Abdellah Ajji, Ebrahim Jalali Dil, Amir Saffar, Zahra Kanani Aghkand

Heat Sealing in Packaging

Also of Interest
Thermoplastic Elastomers.
At a Glance
Scholz, Gehringer, 
ISBN ----, e-ISBN (PDF) ----

Polymer Engineering
Tylkowski, Wieszczycka, Jastrząb, Montane (Eds.), 
ISBN ----, e-ISBN ----

Physical Chemistry of Polymers.

A Conceptual Introduction
Seiffert, 
ISBN ----, e-ISBN (PDF) ----

Polymer Circularity Roadmap.

Recycling of poly(methyl Methacrylate) as a Case Study
D’Hooge, Marien, Dubois, 
ISBN ----

Plastics in the Circular Economy

Voet, Jager, Folkersma, 
ISBN ----, e-ISBN (PDF) ----
Abdellah Ajji, Ebrahim Jalali Dil, Amir Saffar,
Zahra Kanani Aghkand

Heat Sealing
in Packaging

Materials and Process Considerations

Authors
Abdellah Ajji Amir Saffar
Polytechnique Montreal ProAmpac
Chemical Engineering Department Boulevard des Entreprises
C.P. 6079 Succursale Centre Ville Terrebonne J6Y 1V2
Montreal Canada
Canada
Zahra Kanani Aghkand
Ebrahim Jalali Dil Polytechnique Montreal
PolyExpert Inc. Chemical Engineering Department
850 Munck Avenue C.P. 6079 Succursale Centre Ville
Laval H7S 1B1 Montreal
Canada Canada

ISBN 978-1-5015-2458-5
e-ISBN (PDF) 978-1-5015-2459-2
e-ISBN (EPUB) 978-1-5015-1616-0

Library of Congress Control Number: 2023931404

Bibliographic information published by the Deutsche Nationalbibliothek

The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the Internet at http://dnb.dnb.de.

© 2023 Walter de Gruyter GmbH, Berlin/Boston

Cover image: Amir Saffar
Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck

www.degruyter.com
Preface
The polymer packaging market reached $348 billion in 2020 and is growing at about
3–5% annually, especially in applications in the food industry. One of the main func-
tions of a package is to contain and protect the (food) product during shipping and
handling, delivering the product in the best condition intended for its use. Hence, an
efficient sealing of the package is necessary in order to achieve this. In fact, sealing
has such an important role in a package that if the sealing fails, the package fails and
as a result, sealing of polymer films and packages has become the main concern in
the design and development of polymer packages. We have been working on flexible
packaging over the last 15 years, and heat sealing was and is still among the important
topics of our research. Many of the results presented in this book originate from our
previous works.
This book is intended to provide a comprehensive review that covers many as-
pects of heat sealing, from basic principles to materials and process. The main goal is
to provide a sufficiently detailed and organized review of the heat-sealing process to
obtain a deep insight into the involved molecular mechanisms as well as the effects of
material and processing parameters on heat sealing. Readers wishing more details
about any specific aspect discussed here can pursue further studies in the provided
list of references in each chapter.
The molecular mechanisms involved in each step of heat sealing are discussed in
detail in Chapter 2. Chapter 3 summarizes the sealing test methods used in the indus-
try to evaluate the seal performance. Chapter 4 presents different materials com-
monly used as sealant layers in polymer packaging based on their seal performance.
Chapter 5 reviews the literature on the effects of processing conditions as well as mo-
lecular characteristics of sealants on the seal and hot tack performance. Chapter 6 dis-
cusses the modeling and simulation of a heat-sealing process as a tool to reduce the
required cost, energy, and time during sealants design for polymer packages.
Considering the much wider range of properties that polymer blends can offer
compared to single-phase matrices, particularly in easy peel and peelable seals, seal-
ants based on polymer blends have recently received an increasing attention. In Chap-
ter 7, first, the concepts regarding microstructure–property relation in a polymer
blend system are described, and then the seal performance of polymer blend sealants
is discussed.
The environmental concerns regarding petroleum-based and non-biodegradable
polymers that are conventionally used in polymer packages led to a significant inter-
est in replacing these materials with bioplastic (biobased and/or biodegradable/
compostable) sealants. Chapter 8 introduces bioplastic materials used as sealants in
polymer packaging and reviews their seal behavior. Finally, Chapter 9 is dedicated to
case studies in designing sealant layers in some applications to present guidelines for
practical sealant film design.

https://doi.org/10.1515/9781501524592-202
Contents
Preface V

Chapter 1
Introduction 1
1.1 History of polymers in packaging 1
1.2 Plastic joining methods 2
1.2.1 Ultrasonic sealing 2
1.2.2 Induction sealing 4
1.2.3 Heat bar sealing 4
1.2.3.1 VFFS packaging machine 5
1.2.3.2 HFFS packaging machine 7
1.2.4 Impulse sealing 9
1.3 Organization of the book 10
References 10

Chapter 2
Molecular mechanism of heat sealing 13
2.1 Heat sealing from microscopic viewpoint 13
2.2 Melting of polymer materials 15
2.3 Surface rearrangement 17
2.4 Molecular interdiffusion across the interface 18
2.4.1 Polymer interdiffusion dynamics 18
2.4.2 Interdiffusion at polymer–polymer interfaces 22
2.5 Cooling and crystallization 23
References 27

Chapter 3
Seal quality and performance evaluation methods 31
3.1 Seal quality tests 31
3.1.1 Visual inspection 33
3.1.2 Flat bar test 33
3.1.3 Gross leak or bubble test 34
3.1.4 Pressure decay leak test 35
3.1.5 Dye penetration test 36
3.1.6 Pressure-assisted dye penetration test 37
3.1.7 Airborne ultrasound 37
3.2 Seal performance tests 38
3.2.1 Hot tack test 39
VIII Contents

3.2.2 Seal strength measurement 42

3.2.3 Internal pressurization failure resistance 44
References 46

Chapter 4
Sealant layer materials 49
4.1 Polyethylene 49
4.1.1 High-density polyethylene (HDPE) 50
4.1.2 Low-density polyethylene (LDPE) 50
4.1.3 Linear low-density polyethylene (LLDPE) 51
4.1.4 Metallocene polyethylene (mPE) 53
4.1.5 Plastomers 54
4.2 Polypropylene (PP) 54
4.3 Ethylene vinyl acetate (EVA) 56
4.4 Acid copolymers 58
4.5 Ionomers 59
4.6 Polyethylene terephthalate (PET) 61
References 61

Chapter 5
Effect of processing and material properties on seal performance 63
5.1 Sealing temperature 63
5.2 Dwell time 66
5.3 Sealing pressure 67
5.4 Effect of material characteristics 69
5.4.1 Effect of crystallinity 69
5.4.2 Effect of molecular architecture 72
5.4.3 Chain branching 72
5.4.4 Monomer sequence 74
References 74

Chapter 6
Modeling of heat sealing process 77
6.1 Modeling of the interface temperature 77
6.1.1 Heat transfer in contact areas 79
6.1.2 Heat transfer within the film 82
6.2 Modeling of squeeze-out flow 85
6.3 Modeling seal strength development 93
References 96
 Contents IX

Chapter 7
Multicomponent sealant films 101
7.1 Thermodynamics of polymer blends 101
7.2 Morphology of polymer blends 105
7.3 Surface morphology of immiscible polymer blend films 107
7.4 Sealants based on immiscible polymer blends 109
7.5 Polymer nancomoposites 112
References 115

Chapter 8
Bioplastic sealants 119
8.1 Bio-based polyethylene terephthalate (bio-PET) 120
8.2 Bio-based Polyethylene (PE) and Ethylene Vinyl Acetate (EVA) 120
8.3 Poly(lactide) 121
8.4 Polycaprolactone 122
8.5 Aliphatic polyesters and copolyesters 122
8.6 Aromatic copolyesters 124
8.7 Polyhydroxyalkanoates (PHA) 125
References 126

Chapter 9
Case studies 129
9.1 Design of a peelable sealant for cereal packaging 129
9.1.1 Solution 129
9.2 Sealant for liquid packaging 131
9.2.1 Solution 131
9.3 Film for heavy-duty shipping sack (HDSS) 131
9.3.1 Solution 132
9.4 Peelable film for over-the-mountain packaging 132
9.4.1 Solution 133
9.5 Sealant film with caulkability for spouted pouch application 134
9.5.1 Solution 135
9.6 Peelable barrier film for dried seeds packaging 136
9.6.1 Solution 136
9.7 Oxygen barrier sealant for cheese packaging 138
9.7.1 Solution 138
9.8 Film for frozen vegetables 139
9.8.1 Solution 139
References 140

