reactivity at the
interface is the most relevant. However, operating conditions like proper pressure
and contact time (directly controlled by line speed), as well as a sufficiently high
temperature of the molten polymers, especially when maleic anhydride is grafted,
are important, too37.
High moisture levels and presence of gels in the tie layer resin have been proven to
negatively affect adhesion properties. Viscosity mismatch between different layers
could be dangerous, too. Moreover, as repetitiously reported in the dedicated
section, Triple Bubble® processes include an extensive orientation step in the
second bubble having a strong impact on tie layer adhesion due to the great increase
of the contact surface between adjacent layers, which leads to a decrease in chemical
bonding density37.
It is then clear that the factors affecting tie layer choice are of various nature and
involve many different properties of the overall polymeric film and the tie layer
material, in specific. This demonstrates the importance of the current study in
improving the constituent representing one of the most challenging components of
the multilayer structure. Therefore, polyolefin-based tie layers represent a
competitive solution in the market of tie layers for multilayer coextruded films and,
of particular interest for the current study, Triple Bubble® applications37. Bynel®
and Amplify™ MAH-grafted resins are currently the most attractive option offered
by Dow™ for Triple Bubble® tie layers. Bynel® and Amplify™ grades can virtually
meet any need, belonging to an established portfolio with a proven track record of
success and optimized quality and low gel content for the most demanding
structures37.
Starting from current analysis and results, future work will be then dedicated to
other aspects of Triple Bubble® films performance and properties, to approach the
sustainability expectations and goals for the very next future.

32
2.1.1) Film composition and materials properties
Extreme flexibility showed by Triple Bubble® films at responding to different
market requirements by materials modification requires the same adaptability to tie
layers, which need to show wide viscosity ranges to match adhering materials’ ones.
Therefore, current study focused on EVOH to polyolefins adhesion performance of
Dow™ tie layer grades in Triple Bubble® films. This section will be dedicated to the
description of Triple Bubble® films object of the analysis. The main goal was to test
different tie layer resins for polyolefin/barrier layer (EVOH) interface for both
shrinkable (shrink bags) and non-shrinkable applications. Thus, tie layers for
EVOH/polyolefin adhesion were repeatedly modified to test different formulations.
The tie layers used for EVOH/PE and EVOH/PP adhesion were the same for each of
the tested samples.
Structure target of the study was a multilayer PP bulk-based structure having EVOH
as barrier, as will be described in the next section. Structures were characterized by
the presence of both EVOH/PP and EVOH/PE adhesion interfaces, with the aim of
testing both adhesions without the need of producing differentiated structures.
However, the choice was demonstrated to be not appropriate since the nature of the
delaminating interfaces could be recognized only by performing infrared
spectroscopy, which is a time-consuming procedure and cannot be conducted for
each of the tested specimens.
PET/PP tie layer adhesion was already tested, and results were reported in previous
works from DuPont™, demonstrating the good performance of the currently
employed Dow™ formulation not only for PET/PP adhesion, but for PET/ionomer as
well42. Results from DuPont™ study42 will be reported to understand which the
order of magnitude expected from tie layers adhesion was, despite the target of the
study was related to EVOH/ PE and EVOH/PP adhesion. Furthermore, test protocol
validation was first conducted due to relatively new developments in peel strength
testing, as will be recalled.
Analyzed films were characterized by an approximate 50 μm thickness, while each
of the three tie layers represented only the 5% (2.5 μm) of the overall film thickness.

2.1.1.1) Historical data analysis – Structures configuration & Results
Two different types of structures were reported on DuPont™ study42 for testing
DuPont™ tie layer formulations in joining together PET/ionomer and PET/PP,
respectively. Specifically, PET/ionomer adhesion strength was measured on the
following ionomer bulk-based multilayer structure, characterized by PA/EVOH/PA
barrier layer, and by high shrinkage:
PET / Tie layer / Ionomer bulk / Tie layer / PA / EVOH / PA / Tie layer / PE & Sealant

33
During DuPont™ trials, PET/ionomer tie layer was changed between different
samples, but ionomer/PA and PE/PA tie layers were kept constant. Results
comparison is shown in Figure 2.5, where it is possible to compare adhesion values
of proposed tie layers.

Figure 2.5: PET/ionomer adhesion in shrink films – DuPont™ trials42

On the other hand, PET/PP adhesion was tested for both shrink (lower annealing
temperature) and non-shrink (higher annealing temperature) films characterized
by a PP bulk-based multilayer structure, again having the triplet PA/EVOH/PA as
barrier:
PET / Tie layer / PP bulk / Tie layer / PA / EVOH / PA / Tie layer / PE & Sealant
As mentioned above in the previous case, only PET/PP adhesion tie layer was
changed between different samples, but PP/PA and PE/PA tie layers were kept
constant. Results shown in Figure 2.6 allow the comparison within reference and
experimental formulations performance. As previously, literature values were
considered as reference and target tie layers performance were expected to be
comprised in the provided range, even though the current test had the aim of
evaluating EVOH/polyolefin tie layers.

34

Figure 2.6: PET/PP adhesion in shrink films – DuPont™ trials42

Figure 2.7: PET/PP adhesion in non-shrink films – DuPont™ trials42

2.1.1.2) Test validation analysis – Structures configuration
Test validation was performed to verify that the procedure was properly conducted.
Results on PET/PA adhesion on a PA-barrier structure were compared to previous
results obtained for the same reference structure in Meyrin – DuPont™ site and
Tarragona – Dow™ site in 2018. Extensive work was conducted in DuPont™ site in
Meyrin to confirm the performance of tie layers in adhering PET/PA and, therefore,
results were considered completely reliable and used to validate the test protocol
followed during the trials. The multilayer structure for testing PET/PA adhesion was
characterized as follows:
PET / Tie layer / PA / Tie layer / PP layers / PE layers & Sealant

35

2.1.1.3) Experimental tie layer formulations A – Structures configuration
Samples belonging to the group were characterized by a PP bulk-based structure
having EVOH as barrier material. The scope of the project was to test new tie layers
based on Dow™ resins with improved cost and price positioning. The idea was to
select the most flexible resin able to be used as tie layer for EVOH/PO adhesion. Peel
strength was measured after chemical delamination for tie layers performing EVOH
adhesion to adjacent materials (PP, PE). However, as highlighted, further work on
these formulations will be conducted in the future.
Experimental group A was characterized by the following structure:
PET / Tie layer / PP bulk / Tie layer / EVOH / Tie layer / PE & Sealant
EVOH/polyolefin tie layer was changed between different samples. Table 2.1 and 2.2
list group A samples names, for shrink and non-shrink films respectively,
characterized by different annealing temperatures, as reported. The presence of
both PE and PP in contact with EVOH had the aim of measuring both adhesions, but
it was proved inconvenient. Films were produced in Kuhne™ in April 2019.