Index 141
Chapter 1
Introduction

1.1 History of polymers in packaging

The first flexible transparent polymeric film called cellophane was produced from re-
generated cellulose by the Swiss chemist Jacques E. Brandenberger in the 1900s [1].
Cellophane was later commercialized by DuPont for food packaging applications;
however, due to its sensitivity to moisture, it could not be used widely in the food
industry. The first moisture barrier transparent polymer film was prepared by coat-
ing cellophane with nitrocellulose [2]. The first transparent oxygen and moisture bar-
rier polymer film was then introduced by coating polyvinylidene chloride (PVDC) on
cellophane [3]. This allowed cellophane to be introduced as a competitor for tradi-
tional metal barrier films in the food industry with the advantage of transparency
and lightweight. Eventually, polyvinyl chloride (PVC) and polypropylene replaced cel-
lophane in the packaging industry in the 1960s due to the poor performance of cello-
phane at low temperatures, its limited shelf-life, and cost issues. In 1973, the Food and
Drug Administration banned the usage of PVC in beverage bottles due to migration of
residual vinyl chloride monomers [4], and the application of PVC in food packaging
decreased dramatically. The interesting properties of polyethylene (PE), including its
chemical resistance, odorless, toughness, good sealability, high moisture barrier, and
low cost, made it a strong candidate for food packaging applications. Since then,
many other polymers have been widely used in the polymer packaging market, in-
cluding poly(ethylene terephthalate), ethylene vinyl acetate, and polyamide. In addi-
tion, different types of coatings including thin PVDC or metal/mineral oxide coating
(with commercial names such as ALOx and SiOx) allowed combining very high barrier
properties and transparency in plastic packaging without using opaque aluminum
foil layer. The growing needs, especially in the food industry [5], have significantly
increased the market value of polymer packaging that finally reached $348 billion in
2020 [6]. This indicates the significant role of polymer packaging in the future of the
food industry.
The main functions of a package can be listed as containment of the product, pro-
tecting the product during shipping and handling, delivering the product in the best
condition intended for its use, and finally, brand advertisement [5]. An efficient seal-
ing of a package is necessary in order to achieve the first three roles of the package.
In fact, sealing has such an important role in a package that if the sealing fails, the
package fails. As a result, sealing of polymer films and packages has become a main
concern in their design and development. The importance of sealability is such impor-
tant that the lack of sealing properties delayed the use of certain polymers in the past.
For example, despite interesting moisture barrier properties of nitrocellulose-coated
cellophane, this film was used widely in packages only after modifications that

https://doi.org/10.1515/9781501524592-001
2 Chapter 1 Introduction

allowed it to be heat-sealable [3]. Different techniques have been proposed for sealing
polymer packages [7] that will be briefly reviewed below.

1.2 Plastic joining methods

Different techniques have been used to join plastic components ranging from me-
chanical joining using screws, to adhesive bonding and welding techniques. In the
welding methods, polymeric surfaces are melted, and surfaces are joined by polymer
chain diffusion across the interface. Welding methods can be categorized into exter-
nal heating or internal heating methods depending on the method of applying heat.
Figure 1.1 shows the most common welding techniques based on their heating source.

Plastic Welding Techniques

Internal Heating External Heating

Ultrasonic Heated Tools

Vibration Heat Bar Sealing

Impulse Sealing
Laser Welding
Hotwire Sealing

Induction

Figure 1.1: Different welding techniques based on applying heat methods.

In the following sections, we review ultrasonic sealing, induction sealing, heat bar
sealing, and impulse sealing as they are mostly used in sealing plastic packaging.

1.2.1 Ultrasonic sealing

Ultrasonic sealing was initially developed by Robert Soloff in the 1960s. In this tech-
nique, two sides of the seal area are pushed together between an ultrasonic horn and
an anvil. Then the horn vibrates at a high frequency in the range of 20–40 kHz and
amplitude in the range of 10–30 µm [9]. The main components of an ultrasonic sealing
machine are a transducer, a booster, and a horn (known as sonotrode). The trans-
ducer is a piezoelectric material that converts the high-frequency electric signal to
high-frequency mechanical vibration. This vibration is amplified by the booster and
 1.2 Plastic joining methods 3

transferred to the sonotrode. The vibration results in molecular movement and

heat generation due to intermolecular friction. Energy directors with different
shapes are used to concentrate the vibration to the desired sealing area. Conse-
quently, the temperature in the seal area is raised, which melts the sealant mate-
rial. Under the applied pressure by the ultrasonic horn, molecular diffusion across
the interface occurs and seals the two sides of the seal area. The sealed area is
cooled down under force between horn and anvil after stopping the vibration, and
finally, the horn will be opened. Figure 1.2 schematically shows a typical ultrasonic
sealing process.

Sonotrode
Sonotrode

Sonotrode
Sonotrode

Sonotrode

Anvil
Anvil

Anvil
Anvil
Anvil

(a) (b) (c) (d) (e)

Figure 1.2: Ultrasonic sealing steps: (a) approaching, (b) applying force, (c) starting of ultrasonic vibration,
(d) end of ultrasonic vibration and beginning of cooling under force, and (e) removing of the force and
opening of sonotrode.

Ultrasonic sealing has been used in a wide range of applications from aerospace to
medical and food packaging. Ultrasound sealing is known to provide a great seal in
the presence of contamination and is an effective sealing approach for thick sam-
ples. As in ultrasonic sealing, the heat does not transfer from outside to the inside of
the product and is generated directly at the sealing interface, it allows a much faster
sealing process especially in sealing of thick samples such as multiwall paper bag
products. The lack of the need for heat transfer from outside of the film also allows
safe sealing for temperature-sensitive materials such as medications. Some studies
also showed that ultrasound sealing needs less energy consumption compared to
heat sealing [9].
4 Chapter 1 Introduction

1.2.2 Induction sealing

This type of sealing is also known as cap sealing and is very common in the sealing of
rigid containers’ lidding. In this process, the lidding film is made of a structure that
contains four different layers as shown in Figure 1.3.

Paper
Binder
Aluminum Foil
Polymer Sealant

Figure 1.3: A common structure for lidding is used in the induction sealing process.

A schematic of an induction sealing process is shown in Figure 1.4. The lidding is

placed on the container and the cap is closed. Then the container passes through an
induction chamber or induction zone using a conveyor belt. An electromagnetic field
is applied in the induction chamber which interacts with the foil layer and generates
heat. The generated heat melts the sealant layer and results in the adhesion of the
lidding to the container. In addition, the generated heat melted the binder which is
then infiltrated into the paper and resulted in releasing of aluminum from the back-
ing upon cooling.

(i) (ii) (iii) (iv)

Induction Zone

Figure 1.4: Different steps in the induction sealing process: (i) filled container, (ii) closing of the cap with
lidding, (iii) sealing of the cap to the container in the induction zone, and (iv) sealed container after the
opening of the cap.

1.2.3 Heat bar sealing

Heat bar sealing is the most common type of sealing in plastic packaging due to its
ease of use and low maintenance cost. Figure 1.5 schematically shows a heat bar seal-
ing process. In this method, two sides of the seal area are pushed together between
two jaws (bars) that both or only one of them is heated. To seal both sides together,
 1.2 Plastic joining methods 5

the jaws apply a certain pressure, known as the sealing pressure, for a certain period
of time, known as the dwell time or the sealing time. The first sealing machine with
electrically heated jaws was invented in 1942 for the sealing of cellophane bags [3].

(a) (b) (c)

Figure 1.5: Schematics of the heat bar sealing process: (a) approaching the heated jaws, (b) applying
heat and pressure for the duration of dwell time to the seal area, and (c) opening of the jaws.

The main processing parameters in the heat bar sealing process are sealing tempera-
ture, sealing pressure, and dwell time. In addition, the pattern of the surface of jaws
can affect seal properties. For example, Selke et al. [10] and Theller [11] showed that
using serrated jaws with patterns could improve seal performance by increasing the
intimate contact between polymeric films especially when the thickness of the films is
not uniform.
Heat bar sealing can be found in very different packaging machines. Vertical
form fill and seal (VFFS), horizontal form fill and seal (HFFS), and pouch-making ma-
chines are the most common packaging machines that use heat bar sealing. A brief
explanation of VFFS and HFFS processes will be given in the next sections. The same
concepts can be applied for pouch-making machines. In addition to these machines,
heat bar sealing is also used in different bag-making machines, pouch-making ma-
chines and tray-sealing machines.

1.2.3.1 VFFS packaging machine

Figure 1.6 schematically shows how a VFFS machine is used to form, fill, and seal a
package. In this machine, the film is fed in the form of a sheet and passes over a
metal collar to form a tube. The formed tube passes over a metal tube that is known
as a forming tube where a vertical sealer seals two edges of the film together to form
a complete plastic tube around the forming tube.
The films can be sealed in a vertical sealer by sealing inside to inside (known as
the fin seal) or outside to inside (known as the lap seal). These two types of vertical
sealing are schematically shown in Figure 1.7.
Sealing of the vertical seal is commonly done by the heated bar, but other types
such as hot air are also used in special cases. After passing through the vertical sealer,
6 Chapter 1 Introduction

(iii)

(iv)

(ii)

(v)

(i)

(vi)

(vii)

Figure 1.6: Different parts of a VFFS machine: (i) plastic film roll, (ii) dancing arm, (iii) forming tube,
(iv) forming collar (shoulder), (v) vertical sealer, (vi) transport belts, and (vii) heated sealing bars.

Figure 1.7: Different sealing methods for vertical seal in VFFS machine: (left) fin seal and (right) lap seal.
The hatched area shows the sealed area.

the film reaches the end of the forming tube where the end of the plastic tube is
sealed by a pair of heated jaws to create the bottom seal of the bag. The film then is
transported downward to reach the desired bag height. The top of the bag is then
 1.2 Plastic joining methods 7

sealed, and a knife that is inside of the jaws cuts the bag off the plastic tube. In VFFS
machines, the film transport can occur by two means: (i) the jaws grip and pull down
the film, known as the jaw draw-off principle; (ii) a belt is installed on the sides of the
forming tube and pulls down the film, known as belt pick-up principle.
In the first transport form, when the jaws are closed to seal the bottom of the plas-
tic tube, they also have a simultaneous downward movement which results in pulling
down the film to the desired bag height. Therefore, in this form of transport, the friction
between the inside layer of the films and the forming tube is very critical. The machines
that use a jaw draw-off mechanism cannot produce bags with block bottom.
In the belt pick-up mechanism, the film is pushed down due to friction between
belts located on the sides of the forming tube. Therefore, in this form of film transport,
the friction between the inside of the films and the forming tube surface as well as the
friction between the belt and the outer surface of the film becomes important. This has
led to the development of the vacuum transport belts in which the film is sucked to-
ward the belt to reduce the friction between the film and the forming tube and improve
the friction between the belt and the film. One interesting advantage of the belt princi-
ple over jaw drawdown is that it can be used for making any type of bag.
VFFS machines are mostly intermittent machines with a pause in their production.
In the jaw drawdown machines, this time is needed for the jaws to open and return to
their initial sealing position to seal the top of the bag. In machines with the belt pickup
mechanism, this pause is needed for the jaw to open and allow downward film trans-
port equal to the length of the bag. To create such an intermittent motion, most ma-
chines are equipped with what is known as a dancer arm mechanism to translate the
continuous unwinding of the plastic roll into the intermittent motion. In intermittent
VFFS processes, the vertical sealing is also intermittent, which means the vertical sealer
touches the film on the forming tube at the same time as the bottom sealer seals the
bottom of the tube and retracts back during the transportation step. This motion allows
film transport and prevents overheating of the vertical sealing part during the trans-
port phase of the process. The intermittent process reduces productivity and increases
production costs. By reducing the size of the package, the time-lapse between steps is
reduced, and in small snack size packaging, the process is almost continuous. In some
machines, the jaw drawdown and belt pickup mechanisms are combined to provide
continuous film motion. A new patented technology called twin-jaw continuous motion
VFFS was introduced, in which four heated jaws are mounted on two circular shafts.
The jaws rotate in a synchronized manner to provide continuous film motion without a
delay for sealing. This reduces considerably the delay related to jaw motion and could
reach 300 bags per minute packaging speed.

1.2.3.2 HFFS packaging machine

Figure 1.8 and 1.9 schematically show the process flow diagram of the two most com-
mon types of HFFS packaging machines: flow wrapper and HFFS pouch machines.
8 Chapter 1 Introduction

(ii)
(iii)

(iv)

(v)

(vi)

(i)

Figure 1.8: Flow wrapper: (i) plastic roll, (ii) product, (iii) bag/forming, (iv) side/vertical sealers,
(v) bottom/horizontal sealer, and (vi) final packaged product.

(iii)
(ii)
(v)

(vi)

(i)
(iv)

Figure 1.9: HFFS pouch machine: (i) film roll, (ii) film folding and gusset forming, (iii) vertical side sealing,
(iv) horizontal sealing, (v) filling and top sealing, and (vi) cutting and packaging.
 1.2 Plastic joining methods 9

In the flow wrapper machine, the film passes over a forming box to form a tube-
like structure where the edges pass between rolls beneath the product’s conveyor
belt. The edges are sealed by the center sealer beneath the platform. The product is
fed from the center of the forming box into the formed plastic tube. The package end
is sealed using the end sealer, which is usually a rotating heated seal bar.
In pouch-making HFFS machine, the film is folded and, if needed, gusseted. Then
a vertical heat bar seal seals the side sealing of the package and a horizontal sealing
seals the bottom (if needed). The packaging is then filled from the top and then a hori-
zontal heat bar seals the top of the package. Finally, the pouch is cut and packaged.
The HFFS pouch machine can produce pouches with or without zipper. Using HFFS
pouch machine allows combining pouch-making and filling step in one step, which
reduces the time and associated costs.

1.2.4 Impulse sealing

Impulse sealing is a very cheap sealing machine that can be found in kitchens and
small businesses. The impulse sealing machine consists of two jaws, where one jaw is
heated using an electric wire passing beneath a Teflon cover and the other jaw is
used to apply the sealing pressure (Figure 1.10).

Figure 1.10: Manual impulse heat sealer: (A) Teflon-coated sealing wire; (B) dwell time controller;
and (C) pressure applying handle.

When the films are placed between moving and fixed jaws, and after the closing of
the upper jaw, the current in the sealing wire is switched on automatically. The heat-
ing wire is usually made of Nichrome and the heat is generated in the wire due to its
resistance against electrical current. The current remains for the desired time selected
by the dwell time controller or until the jaw is opened by the user depending on the
machine design. In this type of basic impulse heat sealer, control on temperature and
10 Chapter 1 Introduction

dwell time is very poor. On the other hand, as the heating is only applied once the jaw
is closed, this type of heat sealing reduces power consumption compared to constantly
heated jaws in heat bar sealing. In addition, impulse sealers do not require a warm-
up time, which allows for quick start-up.

1.3 Organization of the book

Among different sealing methods in plastic packaging, heat sealing, especially heat
bar sealing, is the most common method used in the polymer packaging industry due
to its convenience, high speed, and low operation cost [8]. Despite its importance in
the packaging industry, a comprehensive review that covers all aspects of heat sealing
is lacking in the literature. The main goal of this book is to provide a detailed and
organized review of the heat-sealing process to obtain a deep insight into the involved
molecular mechanisms as well as the effects of material and processing parameters
on heat sealing. In all parts of the book, these concepts are discussed by considering
their implications in real-life and industrial applications to establish a relation be-
tween knowledge and application.
The molecular mechanisms involved in each step of heat sealing are discussed in
detail in Chapter 2. Chapter 3 summarizes the test methods used in the industry to
evaluate the seal performance. Chapter 4 presents different materials commonly used
as sealant layers in polymer packaging based on their seal performance. Chapter 5 re-
views the literature on the effects of processing conditions as well as molecular char-
acteristics of sealants on the seal and hot tack performance. Chapter 6 discusses the
modeling and simulation of a heat-sealing process as a tool to reduce the required
cost, energy, and time during sealant design for polymer packages. Multicomponent
sealant films are discussed in Chapter 7, as new seal material generation allows wid-
ening seal performance spectrum. Due to the environmental concern of plastic waste,
bioplastic sealant materials have been used to produce environment-friendly packag-
ing. This type of sealant materials will be discussed in Chapter 8. Chapter 9 presents
different case studies and troubleshooting to allow readers to better understand the
implications of the discussed materials.

References

[1] Brandenberger, J.E., Tube en cellophane destiné à contenir des matières grasses FR451485A, 1913.
[2] Hale, C.W. and P.K. Edwin, Moisture proofing composition, US1826696A, 1931.
[3] Kane, W.P., Cellophane Coating Compositions Comprising Vinylidene Chloride Copolymer, Candelilla Wax
and Stearate Salt. 1968, Google Patents.
[4] De La Cruz, P.L., PVC: Packaging issues and regulations. Journal of Vinyl Technology, 1988. 10(3):
p. 117–120.
 References 11

[5] Robertson, G.L., Food Packaging: Principles and Practice. 2013, CRC Press.
[6] Plastic Packaging (Rigid Plastic Packaging and Flexible Plastic Packaging) Market for Food & Beverages,
Industrial, Household Products, Personal Care, Medical and Other Applications – Global Industry
Perspective, Comprehensive Analysis, Size, Share, Growth, Segment, Trends and Forecast. 2016, Zion
Market Research. https://www.marketresearchstore.com/report/plastic-packaging-market-z47941.
[7] Troughton, M.J., Handbook of Plastics Joining: A Practical Guide. 2008, William Andrew.
[8] Morris, B.A., Chapter 7: Heat Seal, in the Science and Technology of Flexible Packaging. 2017, Elsevier,
Cambridge.
[9] Bach, S., et al., Ultrasonic sealing of flexible packaging films–principle and characteristics of an
alternative sealing method. Packaging Technology and Science, 2012. 25(4): p. 233–248.
[10] Selke, S.E.M., J.D. Culter, and R.J. Hernandez, Plastics Packaging: Properties, Processing, Applications,
and Regulations, ed. 2nd. 2004: Hanser Gardner Publications.
[11] Theller, H.W., Heat sealability of flexible web materials in hot-bar sealing applications. Journal of Plastic
Film and sheeting, 1989. 5: p. 66–93.
Chapter 2
Molecular mechanism of heat sealing

2.1 Heat sealing from microscopic viewpoint

In this chapter, the mechanisms involved in heat sealing of polymeric films are dis-
cussed in detail. The following steps can be considered in a common heat bar sealing
process [1, 2]: (i) surface contact between two films; (ii) heat transfer from the jaw(s) to-
ward the interface between films; (iii) surface melting and rearrangement; (iv) molecular
interdiffusion across the interface; and finally (v) cooling and recrystallization after open-
ing the jaws. Figure 2.1 shows a schematic of these steps from the microscopic viewpoint.