2.1.1.4) Experimental tie layer formulations B – Structures configuration
Current samples were characterized by the exact same structure of group A samples:
PET / Tie layer / PP bulk / Tie layer / EVOH / Tie layer / PE & Sealant
The objective of the current project was to test EVOH/polyolefin tie layers
eventually applicable in Triple Bubble® and blown film technologies based on
Dow™ resins for both standard and cook-in food packaging applications. Therefore,
performance of EVOH/polyolefin tie layers was tested. As well as the previous case,
the idea was to use chemical delamination to be selective in measuring target tie
layer peel strength. The choice of locating both PP and PE in contact with EVOH, as
showed in structure configuration, had the aim of theoretically allowing to test
EVOH/PP and EVOH/PE adhesion without the need of producing two differentiated
structures, hence saving time and reducing the number of machine operations. Films
were produced in Kuhne™ in April 2019, as for group A. Table 2.3 and 2.4 report
EVOH/PE tie layer samples names for shrink and non-shrink samples respectively,
together with shrink percentage and annealing temperature. Results in the following
chapter will be focused on the comparison of experimental grades with reference
grades.

36
 Sample Name Shrink % Annealing T
Tie layer
SHRINK FILMS (°C)
MD CD
Reference Ref A #1 - HS Ref A #1 41 51 ≅ 60

Reference Ref A #2 - HS Ref A #2 41 51 ≅ 60

Experimental A #1 - HS A #1 39 50 ≅ 60

Experimental A #2 - HS A #2 41 51 ≅ 60

Experimental A #3 - HS A #3 44 51 ≅ 60

Experimental A #4 - HS A #4 41 51 ≅ 60

Experimental A #5 - HS A #5 40 53 ≅ 60
Table 2.1: EVOH/PO tie layer and annealing conditions for group A samples – Shrink films

Sample Name Shrink % Annealing T

Tie layer
LOW-SHRINK FILMS (°C)
MD CD
Reference Ref A #1 - LS Ref A #1 15 21 ≅ 80

Reference Ref A #2 - LS Ref A #2 11 19 ≅ 80

Experimental A #1 - LS A #1 20 23 ≅ 80

Experimental A #2 - LS A #2 14 20 ≅ 80

Experimental A #3 - LS A #3 16 20 ≅ 80

Experimental A #4 - LS A #4 16 24 ≅ 80

Experimental A #5 - LS A #5 16 22 ≅ 80
Table 2.2: EVOH/PO tie layer and annealing conditions for group A samples – Low-shrink films

37

Sample Name Shrink % Annealing T
Tie layer
SHRINK FILMS (°C)
MD CD
Reference Ref B #1 - HS Ref B #1 41 51 ≅ 60

Reference Ref B #2 - HS Ref B #2 41 51 ≅ 60

Experimental B #1 - HS B #1 39 50 ≅ 60

Experimental B #2 - HS B #2 40 50 ≅ 60

Experimental B #3 - HS B #3 41 50 ≅ 60

Experimental B #4 - HS B #4 41 50 ≅ 60
Table 2.3: EVOH/PO tie layer and annealing conditions for group B samples – Shrink films


Sample Name Shrink % Annealing T
Tie layer
LOW-SHRINK FILMS (°C)
MD CD
Benchmark Ref B #1 - LS Ref B #1 15 21 ≅ 80

Benchmark Ref B #2 - LS Ref B #2 11 19 ≅ 80

Experimental B #1 - LS B #1 12 25 ≅ 80

Experimental B #2 - LS B #2 13 20 ≅ 80

Experimental B #3 - LS B #3 21 29 ≅ 80

Experimental B #4 - LS B #4 21 22 ≅ 80

Experimental B #5 - LS B #5 18 22 ≅ 80

Experimental B #6 - LS B #6 20 25 ≅ 80

Experimental B #7 - LS B #7 16 23 ≅ 80

Experimental B #8 - LS B #8 18 23 ≅ 80

Experimental B #9 - LS B #9 24 26 ≅ 80

Experimental B #10 - LS B #10 13 19 ≅ 80

Table 2.4: EVOH/PO tie layer and annealing conditions for group B samples – Low-shrink films

38
2.2) Design of experiments (DOE)

2.2.1) Peel strength – Test and equipment
Peel strength test is intended to determine the resistance of a film to be delaminated.
Hence, the target is the performance of the tie layer in the multilayer structure. As a
matter of fact, the process is conducted on barrier films containing tie layers,
otherwise delamination does not occur. Delamination occurs in correspondence of
tie layers, which represent one of the most critical points of multilayer structures,
and it can be performed in two different ways: mechanically or chemically. Once
delamination is activated by means of one of the two techniques mentioned above,
peel strength is measured in correspondence of the tie layer of interest38.
A dynamometer as the one reported in Figure 2.8 is used to test adhesion strength.
The specimen, required to be of 15 mm width to guarantee results comparison to
previous data, is introduced by the “ears area”, which is the bottom part where
delamination has already started, into the jaws of the instrument. Dynamometer
operating conditions are 30 mm/min speed and 100 N cell load. The reported values
are the peel strength (N/15 mm width) and its standard deviation. Peel strength
reports the force (N) to be applied to continue the delamination of the specimen,
characterized by 15 mm width38.

Figure 2.8: Dynamometer testing the tie layer performance (peel strength test)

The program registers any force variation and a plateau in the peel strength-
specimen length graph is expected to be visualized if the performance of the tie layer
is homogeneous throughout the whole length of the specimen itself, as shown in
Figure 2.9 as an example.

39

Figure 2.9: Theoretical peel strength approximate behavior – Peel strength vs Specimen length

Next two sections will be dedicated to mechanical and chemical delamination
description, performed before peel strength measurements, highlighting advantages
and limitations of both.