Polymer Crystals
Top

(i)

Bottom

(ii)

Top Interface
(iii)
Bottom

Top

(iv)
Bottom

(v)

Figure 2.1: Different steps in a heat sealing process: (i) surface contact, (ii) heat transfer from the jaws,
(iii) surface melting and rearrangement, (iv) molecular interdiffusion across the interface, and (v) cooling
and recrystallization after opening the jaws.

In the first step, two sealing sides are pushed together by the heated jaws. However, as
in the early stages of the process, the interface temperature (Tint) is below the melting
temperature (Tm); therefore, the micro-roughness on the surfaces limits the contact be-
tween two films at the interface. Figure 2.2 shows an example of the microroughness

https://doi.org/10.1515/9781501524592-002
14 Chapter 2 Molecular mechanism of heat sealing

Figure 2.2: Microroughness profile on the surface of a polyethylene sealant film.

that exists on the surface of a polyethylene sealant film with an average square mean
roughness (Rq) of 95 nm.
Reducing the roughness of the surfaces, reducing polymer hardness, and increasing
the applied sealing pressure are known strategies to increase the contact area in this
step [3]. However, due to the low interface temperature in this step, the molecular mobil-
ity at the interface is very limited, and chain diffusion across the interface does not occur.
As a result, very poor seal strength is obtained if the heat sealing process is stopped at
this stage. Interface temperature increases by increasing the dwell time due to the heat
transfer from the heated jaws. Figure 2.3 schematically shows a typical interface tempera-
ture profile in a heat sealing process. The interface temperature increases rapidly at the

Tjaw
Interface Temperature (Tint)

Dwell
Time Cooling Time

Room Temperature

Time

Figure 2.3: Typical interface temperature variation in a heat sealing process. Tjaw shows the jaw temperature.
 2.2 Melting of polymer materials 15

early stages of the process. Heat transfer from the jaws depends on many parameters,
including jaw interface with films, jaw temperature, dwell time, thermal conductivity of
polymers, film thickness, and polymer crystallinity. The effect of these parameters on
heat transfer in the heat sealing process will be discussed in Chapter 5.
When the interface temperature reaches the melting temperature of the sealant,
a significant deformation in surface asperities occurs due to the applied pressure by
jaws. This allows surface rearrangement and increases the contact area between the
two films to its maximum. In addition, melting of polymer crystals increases signifi-
cantly the molecular mobility of polymer chains and, after surface rearrangement
and establishing surface contact, allows interdiffusion across the interface and forma-
tion of molecular entanglements. In the last step, after opening the jaws, temperature
in the sealed area decreases due to the heat transfer to the surrounding medium. When
Tint falls below the crystallization temperature (Tc) of the sealant, the polymer chains
begin to form polymer crystals. The formed crystals act as physical cross-linking points
and reduce the molecular mobility which increases the seal strength [1, 3].
As will be shown later, the hot tack strength is measured right after opening of the
jaws when the sealant is still in the molten state; therefore, hot tack depends mainly on
chain interdiffusion across the interface (step iv in Figure 2.1). On the other hand, seal
strength is affected by both molecular interdiffusion and recrystallization after jaw
opening as seal strength is measured when the sealant reaches room temperature. As
mentioned previously, molecular interdiffusion begins only after melting and surface
rearrangement; therefore, first, melting of polymer materials will be briefly discussed,
and then surface rearrangement, interdiffusion, and finally, crystallization will be re-
viewed in the rest of this chapter.

2.2 Melting of polymer materials

From the thermodynamic point of view, the melting phenomenon can be explained
by considering the Gibbs free energy of fusion:

ΔGf = ΔHf − TΔSf (2:1)

where ΔHf and ΔSf are molar enthalpy and entropy variations and T is the tempera-
ture. As ΔG becomes zero at the melting temperature of crystals, the melting tempera-
ture can be defined as
ΔHf
Tm = (2:2)
ΔSf

This equation simply shows how changing the molecular parameters such as Mw
(which changes ΔSf ) or intermolecular interactions (which affects ΔHf ) can alter the
melting temperature of crystals. At T ≥ Tm, the ordered crystal structure breaks down
and is transferred into a disordered amorphous phase, which leads to an increase in
16 Chapter 2 Molecular mechanism of heat sealing

1.35

Specific Volume (cc/g) 1.30

1.25

1.20

1.15

1.10

1.05
40 60 80 100 120 140 160
T (°C)

Figure 2.4: Variation of specific volume of a high-density polyethylene (HDPE) with temperature, and the
dashed line shows the peak melting temperature determined from DSC (data from [5]).

the specific volume of the polymer. This causes a discontinuity in the variation of spe-
cific volume with temperature. As polymer crystals have a distribution of crystal size
and crystal perfection due to their high molecular weight (Mw) and molecular weight
distribution (MWD) [4], the variation of the specific volume–temperature curve of pol-
ymers is usually seen as a transition similar to the one shown in Figure 2.4 rather
than a sharp discontinuity at the melting temperature.
The most common and practical method in determining the melting temperature
of polymer materials is dynamic scanning calorimetry (or DSC) analysis. Melting is an
Exo

Tc
Heat Flow (W/g)

cooling

heating

Tm

Temperature (°C)

Figure 2.5: A typical DSC curve of a semicrystalline polymer material showing the peak melting
temperature (Tm) and the crystallization temperature (TC). The marked areas under peaks show the
enthalpies of melting and crystallization.
 2.3 Surface rearrangement 17

endothermic transition; therefore, the DSC technique can be used to determine this
transition from the absorbed heat of fusion. Figure 2.5 shows a typical DSC curve of a
polymer material with the peak melting temperature (Tm). As mentioned previously,
the distribution of crystal size and their different perfection level results in a broad
melting peak in polymers. Therefore, molecular parameters such as Mw and MWD
[6–8] as well as processing conditions such as cooling rate from the melt [9–12] and
orientation [13, 14] influence the breadth of the melting peak in the DSC curve.
It should be noted that the melting temperature and heat of fusion reported from the
DSC data are usually recorded at heating rates of 10 or 20 °C/min recommended in the
ASTM standard [15]. However, polymer materials experience extremely higher heating
rates in a heat sealing process. As an example, when the jaw temperature is set at 140 °C
and for a dwell time of 0.5 s, polymer materials experience a heating rate of 230 °C/s or
13,800 °C/min. Previous studies showed that at heating rates lower than 100 °C/min, in-
creasing the heating rate increased the melting temperature and the breadth of the melt-
ing peak of polymer materials [16]. Recent advances in DSC technology allowed studying
melting of polymers at extremely high heating rates up to 6 × 106 °C/min [12, 17, 18]. It has
been shown that exposing polymer materials to extremely high heating rates can alter
their melting behavior in different ways [12, 18]. For instance, Schawe [19] showed that
increasing the heating rate from 600 to 12,000 °C/min reduced the melting temperature of
isotactic polypropylene (iPP) by almost 10 °C but further increase in the heating rate in-
creased the melting temperature. On the other hand, Hellmuth and Wunderlich [20]
found that increasing the heating rate from 10 to 1,000 °C/min did not have a considerable
effect on the observed melting temperature of polyethylene. Minakov et al. [21] reported
that increasing the heating rate from 60,000 to 216,000 °C/min increased the melting tem-
perature of polyethylene terephthalate by 4 °C. They also studied superheating of isotactic
polystyrene (PS) and found a 10 °C increase in its melting temperature in the abovemen-
tioned heating rates. As a general conclusion, it can be seen that despite different re-
ported behaviors of polymers exposed to high heating rates, the previous studies showed
that the variation of melting temperature was always less than 10 °C, which indicates that
the effect of high heating rates on the melting point of polymers should not be significant.

2.3 Surface rearrangement

At temperatures above the melting point and under pressure applied by jaws, asperities
at the surface of films disappear, and a complete surface contact between the two sides
of the seal is established. In this step, the interface formation between two films occurs
through wetting and spreading mechanisms. Spreading and wetting begin from the re-
gions with the lowest surface roughness and then grow in the two-dimensional inter-
face plane [22–24]. This is shown schematically in Figure 2.6. The rate of surface wetting
increases by increasing the temperature, pressure, and chain mobility [22, 24–28].
18 Chapter 2 Molecular mechanism of heat sealing

Top
(i)
Bottom

Top
(ii)
Bottom

Top
(iii)
Bottom

Top
(iv)
Bottom

Figure 2.6: Schematic of wetting and spreading process in 2D plane of the interface between two seal sides.

The interdiffusion step begins only after establishing contact between two seal
sides through surface rearrangement. This indicates the importance of surface rear-
rangement step in a heat sealing process. The surface rearrangement and wetting can
be hindered by surface impurities resulting from processing or handling of the films.

2.4 Molecular interdiffusion across the interface

At temperatures above Tm of the sealant and after establishing surface contact through
surface rearrangement, polymer chains at the interface will have the opportunity to dif-
fuse across the interface. The interface healing and strength development are directly
related to molecular interdiffusion across the interface [29]. Therefore, understanding
the mechanism and kinetics of molecular diffusion in polymer melts is critical in ana-
lyzing the heat sealing process. For example, estimation of the minimum time required
for interdiffusion and formation of entanglements across the interface allows minimiz-
ing dwell time and increasing the production rate.

2.4.1 Polymer interdiffusion dynamics

Different models have been proposed to explain polymer chain dynamics in the solution
and the bulk. The first model that tried to explain polymer chain motion was presented
by Rouse [30] in which a polymer chain is divided into submolecule segments. Each seg-
ment consists of polymer units (mers) and has enough length to be considered as a
 2.4 Molecular interdiffusion across the interface 19

Gaussian chain. This model was later reformulated by Bird et al. [31] in the form of suc-
cessive repetition of beads and Hookean springs similar to the one shown in Figure 2.7.

Figure 2.7: The schematic representation of the Rouse model including beads and Hookean springs.

In this model, it is assumed that the beads and springs are surrounded by a viscous
medium which, in the case of polymer melts, represents the surrounding polymer
chains. This model allows a significant internal degree of freedom and can explain
chain orientation and extension. An important parameter in this model is the Rouse
relaxation time which is defined as
6ηM
τR = (2:3)
π2 ρRT

where ρ, M, R, η, and T are density, Mw, universal gas constant, viscosity, and temperature,
respectively. The diffusion coefficient of a polymer chain (Dc) in this model is defined as
Dc = D/M, where D is the diffusion coefficient of a statistical segment. Based on the Rouse
model, the mean square displacement of a polymer chain, < X2 >, obeys two regimes:

(i) at t < τR:

1=2
12MDc b2
< X2> = t1=2 (2:4)
π

(ii) at t > τR:

< X 2 > = 6Dc t (2:5)

In equation (2.4), b is the statistical chain segment length. Considering the definition of Dc,
it can be seen that the movement of a polymer chain at t < τR is independent of the mass
of the chain and depends on time by t½. On the other hand, at t > τR, the Rouse model
predicts that the displacement of a chain is inversely related to its mass and depends line-
arly on time. In fact, based on the Rouse model, at t > τR, the whole chain diffuses and, as
a result, the chain movement is independent of the statistical segment selection.
As the Rouse model does not consider the effect of chain–chain interactions, it
cannot predict the effect of molecular size and entanglements on polymer properties.
20 Chapter 2 Molecular mechanism of heat sealing

For example, the Rouse model predicts that the viscosity of a polymer melt depends
proportionally to its Mw which is in a relatively good agreement with reported depen-
dency of M1.8 for very low Mw polymer melts [32]. However, it has been shown that
the viscosity of high Mw polymer melts, where chain entanglement is significant, de-
pends on the Mw by M3.4 [33], which is far from the Rouse model prediction.
In order to explain the movement of large polymer molecules, de Gennes [34] pro-
posed the reptation model in which the restriction imposed by neighboring polymers
is considered as a temporary tube surrounding the polymer chain. Figure 2.8 schemat-
ically shows the tube model surrounding a polymer chain.

Figure 2.8: Schematic of the de Gennes tube model showing the initial tube around a polymer chain with
the surrounding obstacles (shown as black points).

The polymer chain in this model can only diffuse along the axis of the tube. As the
chain diffuses, it leaves a part of the initial tube and enters a new tube. This process is
called reptation. Based on this model, displacement of polymer molecules over long dis-
tances occurs when the polymer chain leaves its initial tube completely. The polymer
chain in this model is a Gaussian chain and consists of beads and Hookean springs simi-
lar to the one in the Rouse model. Compared to the Rouse model, the reptation model
has two additional parameters: the tube diameter and the tube length. Three important
relaxation times determine the different regimes of diffusion in the reptation model: (i)
the entanglement time (τe), (ii) the Rouse relaxation time (τR), and (iii) the disentangle-
ment time (τd). The entanglement time (τe) is the time that a Rouse bead needs to travel
the tube diameter to feel constraints of the tube. τe is defined as


Me 2
τe = τR (2:6)
M

The definition of the Rouse relaxation time (τR) is the same as equation (2.3). Finally,
the disentanglement time (τd) in the reptation model is defined as the required time
for a chain to completely leave the initial tube and is defined as
 2.4 Molecular interdiffusion across the interface 21


M
τd = 6 τR (2:7)
Me

At times smaller than τe, the beads do not feel constraints of the tube; therefore, the
mean square displacement of a polymer chain in this region is the same as equation
(2.4) and depends on time with t½. At τe < t < τR, the beads move randomly but the
whole chain does not move; therefore, the initial tube does not change. The mean
square displacement in this regime can be explained by the following equation:

1=4
4Db2
<X 2 > = t1=4 (2:8)
3π

For τR < t < τd, the mean displacement is proportional to t1/2. Finally, at t > τd, the
whole chain moves and the mean square displacement of the chain in this region is
linearly related to time. Figure 2.9 schematically shows different regimes of molecular
interdiffusion described earlier.

1
log <X2>

¼
½

τe τR τd Log(t)

Figure 2.9: Different interdiffusion regimes of a polymer chain in the entangled system based on the
reptation model. The shown values are the slope of the lines.

Based on the reptation model, the diffusion coefficient at t > τd is related to Mw by M−2.
This relation was later proved by experimental measurements on diffusion of linear
polymer chains in the melt state [35–37]. In addition, the reptation model predicts that
zero shear viscosity of linear polymer melts with narrow MWD depends on Mw by M3
which is close to the well-known empirical relation of ηo ~ M3.4 [32, 33]. These results
indicate that the reptation model can successfully predict molecular dynamics of en-
tangled linear polymer chains.
It should be noted that both the Rouse and the reptation models were based on
the assumptions of narrow Mw and linear polymer chains. However, many polymers
used for sealant layers have broad MWD and short or long chain branches. These
22 Chapter 2 Molecular mechanism of heat sealing

parameters have been shown to affect molecular interdiffusion [29, 38, 39] and their
effects on heat sealing will be discussed later in Chapter 6.

2.4.2 Interdiffusion at polymer–polymer interfaces

The models described in the previous section were proposed for interdiffusion in the
bulk of polymers but in a heat sealing process, diffusion occurs at the interface between
two films. Polymer diffusion across the interface has been widely discussed in the litera-
ture of welding and healing of polymer–polymer interfaces [23, 40, 41]. The diffusion
mechanism at the interface significantly depends on the configuration and situation of
the chain ends relative to the interface as well as the free volume at the surface. It is
known that the free volume increases by approaching the surface, which increases the
diffusion rate at the surface compared to the bulk. The thickness of the surface layer with
higher free volume has been estimated to be in the order of 1–10 nm [42]. Wool [25, 43]
studied diffusion across the interface of a deuterated PS and a hydrogenated PS surface
using secondary ion mass spectroscopy and found that the variation of the interpenetra-
tion distance with time follows t1/4, which corresponds well with the reptation model pre-
diction. Considering the common dwell times in heat sealing processes and the reptation
timescale of high Mw entangled polymer chains, the sealing process is usually done at
dwell times much shorter than the disentanglement time (τd). The minimum required
dwell time for diffusion and entanglement formation in a heat sealing process can
be estimated as the time required for polymer chains to diffuse a distance equal to
their radius of gyration (Rg). This time is commonly named the interdigitation time
and is defined as [44, 45]