2.2.1.1) Peel strength – Mechanical delamination
Mechanical delamination is a non-selective delamination technique employed to
perform peel strength test afterwards. Historically, mechanical delamination has
been employed for the adhesion strength evaluation of conventional multilayer
structures, in which tie layers’ sides were in contact with the same materials, such
as the following case:
PE / Tie layer / EVOH / Tie layer / PE
Delamination is achieved by cutting the specimen and propagating the damage
manually in order to detect a separation between two of the layers constituting the
structure. If the process is not sufficient to activate delamination, sealing of two
specimens at high temperature can be performed37. Then, specimens are pulled
apart by performing the seal strength test. As a matter of fact, high sealing
temperatures generally lead to a seal force higher than tie layer force and, therefore,
delamination is likely to take place instead of seal opening37.
However, current technique does not allow selectivity in delamination. Only the
weakest adhesion tie layer can be tested due to the possibility of activating
delamination uniquely in correspondence of such point. Consequently, when
selectivity in testing a specific adhesion layer, of which it is not known whether it
represents, or not, the weakest spot, chemical delamination needs to be used, as will
be described37. Mechanical delamination is followed by peel strength measurements
by means of a dynamometer as reported in the previous section.

40
2.2.1.2) Peel strength – Chemical delamination
Chemical delamination is a delamination technique performed before peel strength
test, alternatively to mechanical delamination. Chemical solvents are chosen to be
selective in delaminating the adhesion layer of interest for the analysis37. In fact, the
process is the results of work conducted in DuPont™ Meyrin site due to the need of
testing specific adhesion layers recognized not to be necessarily the weakest of the
structure. Two different chemical solvents have been tested: chloroform and formic
acid. Further insights will be given after detailed procedure description.
Samples are cut into specimens characterized by 15 mm width and 200 mm length.
A high number of specimens is required, generally 15, because not all of them will
be able to be tested during the procedure, and at least 8 specimens need to be
analyzed as required by test protocol, to reduce standard deviation37.
A jar containing the solvent (chloroform or formic acid) is located into the fume hood
with related labels for the description of the risks associated to solvent nature.
Specimens are then partially allocated into the jar, as shown in Figure 2.10. Only the
end side of the specimens is immersed into the solvent to limit the delamination
area. In fact, test protocol requires delamination to be just activated during this step
and consequently continued by the dynamometer when peel strength is recorded37.

Figure 2.10: Samples immersed into the solvent for delamination activation

Characteristic time for dissolution is established to be of at least 2 hours when
chloroform is used, and at least 24 for formic acid. Accurate washing is performed
to remove any trace of solvent, and specimens are hung into the fume hood to dry
off, afterwards (Figure 2.11), before performing peel strength test37.

41

Figure 2.11: Samples hanging to be dried off

2.2.1.2.1) Chloroform selective delamination
Chloroform, also known as trichloromethane, is a commonly used laboratory
solvent, with chemical formula 𝐶𝐻𝐶𝑙( . As reported by the Hazardous Substance Fact
Sheet44 from the New Jersey Department of Health, “chloroform is a colorless liquid
with pleasant, sweet odor. It is used as a solvent and to make refrigerants, resins,
and plastics”.
Chloroform is toxic, irritant and hazardous for health. Its molecular weight is 119.37
g/mol. Chloroform is highly volatile, the boiling point is fixed at 61.1°C at 760 mmHg.
At the same atmospheric pressure, the melting point is -63.3°C.
Chloroform reacts with potassium, sodium, magnesium and zinc (chemically active
metals), but also with strong bases, as sodium and potassium hydroxides, and
oxidizing agents (perchlorates, peroxides and others). This aspect is important for
safety reasons, because of the risk of fires and explosions when it gets in contact with
the abovementioned substances. On the other hand, chloroform has been shown to
be not compatible with alkali metals such as lithium, mixtures of water and strong
alcohols, acetone, perchloric acid and many others.
Due to its high volatility and reactivity with oxidizing agents, the Hazardous
Substance Fact Sheet44 suggests the employment of a closed, dark container in a
ventilated area to store the product, to avoid contact with light and combustibles.
Moreover, chloroform decomposes to toxic gases on hot surfaces and attacks
plastics, rubbers and coatings. Due to its properties, safety gloves and glasses are
required while dealing with this substance to prevent skin irritation or intoxication.
When chloroform is used as dissolving agent to activate chemical delamination, its
preferential interaction with polyolefins in the bulk layer in Triple Bubble®
structures is expected. For a target structure belonging to group A or group B, the
expected layers separation after chloroform dissolution is reported in Figure 2.12.

42
Due to the need of testing EVOH/PO adhesion, chloroform was not used as a solvent.
However, it will be repeatedly pointed out when results will be shown that further
infrared spectroscopy investigation is always required to recognize the nature of
delaminating interfaces. As a matter of fact, due to chloroform predictable tendency
of attacking plastics, a specific and constant pattern of interaction is not likely to be
recognized.

2.2.1.2.2) Formic acid selective delamination
Formic acid, or methanoic acid, is the simplest carboxylic acid, with chemical
formula 𝐻𝐶𝑂𝑂𝐻, and it is a colorless liquid with a pungent odor. Corrosiveness is
reported as formic acid’s feature in the Chemical Safety Datasheet45 for the
substance, as well as toxicity and flammability.
Its main application is as preservative and antibacterial agent, and it is extensively
corrosive to metals and tissues. Formic acid is an important intermediate for many
chemical reactions, and occurs naturally in the venom of bees and ant strings.
The molecular weight of formic acid is 46.025 g/mol, and the boiling point at
atmospheric pressure is fixed at 101°C, while the melting point at 8.3°C. The
reactions given by formic acid are numerous, and between them the deprotonation
with CO2 and hydride formation.
When plastic multilayer films target of the analysis are dissolved into formic acid,
the preferential interaction with EVOH is expected. Hence, Figure 2.13 reports the
theoretical two scenarios for peel strength measurements, depending upon the
weakest adhesion link (EVOH/PP or EVOH/PE), for group A and group B samples.
However, as previously pointed out for chloroform, the high reactivity of formic acid
with plastic materials makes more complicated to recognize a constant pattern of
interaction between solvent and polymeric layers in the Triple Bubble® structure.
Therefore, only infrared spectroscopy can properly characterize the delamination
interfaces after formic acid dissolution. In fact, formic acid was the unique solvent
used during current trials. Due to formic acid properties, safety gloves and glasses
are required while dealing with this substance.