R2g
τi = (2:9)
4DC

Qureshi et al. [46, 47] estimated the interdigitation time and diffusion distance for a
PE matrix with Mw = 120 kg/mol as 0.04 s and 280 nm, respectively. However, they
found that the time required for hot tack strength to reach its maximum value was
almost two orders of magnitude greater than the estimated interdigitation time. They
attributed this observation to an assumption of the presence of a thin layer of low
Mw amorphous chains at the surface of the films. The presence of such amorphous
layer on the surface of polymer films has also been reported by some other research-
ers [48]. Qureshi et al. argued that in order to develop seal strength, large polymer
molecules should diffuse through this thin low Mw layer which increases the time re-
quired for seal development compared to the estimated interdigitation time.
 2.5 Cooling and crystallization 23

2.5 Cooling and crystallization

Jaws are opened after dwell time and usually the sealed area begins to cool down by con-
vection heat transfer to the surrounding atmosphere/media. As the temperature of the
sealed area decreases, molten polymers in the sealed area begin to solidify and, in the
case of polymers with fast crystallization, form dense ordered structures called crystals.
The formation of polymer crystals reduces the mobility of polymer chains diffused across
the interface and increases the seal strength [1, 3]. The crystallization of semicrystalline
polymers from the melt has been the subject of many studies as it directly affects the
final properties of polymer matrices, including (but not limited to) mechanical properties
[49], moisture [50], and gas permeability [51]. Before reviewing thermodynamics and ki-
netics of crystallization, first, the structure of a polymer crystal needs to be briefly dis-
cussed. It has been shown that in polymer crystals formed from dilute polymer solutions,
polymer chain axes are perpendicular to the basal face of crystals. Based on these obser-
vations, it was proposed that polymer chains fold in these crystal structures with adjacent
reentry into crystals [52]. This model is called the folded chain model and is illustrated in
Figure 2.10(a). Flory [53] showed that the adjacent reentry assumption is not valid for
crystals formed from polymer melts. He proposed the switchboard model in which poly-
mer chains that leave the basal face of a crystal reenter the crystal but with varying
length of the loops, and some chains do not return to the same crystal but enter another
crystal and link the crystals. This model is schematically shown in Figure 2.10(b).

(a) (b)

Figure 2.10: Polymer crystal models: (a) the folded chain model and (b) the switchboard model.

Crystallization of polymer melts is a nonisothermal process and consists of two main

steps: (i) nucleation and (ii) crystal growth. Figure 2.11 shows a typical nonisothermal
crystallization rate as a function of temperature for semicrystalline polymers.
As can be seen, by increasing the supercooling degree (which is defined as ΔT =
Tm–T), the crystallization rate increases up to a maximum and then decreases gradu-
ally. The crystallization process begins with the formation of very small crystals known
as primary crystals or crystal nuclei. If the primary crystal is formed without the influ-
ence of any foreign particle or surface, the nucleation is called homogeneous nucle-
ation. This type of nucleation is rarely observed in bulk polymers [54]. By contrast, if
24 Chapter 2 Molecular mechanism of heat sealing

Tc

Linear Growth Rate (mm.s–1)

Tm

Temperature (°C)

Figure 2.11: Typical crystal growth rate as a function of temperature in nonisothermal crystallization of
semicrystalline polymers.

the nuclei are formed on the surface of a foreign particle, the nucleation is called het-
erogeneous nucleation.
In the case of homogeneous nucleation, the free enthalpy of crystallization (ΔGC)
for a nucleus varies with its size as shown in Figure 2.12. ΔGC of a homogeneous nucle-
ation is positive for small nuclei and increases by increasing the nuclei size until it
reaches a maximum. The nucleus with the maximum ΔGC is known as a critical nu-
cleus. By further increasing the nucleus size, at a certain size, ΔGC becomes zero. This
certain size is known as nucleus stable size.

ΔGc
Subcritical Supercritical Stable

Critical Nucleus Size

Size

Figure 2.12: Variations of the free enthalpy of crystallization by the nucleus size in homogeneous nucleation.

As shown in Figure 2.12, three different regions of ΔGC curve indicate three types of nu-
clei at the beginning stages of crystallization. Nuclei formed with sizes smaller than the
critical size are called subcritical nuclei and have the least probability of growth and
 2.5 Cooling and crystallization 25

most likely will be disintegrated. When the nucleus size is between the critical size and
the stable size, the formed nuclei have a positive ΔGC, but increasing the nucleus size
reduces the enthalpy of crystallization. These nuclei are much stable and are called su-
percritical nuclei. Finally, when nuclei size is greater than the stable size, their ΔGC is
negative and they are thermodynamically stable. It has been shown that the enthalpy
of crystallization of a primary nucleus with the critical nucleus size, or in other words
the energy barrier against nucleation, decreases with supercooling as ΔT −2 [55, 56]. As a
result, the rate of primary nuclei formation decreases dramatically by approaching the
melting temperature. In the case of heterogeneous nucleation, it has been shown that
the free enthalpy of crystallization of a heterogeneous nucleus (ΔGhetero) and a homoge-
neous nucleus (ΔGhomo) are related as [57]

ΔGhetero = ΔGhomo × ϕ (2:10)

where ϕ can vary between 0 and 1. This relation shows that the energy barrier against
the formation of heterogeneous nuclei is lower than that of homogeneous nucleation,
which indicates that the heterogeneous nucleation is thermodynamically favored.
After the formation of a stable nucleus, the crystal growth step begins. Hoff-
man classified the crystal growth into three regimes based on the degree of super-
cooling [52, 58]. Regime I is at small supercooling and close to the melting temperature. In
this regime, one chain is crystallized at the surface of a nucleus at a time. This requires
adjacent reentry of the chain. On the other hand, the high temperature of this regime
provides high molecular mobility which allows high crystal growth rate. Regime II is ob-
served at moderate supercooling, where multiple polymer chains are crystallized at the
same time on the surface of nucleus, with a distance between growth sites known as the
niche distance. Hoffman [58] showed that in polyethylene, the transition between regime
I and II occurs at a supercooling of 16 °C. Finally, regime III is observed at high supercool-
ing, and the crystallization rate in this regime is very rapid, and the adjacent reentry
does not happen, but the formed crystals in this regime show structures similar to the
switchboard model. It was shown that in the case of polyethylene, the transition between
regime II and III occurs at a supercooling of 23 °C [58]. The crystal growth rate in these
regimes can be compared as regime I ~ regime III > regime II. Considering the low nucle-
ation rate in small supercooling region of regime I, regime III is the most desirable re-
gime for crystallization to achieve high crystallinity in industrial applications. As
crystallization is an exothermic phenomenon, DSC is widely used to study crystalliza-
tion of polymers. Figure 2.5 shows schematically the nonisothermal crystallization
curve of a polymer material in a DSC test. The crystallization is observed as an exother-
mic peak in DSC curves. The temperature of the maximum in the crystallization curve
is known as the crystallization temperature (Tc). It has been shown by many research-
ers that increasing the cooling rate shifts the crystallization temperature of polymers
to lower temperatures and reduces the enthalpy of crystallization [16, 59–61]. This is
attributed to the imperfection induced into the crystal structure at higher cooling
rates. In order to analyze the crystallization phenomenon in a heat sealing process, it
26 Chapter 2 Molecular mechanism of heat sealing

100
T
m

80 T
Temperature (°C)

60

40

20
0 10 20 30 40 50
Cooling Time (s)

Figure 2.13: Interface temperature as a function of cooling time in a heat sealing process between two
PE sealants with Tjaw = 100 °C. The marked Tm and Tc were determined from DSC analysis at a
heating/cooling rate of 10 °C/min (unpublished data).

is necessary to determine the cooling rate of the sealant layer after opening of the
jaws. Figure 2.13 shows the estimation of the interface temperature between two poly-
ethylene sealants as a function of cooling time after heat sealing at a jaw temperature
of 100 °C.
The interface temperature decreases at an average rate of 3.75 °C/s or 225 °C/min
in the first 10 s of the cooling step. Most of the previous works that studied the effects of
cooling rate on polymer crystallization were performed using conventional DSC at cool-
ing rates lower than 60 °C/min. This indicates that the effect of high cooling rates used in
heat sealing on polymer crystallinity needs to be addressed. It has been shown that the
cooling polymer melts at extremely high cooling rates can finally vitrify polymer melts at
Tg and form an amorphous polymer [62]. However, this phenomenon happens at cooling
rates much higher than the cooling rates in a heat sealing process. For example, it has
been shown that cooling HDPE at 60 × 106 °C/min [21, 63] or iPP at 60,000 °C/min [64] pre-
vents crystallization and results in the formation of a completely amorphous polymer.
Schawe [12] studied the effect of different cooling rates on crystallization of iPP in a wide
range of cooling rates by combining the results of conventional DSC and high cooling rate
Flash® DSC. He found that increasing the cooling rates reduced TC but observed a consid-
erable reduction in the enthalpy of crystallization only at cooling rates greater than
1,800 °C/min. Based on all aforementioned cases, it is expected that experiencing higher
cooling rates compared to the one used in conventional DSC analysis of polymers shifts
TC and reduces the enthalpy of crystallization; however, the extent of these effects de-
pends on polymer types.
 References 27

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Chapter 3
Seal quality and performance evaluation methods

Evaluation of seal area after sealing is of great importance as it provides valuable in-
formation about the integrity, quality, and strength of the seal. Presence of micro-size
defects could be very difficult and challenging to detect but they can have detrimental
effects on packaging performance. For instance, Kirsch [1] showed that the probability
of microbial ingress increases significantly when the leak size in nonporous packag-
ing film is greater than only 1 μm. Test methods that are used to examine the seal
area in polymer packaging can be generally categorized into two main groups: (i) seal
quality and (ii) seal performance tests. The focus of seal quality tests is on detection of
any imperfection in the sealed area such as channels and unsealed area. These defects
can cause deterioration or contamination of the product. The seal quality tests do not
provide any information about the strength of the seal and the results of these tests is
binary results of fail or pass. On the other hand, seal performance tests examine the
strength of the seal and package integrity. However, in some cases, the results of
these tests cannot provide much information about the seal quality and presence of
defects in the seal. For example, presence of few micro-channels does not affect seal
strength considerably, however, it can cause leaking and contamination of the prod-
uct. Therefore, seal quality and seal performance tests are complimentary tests and
both tests are needed to obtain a comprehensive overview of the seal and package
quality/performance.