Figure 2.12: Expected film Figure 2.13: Expected film delamination for
delamination for target target structures due to formic acid
structures due to chloroform dissolution, with EVOH/PP (a) or EVOH/PE
dissolution (b) as weakest adhesion links

43
2.2.2) Fourier Transform Infrared Spectrophotometer – Test and equipment
In the previous section, the difficulties in defining delamination interfaces without
proper analysis has been highlighted.
A Fourier Transform Infrared Spectrophotometer, abbreviated as FTIR, can
generate an infrared spectral scan of samples that absorb infrared light to identify
materials surface nature. If the material does not absorb infrared light, a spectral
scan cannot be obtained.
FTIR is the first logical step in identifying a polymer, also used for additives
characterization, comonomer identification and additive analysis46.
Infrared light’s electromagnetic region lies between visible light and microwaves.
Three regions of infrared light are identified, so called near-infrared (from 13300 to
4000 wavenumbers (cm-1)), mid-infrared (from 4000 to 400 wavenumbers (cm-1)),
and far-infrared (from 4000 to 10 wavenumbers (cm-1)). However, the mid-infrared
region is the most commonly used in FTIR, generating a typical infrared scan of the
light spectrum, which can be then easily recognized46.
FTIR polymer identification of an unknown polymeric film is done by matching the
material’s infrared peaks to peaks of similar infrared scans of known materials. In
such a way, an FTIR spectral analysis can easily identify classes of polymers such as
polyethylene, nylon, polyesters, polypropylene, polycarbonates or acetals. However,
an FTIR spectral scan alone should not be expected to identify the type of nylon or
polyester or others, identify a polypropylene or acetal as a homopolymer or
copolymer, or determine whether the polyethylene is a high density or low density
material46. Hence, the discrimination is done within classes of materials but not
within the same class. A typical spectrum obtained by FTIR analysis is shown in
Figure 2.14, in which different
peaks refer to different classes of
materials present in the structure.
Specific knowledge of the
technique is required to analyze
the outcome, and the process is
extensively time-consuming46. Due
to this reason, current work was
perform by Dow™ Tarragona
analytical lab team and it was
focused on testing only two
Figure 2.14: FTIR spectrum
selected samples by infrared
spectroscopy, as will be shown in
the next chapter.

44
2.2.3) Thickness distribution – Test and equipment
Chapter 1 reported the description of Triple Bubble® process. As highlighted,
second bubble is dedicated to the orientation step, which provides several positive
features to the resulting film. Between them, uniformity in performance along the
whole film width and length is expected to be shown, according to a theoretical
uniform thickness distribution and material performance, unless extensive bubble
instability is detected37.
Thickness distribution test is performed to determine the thickness of a plastic film.
A gaugemeter, as the one showed in Figure 2.15, is
employed to measure the thickness of the film, measuring
it 20 times along the whole film width and length and
calculating an average. In fact, the reported values are
average thickness (µm) and thickness standard deviation
(µm)37. Group A and group B samples were characterized
by a theoretical thickness of 50 µm. Results in thickness
distribution average and variability will be shown in the
next dedicated chapter of this work, especially relevant for
helping explaining results for the second group (B). Figure 2.15: Gaugemeter

45
2.2.4) Interferometer – Test and equipment
Dow™ TS&D lab interferometer was employed to detect the presence of all the
expected layers characterizing group A and group B samples, as well as their actual
thickness.
A beam splitter, as part of the apparatus, is used to split a light beam into equal
halves. The reference beam shines onto a mirror and reaches the instrument
detector, while the second beam passes through the object of interest for the
measurement, in this case the multilayer structure, traveling an extra-distance due
to pattern deviation to become slightly out of phase with respect to the reference
beam47. Once the deviated beam reaches the detector, a pattern of light and dark
areas is recognized due to interference, constructive or destructive, between the two
beams, the reference and the deviated, as
reported in Figure 2.16, respectively.
Interference can be constructive or destructive
depending upon the extra-distance traveled by
the deviated beam, hence the film surfaces
composition47.
The expected layer subdivision in the analyzed
structures must be given to the program as a
reference to elaborate the results. As a matter of Figure 2.16: Beams constructive
fact, the program requires at least a rough interference (left) vs beams
indication of how the film should be constituted, destructive interference (right)
and it is able to show a comparison between the
expected composition and the actual detected layers thickness. Therefore, a general
idea of the film configuration is required in the first place, to proceed with the
analysis49. In the current study, few reference samples were tested by
interferometer analysis to detect the eventual tie layer rupture or damage during
film synthesis process. Further insights related to the reasons for which the test was
performed will be given once peel strength results will be commented, in Chapter 3
of the current work.

46
2.2.5) Water-bath technology testing (cook-in applications)
In recent years, the requirements for practical packaging allowing food to be cooked
directly inside the container have significantly grown. During the cooking
procedure, packaging must provide not only mechanical strength, but also
protection from vapors and gases in a controlled way. Moreover, the packaging must
withstand the demanding operative conditions at which the cooking process is
conducted. As a matter of fact, the working environment is harsher than a
conventional water bath process for shrinkage only. Shrinkage remains in fact a
fundamental parameter to tune during the process, despite cooking gains
importance, as well. As shown in Figure 2.17, a good adhesion between food and
packaging needs to be provided after shrinkage of the plastic film, which generally
occurs in the first seconds in which the complex is immersed into the water bath.
However, a longer time, generally of 4 to 10 hours depending upon the temperature
and application of the final product, is required to perform the cooking. Cook-in
technology avoids an additional and separated step after packaging shrinkage,
reducing the number of industrial unit operations that need to be conducted.

Figure 2.17: Packaging after shrinkage during industrial trials

Growing market demand demonstrates the need of developing and testing novel
packaging solutions for cook-in applications. Triple Bubble® films, due to their
improved mechanical performance and thermal resistance, represent a possible
option.
As previously highlighted, being the tie layer a critical component of the multilayer
structure, further analysis regarding adhesion strength when the film is subjected to
high temperature for a long time into the water bath must be conducted on
commercial products. With this objective in mind, current work mainly focused on
the development and validation of the laboratory test for cook-in applications,
considering the possibility of testing the peel strength for group B samples
afterwards, to understand how their performance was affected by water bath
operative conditions.

47
2.2.5.1) Laboratory test
The test simulates the conditions to be withstand by the plastic film under high
temperature for a long time as for cook-in applications. Conditions and performance
level requirements are very demanding. As a matter of fact, the temperature of the
water bath is fixed at 80°C for 8 to 10 hours or 100°C for 4 to 6 hours, depending
upon the case, to guarantee not only shrinkage of the film, but cooking of the food as
well. During the test, the polymeric film must remain intact and the packaging color
has not to be affected by operative conditions.
The water bath employed for test validation in Dow™ Tarragona TS&D laboratory is
usually dedicated to the stress cracking test. Water is mixed with monopropylene
glycol in a ratio of 2:3 to favor an increase in boiling point and, hence, reduce
evaporation during the operation. A metallic structure is used to fix the samples with
some clips in order to avoid their movement during the heating process performed
by the engine. The water bath and the metallic structure to locate samples during
the trials are shown in Figure 2.18 below.