3.1 Seal quality tests

Before discussing seal quality tests, first, we need to explain different possible defects
that may occur in a sealing process. The most possible defects can be listed as follows:
– Unsealed area: unsealed area can be created due to different reasons including
(but not limited to) misalignment of package to seal bars, surface contamination
of films, presence of external object (product, dust, etc.) between seal sides, par-
tial seal rupture opening due to sterilization, handling, or weight of product.
– Microchannels: fine pathway across the sealed area that can be created due to
different reasons including the ones mentioned earlier.
– Narrow seals: This is a phenomenon when the width of the sealed area is reduced
at certain part over the whole sealed area. This can be caused by misalignment of
the heated bars and the films, due to misalignment of cutter/slitters or due to par-
tial opening of the seal.
– Oversealed area: if the temperature and pressure of sealing machine is too high
or the dwell time is long, other layers of the film can also be melted and cause
brittle sealing.

https://doi.org/10.1515/9781501524592-003
32 Chapter 3 Seal quality and performance evaluation methods

– Tears/pinholes: it can happen in the material or substrate.

– Microbubbles: bubble formation can happen due to the low and nonuniform seal
pressure or due to the presence of contamination at the surface.
– Wrinkle and fold overs: when the film is folded over before sealing, it can form
channels in the folded area.

Some examples of these defects are shown below. Figure 3.1(a) shows a microchannel
in the seal area which connects two sides of the seal area. Figure 3.1(b) shows a sealed
area with unsealed regions in this case due to the presence of a liquid product in the
seal area. Figure 3.1(c) shows folding over issue in seal area, and finally Figure 3.1(d)
shows a seal with microbubbles in the seal area.

(a) (b)

Sealed Area
Sealed Area

Unsealed regions

Channel

(c) (d) Micro-bubbles

Sealed Area

Sealed Area

Fold

Figure 3.1: Examples of different types of defects in the sealed area.

In the case of channeling, unsealed area and defects that are across the seal area and
connect two sides of the seal, leakage rate is a very important parameter that is used
to indicate the size of the defect. Different units of leakage rate and their conversion
are shown in Table 3.1.

Table 3.1: Seal leakage rate units [2].

Pa.m/s Std cm/s Std L/day Air at

 °C kg/year

   
 3.1 Seal quality tests 33

The most common unit is standard cubic centimeter per second (sccs). From leak-
age viewpoint, a package is called leak free if the leakage rate is small enough than it
will not affect the package quality, protection role and performance. Therefore, men-
tioning a leak-free package without specifying the limit leakage rate for the desired
application is meaningless. Figure 3.2 shows different leakage rates with their practi-
cal significance.

101 100 10–3 10–6 10–9 10–12

Audible Visible Ultrasonic sound Microbes Gases Helium

Figure 3.2: Different leakage rate in sccs units with their significance.

3.1.1 Visual inspection

The first and simplest method for examining seal quality is the visual inspection of
the sealed area. This method can be used for channels with width down to 75 μm.
ASTM F1886 [3] provides a standard test procedure for visual examining of the seal
quality. In this method an illumination of 540 lumen/m2 is required and the sealed
area is examined from 30 to 40 cm distance and the number of defects are recorded.

3.1.2 Flat bar test

This method is a common and handy method for initial examining of the seal area
integrity. In this method, a special-shaped flat bar is placed inside the package and is
gently forced to the sealed area to make sure no-peeling occurs. The bar is designed
so that the curved area such as gusset area and the flat area such as side sealed area
can be easily examined. This test provides quick and simple qualitative evaluation of
sealed area integrity before doing further tests. The main disadvantage of this testing
method is its significant dependency on the pressure applied by the operator which
can be different (Figure 3.3).
34 Chapter 3 Seal quality and performance evaluation methods

(a) (b)

(c)

Figure 3.3: Flat curved bar for examination of the sealed

area: (a) the bar, (b) examining side seal,
and (c) examining corners and gusset seal.

3.1.3 Gross leak or bubble test

This test method is aimed to detect leaks and channels down to 250 μm. According to
ASTM F2096 [4], the package is inflated underwater using an internal air pressure in-
troduced into the package by an airway. The package is inflated to a predetermined
pressure and then it is checked for air bubbles streams exiting the package. In order
to determine the pressure, a defect with known size is created in a package and then
the package undergoes inflation. The pressure at which the first air bubble is ob-
served is considered as the minimum inflation pressure that is used in testing. This
test method can also be used for vacuum packing products.
In a similar standard test method in ASTM D3078 [5], the package is placed in a
sealed water reservoir and then vacuum is applied to the reservoir. The package is in-
flated under vacuum and air bubble stream can be observed from the leak points/area.
This test method can be used for packaging with headspace gas and is not suitable for
testing vacuum packaging. Reported laboratory results [5] indicated that high vacuum
(~24 in Hg = 600 mm Hg) was required to detect very small leaks (10−2 sccs) and those
leaks could not be detected in medium vacuum (18 in Hg = 460 mm Hg) that is commonly
used to test flexible packages. Similar test technique is used to determine the effect of
altitude on packaging [6]. The required vacuum should be determined by creating a leak
with known size and then determining the vacuum required to observe air bubbles from
that leak. The package is considered to pass the test if no bubble is observed at least for
 3.1 Seal quality tests 35

(a) (b)

Pack-Vac Leak Detector

(c)
Water bath

Pack-Vac Leak Detector

Pressure Gauge Exiting

Air Bubbles
Pack-Vac Leak Detector

Figure 3.4: Vacuum leak test: (a) testing machine, (b) a package with no leak during the test,
and (c) a package with air bubbles emerging from the leaks.

30 s after reaching 18 in Hg. Figure 3.4 shows the testing reservoir and a sample that
passed the test (Figure 3.4b) and a sample that failed the test (Figure 3.4c).

3.1.4 Pressure decay leak test

In pressure decay leak test method, the package is pressurized by air to a certain pres-
sure and then air flow is closed and internal pressure of the package is monitored.
Decrease in the internal pressure of the package indicates the presence of leaks. This
test can be done according to ASTM F2095 [7]. This test method provides a rapid test
to detect small leaks in order of 10−4 sccs. The following relation can be established to
determine the leak rate (Q) from pressure decay results:

 
ΔP ðatmÞ × V cm3
Q ðsccsÞ = (3:1)
Δt ðsÞ

where ΔP is the pressure decay, V is the package volume, and Δt is test duration. For
example, a pressure decay of 1 mbar from a package of 100 cm3 in 30 s indicates a
leak rate of 3.3 × 10−3 sccs.
The test can be done with or without a restraining plate. The restraining plate has
two main roles: (i) limits the volume of the inflated bag and therefore reduces test time
and increases sensitivity of the test results, (ii) reduces the chance of bursting or peeling
the seals. In order to avoid the restraining plate to block the leaks, the restraining plate
36 Chapter 3 Seal quality and performance evaluation methods

should be selected from semiporous plastics or surface scored plates or from screen-
type materials.
Similar approach is used in ASTM F2338 [8] for vacuum decay leak test in which
the package is placed in a chamber and then the chamber is vacuumed. The vacuum
valve is then closed, and the chamber pressure is monitored by time. Any increase in
chamber pressure indicates leak from the package headspace gas. This test method
can detect very small leak rates in order of 10−6 sccs and leak sizes down to 5 μm [8].