Figure 2.18: Water bath and metallic structure for cook-in applications

Since the maximum temperature that can be reached by the available apparatus is
80°C, the required operative hours are at least 8, as reported above.
A4 sheets were cut from the bubble films object of the analysis, to be put onto the
metallic structure, where they were kept still by means of some clips located on one
edge of the sheet itself, as in Figure 2.19. In fact, the metallic structure was later
located into the water bath as shown on the left side of Figure 2.18. After 8 hours
into the water bath at 80°C, the metallic structure was removed, and the plastic
sheets, characterized by different shrinkability percentages, collected to dry off.
Specimens of 15 mm width were then cut from the sheets to be eventually tested
with the peel strength instrument. Chemical or mechanical delamination activation

48
can be employed to start delamination. Refer to the previous section for the
description of the two procedures.
As will be recalled, peel strength measurements on group B samples were not
conducted due to poor adhesion performance of samples already in standard
conditions. Therefore, current work uniquely focused on cook-in test development,
and samples specifically thought for cook-in applications will be tested in the next
stage.

Figure 2.19: Sheets located onto the metallic structure

49
2.2.6) Stand-Up Coffee Pouches
Stand-Up Pouches (SUP) represent an attractive solution to be used as substitute of
rigid containers, due to their lower weight coupled to their ability of standing up,
despite the lower rigidity, allowing them to be employed in a wide variety of
different fields. Fundamental properties they need to report are:
• Stiffness, to maintain the shape while standing;
• Toughness, to contrast eventual harsh transportation and handling
conditions;
• Sealing, to assure packaging integrity;
• Eventual barrier, optical and abrasion resistance properties, depending
upon the application.
Stand-Up Pouches are often manufactured in form-fill-seal lines, therefore the
required temperature operating window must be wide enough to withstand
temperature changes throughout the overall process, from step zero to the final
product formation.
Original pouches solutions, as reported in Figure 2.20 below, are characterized by a
thick polyethylene layer in the core of the structure (105 to 125 μm thickness)
laminated to an external PET layer of 12/15 μm thickness. Key properties of the
structure are a very high stiffness, high thermal resistance and low elongation. Due
to the differences in melting point between PET (260°C) and PE (100-125°C), the
temperature operating window is wide.

Figure 2.20: Original structure of PE//PET-based pouches

However, despite advantageous features are shown by these products, a significant
issue is related to the impossibility of recycling it due to the combination of
differentiated materials in the composition. Therefore, conventional disposal
techniques such as landfill and incineration are used.
To respond to this limitation, Dow™ proposed different solutions constituted by PE-
based structures for increasing recyclability. Requirements for improved
sustainability are approached thanks to the use of a single-polymer packaging, and
the cost is competitive, even though this also depends upon PET cost and availability
in the specific market. Figure 2.21 shows a schematic representation of 100% PE-
based laminated (a) and non-laminated (b) pouches solutions. With or without the

50
presence of an adhesive, products are characterized by a total average thickness of
125 μm, while the lamination adhesive, when present, of 3 μm. Entirely PE-based
pouches find application in solid, powder and liquid packaging with no need of gas
and aroma barriers, but in principle they are not suitable for hot-fill applications
where sealing temperature can overcome 90°C.

Figure 2.21: Laminated (a) and non-laminated (b) PE-based Dow™ pouches solutions

A patent application, so-called “Single Polymer Film Structures for Use in Stand Up
Pouches”, in which no lamination is present, was developed by Dow™ in 2013. The
structure is constituted by three differentiated polyethylene layers, each of them
providing a specific functionality to the final product. Layers can be described as
follows:

Layer Monomodal/Multimodal
Multimodal PE derived from ethylene
Inner
and 1-octene
Core Monomodal LLDPE
Monomodal LLDPE derived from
Outer
ethylene and 1-octene
Table 2.5: Resins used in Dow™ patent application

With the aim of broadening the fields of application of Triple Bubble® films, and
avoid laminated films’ use for pouches production, Dow™-Kuhne™ Triple Bubble®
team developed PE-rich Triple Bubble® film solutions potentially available for
stand-up coffee pouches. Structures are characterized by the following
configuration:
PET / Tie layer / PE bulk / Tie layer / EVOH / Tie layer / PE & Sealant

51
As huge innovation for the field of Triple Bubble® technology, thickness of coffee
SUP Triple Bubble® films is higher than conventional Triple Bubble® films, as it can
reach up to 100 μm. In this way, stiffness and mechanical resistance are increased,
without losing in optical properties. Moreover, higher rigidity of the films due to
higher thickness guarantees the capacity for pouches to stand, as fundamental
requirement for current applications.
Triple Bubble® stand-up pouches were produced in Dow™ facilities in Tarragona
(Spain) and Horgen (Switzerland) in October 2019. Films available were folded and
sealed according to standard pouches dimensions, as reported in Figure 2.22 below.
Pouches height is not reported because it can be adjusted depending upon
requirements and final application.
Figure 2.23 shows a sample as proposed to customers during 2019 K Show plastics
fair taking place in Düsseldorf from October 16th to October 23rd.

Figure 2.22: Template for manual production of coffee SUPs

Figure 2.23: PE-rich Triple Bubble® coffee SUP

52
CHAPTER 3: RESULTS AND DISCUSSION

3.1) Peel strength test – Results

3.1.1) Test validation analysis – Results
PET/PA adhesion was measured on a structure with PA as barrier material in Meyrin
DuPont™ site in 2018 (“Meyrin”) and Tarragona Dow™ site in 2018 (“Tgn #1”) and
2019 (“Tgn #2”). The reliability of results from Meyrin DuPont™ site was given for
granted due to extensive work conducted to verify tie layers performance as well as
delamination interfaces nature. The good correspondence between results obtained
during the three distinguished trials, as shown in Figure 3.1, confirmed the test
protocol for peel strength test was correctly followed. This aspect allowed to further
proceed in testing the adhesion strength for target samples belonging to group A and
group B.

Figure 3.1: PET/PA adhesion results comparison – Meyrin vs Tarragona 1st trial vs Tarragona 2nd trial

53
3.1.2) Experimental tie layer formulations A – Results
The objective of the current analysis was to evaluate the performance of tie layer
formulations characterized by a broad application range eventually providing
adhesion for PET, PA, EVOH to PE, PP, ionomers for shrinking and non-shrinking
films. EVOH/PE and/or EVOH/PP adhesion were tested for shrink and non-shrink
films. Structure configuration was chosen with the aim of being able to test both
EVOH/PE and EVOH/PP tie layer adhesion strength without the need of producing
two separated films to be dedicated to the two different measurements and, hence,
to reduce the number of operations required and the time needed for the overall
process. However, current work demonstrated the impossibility of recognizing the
nature of the layer adhering to EVOH, as reported above, unless FTIR was
performed. Due to the extremely long time associated to infrared spectroscopy, the
suggestion for future work is to produce structures in which either EVOH/PE or
EVOH/PP interface is present, and not both together, so that the recognition of the
layer adhering to EVOH will be straightforward.

§ Results – Shrink films
7 samples were tested for shrink film applications. Samples name is associated to
EVOH/polyolefin tie layer formulation, as well as shrink percentage.
Figure 3.2 shows the adhesion performance comparison for shrink films between:
v Reference formulations (in green colour);
v Experimental grades (in orange colour).
Reference A #2 is today the reference grade for the current application with the best
EVOH adhesion. Reference A #1 showed a lower performance with respect to
Reference A #2, but in general better than experimental grades tested. Experimental
formulations in shrink films showed a similar performance between them, with A #4
and A #5 having a slightly higher adhesion strength over the others. As already
recalled, the nature of the delaminating interface, either EVOH/PE or EVOH/PP, was
not easy to be detected unless FTIR analysis was conducted. Therefore, the values
reported might refer to EVOH/PE or EVOH/PP adhesion, or both of them, for the
same sample. Since tie layer formulations are expected to work better for EVOH/PE
adhesion due to their intrinsic nature, it cannot be excluded that samples showing a
higher peel strength are reporting values referred to EVOH/PE adhesion, and the
others to EVOH/PP adhesion. However, it is not practically possible to conduct FTIR
analysis for all the specimens of all the samples, and on the entire specimens’
surface, due to the time and research effort required.

54

Figure 3.2: EVOH/PO adhesion for group A samples – Shrink films

§ Results – Non-shrink films
7 samples were tested for non-shrink film applications, as it was done and discussed
in the previous section for shrink films. Samples name is associated to
EVOH/polyolefin tie layer formulation, as well as shrink percentage.
Figure 3.3 shows the adhesion performance comparison for non-shrink films
between:
v Reference formulations (in green colour);
v Experimental grades (in orange colour).
Reference A #1 and Reference A #2, references for EVOH adhesion to polyolefins, are
still the best options for EVOH adhesion, as shown for shrink films. However, A #5
experimental grade also represents a good solution for non-shrink applications,
with higher adhesion than other grades and performance almost comparable to
reference formulations, Reference A #2 in particular. As reported in the previous
section for shrink films, also in the current case the results can be either referred to
EVOH/PE, EVOH/PP or both adhesions, and only FTIR can give the proper answer.

55

Figure 3.3: EVOH adhesion for group A samples – Low-shrink films

In this section, peel strength results for both shrink and non-shrink films were
reported. A summary regarding the main outcomes of the analysis follows:
• Reference A #1 and Reference A #2 benchmark formulations are the best
performing tested grades for both shrink and non-shrink films;
• A #5 and A #4 are the most promising solutions for shrink applications within
the experimental grades tested;
• A #5 gave the highest adhesion strength within experimental non-shrink
films;
• Therefore, A #5 is suggested to be prioritized in a second stage analysis.

56
3.1.3) Experimental tie layer formulations B – Results
The objective of the current analysis was to test new tie layer options using Dow™
resins for being used in standard and cook-in Triple Bubble® and blown film
applications. EVOH/PE and/or EVOH/PP adhesion were tested for shrink and non-
shrink films. Structure configuration was chosen with the aim of being able to test
both EVOH/PE and EVOH/PP tie layer adhesion strength without the need of
producing two separated films to be dedicated to the two different measurements
and, hence, to reduce the number of operations required and the time needed for the
overall process, thanks to specific chemical solvents used for dissolution. However,
current work demonstrated the impossibility of recognizing the nature of the layer
adhering to EVOH, as reported in the previous section, unless FTIR was performed.
Due to the extremely long time associated to infrared spectroscopy evaluation, the
suggestion for future work is to produce structures in which either EVOH/PE or
EVOH/PP adhesion is present, and not both together, so that the recognition of the
layer adhering to EVOH will be straightforward and will not require infrared
spectroscopy evaluation.

§ Results – Shrink films
5 samples were tested for shrink film applications. Samples name is associated to
EVOH/polyolefin tie layer formulation, as well as shrink percentage.
Figure 3.4 shows the adhesion performance comparison for shrink films between:
v Reference formulations (in green colour);
v Experimental grades (in orange colour).
Reference B #1 and Reference B #2 clearly gave the best response in terms of
adhesion strength for EVOH/polyolefin adhesion. On the other hand, EVOH adhesion
was estimated to be very low for target tie layers when compared to reference
grades. No sample showed a sufficient resistance against peeling while tested.

§ Results – Non-shrink films
12 samples were tested for non-shrink film applications. Samples name is associated
to EVOH/polyolefin tie layer formulation, as well as shrink percentage.
Figure 3.5 shows the adhesion performance comparison for non-shrink films
between:
v Reference formulations (in green colour);
v Experimental grades (in orange colour).
Again, Reference B #1 and Reference B #2 showed the best response in terms of
adhesion strength for EVOH/polyolefin adhesion. On the other hand, EVOH adhesion
was estimated to be very low for target tie layers when compared to reference
grades. Due to the unexpected results for both shrink and non-shrink films, next
section will be focused on possible causes of failure for target samples.

57

Figure 3.4: EVOH/PO adhesion for group B samples – Shrink films

Figure 3.5: EVOH/PO adhesion for group B samples – Low-shrink films

58
3.1.3.1) Experimental tie layer formulations B – Fault tree analysis
Possible causes for poor adhesion performance of target tie layers will be pointed
out and discussed. Before proceeding with the discussion, a summary related to
possible explanations is reported in Table 3.1, associating each process step to the
eventual cause of failure.

Process Hypothesis Validation

Damaging storing
None (very unlikely to take
Pellet shipping conditions (ex. high
place)
humidity)

Compound Procedure verification &

Error in compounding
production Pellet analysis (NA)

Harsh operative conditions

Film production Blown film check (NA)
in 3B

Interferometer analysis &

Film processing Bubble instability Thickness distribution
measurements

Chemical Damaging interaction

Mechanical delamination
delamination solvent-polymeric layers

Error in testing Test validation

Peel strength test

Different delaminating
FTIR analysis
interfaces

Table 3.1: Possible causes and hypothesis validation of failure

59
 § Pellet analysis
As reported in Table 3.1, damaging storing conditions of pellets for tie layers
compounding have not been considered a probable cause of failure during the
process, despite reported in the list. As a matter of fact, pellets were stored in
standard conditions and no damage was detected once delivered to formulation
synthesis Dow™ site in Freeport, Texas.

§ Error in compounding
Error in compounding tie layer formulations is currently considered the most
probable cause of failure for which a poor adhesion of expected greatly performing
group A tie layers was detected. To confirm the hypothesis, new compounds are
currently under synthesis in Dow™ site in Freeport with the aim of using them as tie
layers in same-type Triple Bubble® films to compare the results to currently
available outcomes of the study. This conclusion was drawn after discarding other
hypothesis that will be discussed in the next paragraphs, according to steps order
during the overall process.

§ Blown film check
Trials testing materials response when produced on conventional single-bubble
blown lines are under exam. Results on the validation procedure are unfortunately
not yet available as the procedure is still ongoing. Tie layer formulations were
thought to be applicable for both blown and Triple Bubble® film synthesis
technologies. However, the orientation step in Triple Bubble® technology seems to
strongly affect the final performance of the films under analysis, as the results
confirm.

§ Interferometer analysis
As reported in Table 3.1, interferometer measurements were conducted to further
verify eventual bubble instability affecting tie layers’ and film’s performance and
effect of operative conditions. Interferometer results will be uniquely shown for B
#1 - LS sample, demonstrated to be representative for the tested samples. Table 3.2
summarizes the outcome obtained from interferometer analysis in correspondence
of five differentiated points of the film. The choice of reporting measurements for
five points of the selected sample had the aim of favouring the comparison and
detect the thickness and distribution differences.

60
 Nominal Actual Actual Actual Actual Actual
Material thickness thickness thickness thickness thickness thickness
(%) (%) - #1 (%) - #2 (%) - #3 (%) - #4 (%) - #5
PET
10 10 10.6 10.4 10 10.2
structural
Tie layer Not Not Not Not Not
5
(PET/PP) detected detected detected detected detected

PP bulk 33 37 35.8 35.2 36.8 37.2

Tie layer
5 4.8 5.4 4.8 4.8 5.6
(EVOH/PP)
EVOH
5 5.6 5.8 5 5 5.2
barrier
Tie layer
5 5 5.4 4.6 5 5
(EVOH/PE)

PE 5 4.6 5.6 4.8 5.4 5.6

Sealant 32 30.2 32.4 30.8 31.4 32

Table 3.2: Interferometer results for B #1 – LS

The separation between the three most external layers characterizing the structure
was difficult to be detected (PET / Tie layer / PP), probably due to the extremely low
thickness of the tie layer involved, since there is no reason to think that the tie layer
was not there anymore due to breakage, according to results that are not shown in
current work for PET/PP adhesion. However, the study was focused on tie layers for
EVOH/PE adhesion performance, which were in fact recognized into the structure
in correspondence of the five analysed points, even though the thickness was
extremely low and, in fact, equal to tie layer for PET/PP adhesion, which on contrary
was not recognized by the instrument. Interferometer accuracy is established at 2.5
μm, so it can be directly expected that, due to the extreme thinness of tie layers, it
becomes difficult for the instrument to recognize their presence. Results led to the
deduction that, despite harsh operative conditions during films’ production might
damage or lower the performance of tie layers due to their extremely low thickness,
it could not be concluded that tie layers target of the analysis for EVOH/polyolefins
adhesion were broken and, hence, not detected by the interferometer itself.
Therefore, current analysis did not bring to the conclusion that tie layers were
extensively damaged by processing conditions, at least in correspondence of the five
analysed points. However, as already reported, further work testing the behaviour

61
of compounds when conventional blown process is applied needs to be conducted
to compare the outcomes to what obtained after Triple Bubble® processing.

§ Film overall thickness distribution measurements
Thickness distribution results are reported for sample B #1 – LS. Standard deviation
generally reported by all the samples was relevant in many cases, demonstrating the
difficulties in maintaining constant thickness throughout films’ width and length.
Specific materials used are sensitive to Triple Bubble® operative conditions and,
despite theoretically a good uniformity in thickness is expected thanks to biaxial
orientation, practically materials were clearly strongly affected by the processing
conditions in terms of thickness homogeneity, reporting extensive bubble
instability. To better understand the variability shown by samples during thickness
distribution measurements, refer to Table 3.3 and Table 3.4 where average
thickness, highest and lowest values and each single thickness value collected for
sample B #1 – LS are reported, respectively, as anticipated. As specified during
interferometer analysis discussion in the previous subparagraph, B #1 – LS was
chosen as tester because representative of the general behaviour of the group to
which it belonged.

Average thickness Thickness Thickness
58.87 Measure Measure
(μm) value value
# #
Thickness SD (μm) 3.56 (μm) (μm)
Highest value (μm) 64 1 60 11 58
Lowest value (μm) 51 2 57 12 55
Table 3.3: B #1 – LS thickness 3 61 13 54
measurements (average, highest and 4 61 14 57
lowest) 5 61 15 51
6 62 16 57
7 60 17 61
8 64 18 63
9 63 19 55

10 59 20 59
Table 3.4: B #1 – LS thickness measurements

62
 § Mechanical delamination
Mechanical delamination preceding peel strength test was considered for the
adhesion measurements of some of the tie layers analysed during the study,
representative of the whole group. As a matter of fact, a damaging interaction
between the solvent used during chemical delamination activation and some of the
materials constituting the structure was considered to be possibly responsible for
the final bad adhesion performance. Peel strength results shown by the same three
target samples after mechanical delamination are compared to what obtained, and
already reported, after chemical delamination activation in Figure 3.6 for shrink
films and Figure 3.7 for non-shrink films. Light yellow bars refer to peel strength
results after chemical delamination, orange ones to the same analysis but after
mechanical delamination. It is likely to conclude that the chemical interaction of
formic acid solvent with the materials constituting the film, which occurred during
the trials, did not seem to affect the final result. Yet, peel strength after mechanical
delamination was still very low, and comparable to previous outcomes. Therefore,
the hypothesis of damaging interaction solvent-film was discarded as possible cause
of low tie layers adhesion performance.

Figure 3.6: Adhesion for group B tie layers – Chemical vs Mechanical delamination – Shrink films

63

Figure 3.7: Adhesion for group B tie layers – Chemical vs Mechanical delamination– Low-shrink films

§ Test validation
As recalled in Table 3.1, remaining hypothesis to explain the results are directly
referred to peel strength test. Test protocol was verified as very first step of the
process on a reference sample and results were compared to previous outcomes
obtained in DuPont™ Meyrin site (2018) and Dow™ Tarragona site (2018). The good
agreement shown between the three cases, as reported in Figure 3.1 at the beginning
of Chapter 3, confirmed the test protocol was properly followed.

§ FTIR analysis
Delamination interfaces were analysed after testing to understand whether the peel
value obtained was referred to EVOH/PP or EVOH/PE adhesion. Due to the
extremely time-consuming process for testing by infrared spectroscopy all the
specimens, only two specimens referred to two different samples were analysed by
FTIR in Dow™ analytical laboratory in Tarragona. Figure 3.8 refers to B #1 – LS and
Figure 3.9 to B #9 – LS layers’ separation. As clear, FTIR analysis pointed out a
divergence in delamination interfaces nature in the two cases. As a matter of fact,
EVOH/PP delamination was activated due to solvent dissolution for B #1 – LS, while
EVOH/PE adhesion was tested for B #9 – LS. Therefore, FTIR analysis would always
be required to detect the specific layers delaminated in each case, but the extremely
long time and research efforts required for the test make it impossible to conduct
the process on each of the targets. Moreover, the two results showed for target
samples B #1 – LS and B #9 – LS have been demonstrated referring to different
adhering materials and, hence, not comparable, at least in correspondence of the
specific zone in which FTIR was conducted on films surface. Structure configuration

64
was thought to guarantee the testing of EVOH/PP and EVOH/PE adhesion by simply
considering different solvents for the delamination, so that it would have not been
required to produce separated films, but a single sample would have been enough
for both measurements (EVOH/PP & EVOH/PE). However, current work established
that differentiated structures, the first one characterized just by PP in contact with
EVOH and the second one by EVOH/PE adhesion only, are necessary to be faster in
understanding which of the two adhesions is measured without the need of FTIR
analysis.

Figure 3.8: B #1 – LS FTIR analysis – Actual Figure 3.9: B #9 – LS FTIR analysis – Actual
sample delamination sample delamination

After referring to all the possible causes that could bring to poor results obtained for
group B samples in the current trials, the analysis led to the conclusion that the most
probable explanations for performance failure are either an error in compounding
or too harsh operative conditions of Triple Bubble® technology when applied to
materials characterized by a narrower operative window with respect to materials
conventionally used in the synthesis of Triple Bubble® structures. As a matter of
fact, the hypothesis of damaging interaction of formic acid with polymeric layers was
discarded after mechanical delamination activation testing. Moreover, test
validation anticipating target samples testing allowed to verify the correct test
protocol. On the other hand, FTIR analysis demonstrated the possibility of having
different delaminating interfaces depending upon the weakest adhesion link
activated by the solvent between EVOH/PP and EVOH/PE. Therefore, uniquely
EVOH/PP or EVOH/PE should be present in the structure since FTIR analysis cannot
be conducted on each of the analyzed specimens. As a matter of fact, in that case,
there would be no doubt about the nature of the tested adhesion.
However, only further work could discard or confirm with the highest certainty the
hypothesis proposed in the current study. Blown technology trials as well as
compound checking will help clarify the reason for which tie layers expected to show
a very high adhesion performance were characterized by a peel strength at least one
order of magnitude lower than prospects, instead.

65


66
CHAPTER 4: CONCLUSION REMARKS

Multilayer structures are characterized by the presence of different materials
providing a wide range of variable functionalities. In the field, Triple Bubble® films
represent an interesting alternative which embraces circular economy and
sustainability goals for the next future. As a matter of fact, the absence of adhesives,
the low thickness of the final film (downgauging), and the “design for recycling”
(D4R) proposal are only some of the aspects that make Triple Bubble® films
competitive in the food packaging market, with respect to other solutions such as,
for instance, laminated films.
However, as pointed out, innovations always come with challenges. In fact, tie layers
constitute one of the most challenging components in the overall structure, mainly
due to the orientation step to which the second bubble is dedicated in Triple
Bubble® processes.
As a consequence, a dramatic reduction in adhesion performance takes place during
the orientation step and, therefore, studies related to tie layer improvement are
constantly required.
Current work focused on the evaluation of tie layer performance for EVOH adhesion
to polyolefins. Experimental grades were compared to reference grades to evaluate
whether these grades are competitive and, eventually, ready to be commercialized.
Two different groups of samples were analyzed:
• Group A samples;
• Group B samples.

In the first case, the idea was to test tie layers that will be employed as adhesion
layers for a wider adhesion range than conventional solutions. This project pointed
out that the best formulation is the A #5, which is suggested to be the first prioritized
in the next stage analysis.
As for group A, also in the case of group B samples the target of the analysis was the
adhesion performance of tie layers joining EVOH and polyolefins in the multilayer
structure. However, the main scope in this case was to evaluate the best
experimental grade(s) eventually suitable for cook-in applications, as well. As a
matter of fact, harsher operative cook-in conditions in terms of temperature, water
presence and long processing time, represent an additional challenge for tie layers
performance. However, in this analysis, testing started from considering standard
conditions as operative background. Despite experimental grades were thought to
be ready to be commercialized, at least under standard conditions as described,
results contradicted expectations due to poor adhesion showed by target samples

67
for this group. A series of possible hypothesis have been proposed to explain
reported outcomes, as listed below:
• Damaging conditions during pellets storing and shipping;
• Error in compounding tie layer formulations;
• Too harsh operative orientation conditions for the reduced operative widow
characterizing the components of films under study;
• Bubble instability during film production process leading to a non-
homogeneous performance of the films throughout their width and length;
• Damaging interaction between formic acid and polymeric layers during
chemical delamination activation preceding peel strength test;
• Error in performing the peel strength test;
• Different delaminating interfaces causing a discrepancy between different
samples testing and, therefore, making worthless to compare their results.

Some of the listed hypotheses are still under investigation. According to the analysis,
the most probable explanation for poor adhesion relays on a combination between
harsh Triple Bubble® operative conditions, bubble instability and, more than the
others, error in compounding tie layer formulations. To confirm or discard these
hypotheses, blown film check is under investigation and new compounds
characterized by the same formulations are under production in Dow™ Freeport
site, Texas.
Since these experimental grades were thought to be extended to cook-in
applications, a test simulating industrial cook-in conditions was developed, as well.
However, due to poor performance of the films under standard conditions, cook-in
test development was not followed by peel strength testing, as thought during
design of experiments. Therefore, test still needs to be validated in further trials,
with solutions specifically produced for cook-in applications.

68
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