3.1.5 Dye penetration test

This technique can be used for nonporous packages and can be done in two methods:
(A) testing for channels and leaks in the seal or (B) testing for holes or leaks in the flat
area. Dye penetration testing procedure is explained in ASTM F3039 [9]. Considering
the scope of the book, only the first group of testing is of our interest. This type of
testing can be used to detect leaks with the size greater than 50 μm. In this method, a
dye penetrant is injected in the package to reach 25 mL of dye per inch (2.54 cm) of
the seal area. The injection is usually done from the middle of the package and the
package is rotated slowly to make sure the solution is in contact with all sealed edges.
The solution remains in contact with the seal area for 5 s. The sealed area in transpar-
ent packaging can be examined by eye or by optical device with 5× to 20× magnifica-
tion. In the opaque packaging, the outside of the sealed area is placed in contact with
a dye absorbent.
Due to the contrast between the dye solution and the film, channels, leaks, and
unsealed area are shown as lines or strips with the dye solution color. In most sealing
companies and converting companies, the dye is placed in the pouch and then the
pouch is sealed, and the dye is pushed by hand around the seal area to find out any
channel or defect in the sealed area. Figure 3.5 shows an example of a package filled
with iodopovidone as the dye and package is examined around the corner and close
to the zipper area.

Zipper area Side Seal Gusset Area

Figure 3.5: Dye penetration test using iodopovidone in a transparent PE zipper bag.
 3.1 Seal quality tests 37

3.1.6 Pressure-assisted dye penetration test

Applying pressure to the package during dye penetration test is a method to reduce
the test time and increase the accuracy. In this method, the dye liquid is placed inside
the package and then the package is sealed. The sealed package is placed between two
plates that apply the pressure. The pressure is applied manually or using a motorized
machine to reach the desired pressure. Generally, a pressure around 6 psi or 40 kPa is
applied to the package. However, the applied pressure can be increased based on the
final application. While the package is kept under the applied pressure, sealed area is
examined visually for any dye penetration or leak. Figure 3.6 shows a pressure-
assisted dye penetration test in which the pressure is applied by an electronic com-
pression tester.

(a) (b)

Figure 3.6: Pressure-assisted dye penetration test: (a) the machine and (b) the package under pressure.

3.1.7 Airborne ultrasound

Ultrasound seal quality verification is based on the concept that the ultrasound wave
is reflected or absorbed in an unsealed area instead of propagating through the film
layers, Figure 3.7. Therefore, defects can be detected by a drop in ultrasound signal
received by the detector on the other side of the sealed area.

(i) (ii)

Figure 3.7: Detecting seal defects by airborne ultrasound method: (i) seal without defect and (ii) seal with
defect. The curved line represents ultrasound waves. The dashed line shows the interface between two
sides of the seal area.
38 Chapter 3 Seal quality and performance evaluation methods

Airborne ultrasound is a noncontact, nondestructive technique that allows analysis

of material without contacting to the sensor. The analysis can be done in two modes:
linear analysis (L-scan) and 2D analysis (C-scan). The defects are shown typically similar
to the one showed in Figure 3.8. ASTM F3004 [10] explains the procedure to perform the
seal quality verification using airborne ultrasound. Compared to previous seal quality
methods, airborne ultrasound is a much costly technique and requires more training
and maintenance costs, but it is the only industrially available technique to monitor
seal quality in-line and during sealing process. This unique feature allows higher con-
trol on package quality during production and increases considerably the reliability
and reduces the production costs especially in the trial step. However, it should be
noted that the current airborne ultrasound machines can only be used to monitor seal
quality in the sealing lines with line speeds below 30 m/min.

(a)

(b)

Figure 3.8: Airborne ultrasound scan of a sealed area (a) C-scan and (b) L-scan. The dashed gray line in
(a) shows where L-scan was taken. The green area shows the sealed area, pink area is the outside of the
package and the red line shows the channel.

3.2 Seal performance tests

Testing techniques used for evaluation of seal properties can be categorized based on
the temperature in which the test is done: (i) hot tack tests where the test is done
when sealed area is at temperatures above room temperature, and (ii) seal tests
where the test is done when the seal area is cooled down to ambient temperature.
Both these tests provide the strength of the sealed area as the average required force
 3.2 Seal performance tests 39

per unit width of the sealed area to pull apart two sealed films. The first set of test
result is called hot tack strength and the second test results are reported as seal
strength. The common units of hot tack and seal strength with their conversion coeffi-
cients are listed in Table 3.2.

Table 3.2: Conversation factors for seal strength and hot tack units conversion.✶

g/ mm g/ mm N/m N/ mm N/ mm lb/in

g/ mm  . . . . .

g/ mm .  . . . .
N/m . .  . . .
N/ mm     . .
N/ mm .   .  .
lb/in    . . 
✶
Values are rounded upward to simplify calculations.

Hot tack strength provides important information about seal performance at high
temperatures. For example, hot tack is an important factor in vertical form fill seal
(VFFS) machines as the package is usually filled when the bottom seal is still hot and
should withstand the weight of the product. Hot tack is also important in some hori-
zontal form fill seal (HFFS) applications, for example, when hot tack strength is
needed to resist springback forces in gusseted areas (where the films are folded).
From industrial viewpoint, achieving required hot tack strength at lower tempera-
tures is desired to increase the production rate and reduce the final cost.
On the other hand, seal strength measured at ambient temperature is an impor-
tant factor during transportation, storage, and final customer use. Generally hot tack
strength is lower than seal strength due to the higher mobility of polymer chains and
less crystallinity at higher temperatures which results in entanglement opening and/
or pull out of the chains at lower forces [11]. This point will be explained more in
Chapter 6, where the effects of processing conditions on seal performance will be dis-
cussed in detail.
It should be noted that based on ASTM, all samples are recommended to be condi-
tioned following ASTM E171 [12] at 23 ± 2 °C and humidity of 50 ± 5% RH for at least
24 h before testing.

3.2.1 Hot tack test

Hot tack measurement tests are done based on ASTM F1921 [13] standard method.
This standard method is restricted for testing by a hot tack machine fulfilling require-
ments mentioned in ASTM F2029 [14]. The instrument should have a cycle with the
40 Chapter 3 Seal quality and performance evaluation methods

(a) (b) (c) (d)

Figure 3.9: Different steps needed in a hot tack test: (a) approaching of the jaws, (b) sealing, (c) delay
step, and (d) withdrawal and force measurements. The pointers on the jaws and films show the direction
of jaw movement and the applied stress direction to films, respectively.

four following phases: (i) sealing, (ii) delay, (iii) withdrawal, and (iv) force measure-
ment. These testing steps are schematically shown in Figure 3.9.
Based on ASTM F1921, sample strips for hot tack measurements should have length
of 25–35 cm (10–14 in) and width of 25 mm (1.00 in) or 15 mm. These sample strips are
pressed together between the heated jaws for a predefined dwell time (Figure 3.9(b)).
Dwell time should be long enough for the interface between sample strips to reach the
desired sealing temperature. A sealing pressure of 40 or 72 psi is common in lab testing
but other pressures can also be used. At the end of the sealing phase, the grips move
apart after a preset delay time (Figure 3.9(c)). The delay time is defined as the time pe-
riod between opening of the jaws (end of the sealing phase) and applying the force (the
beginning of the withdrawal phase). During the delay time, the seal area is cooled
down by heat transfer to the surrounding environment. During withdrawal phase, the
machine applies forces to the sample strips to separate them apart ideally at the inter-
face between them. Two hot tack methods were mentioned in the standard method to
measure the hot tack strength. The hot tack strength is reported as the maximum force
measured during grip separation (withdrawal phase). Figure 3.10 shows a typical shape
of the force–distance curve during a hot tack test.
At the beginning of the withdrawal phase, the grips begin to travel apart and
stretch the film. The force at this early stage of the withdrawal phase is small until
the film is completely straight. At this point, the applied force begins to increase.
When the applied force exceeds the hot tack strength, the sealed area begins to be
peeled. The peeling continues until the end of the length of the sealed area and drops
to zero at the end of the sealed area. According to ASTM F1921 Method B, the maxi-
mum applied force recorded is reported as the hot tack strength. In addition to hot
tack strength, examining the sample and determining the failure mode is very impor-
tant in analyzing the results. Figure 3.11 shows the different separation modes during
seal test. In the adhesive peeling, the seal is opened under the applied force at the
interface between two sealant layers. Adhesive peeling occurs when seal strength is
lower than the strength of layers. On the other hand, cohesive peeling is observed
 3.2 Seal performance tests 41

Force

Fmax

Distance

Figure 3.10: A typical hot tack curve showing applied force to the sealed area as a function of the distance
traveled by the grips. L is the length of the sealed area and Fmax is the maximum recorded peeling force.

when hot tack strength is greater than the strength of each sealant layer. This occurs
when sealant layer contains some defects that cause stress concentration and crack
propagation in the sealant layer. Some common defects could originate from the pres-
ence of gel particles, another phase or solid particles present in the sealant layer.
The delamination mode is observed when hot tack strength is greater than the adhe-
sion strength between abuse layer (outer layer) and the film. In addition, there are
some other modes of failure that can occur during seal test which are shown in Figure
3.12. In the case of break and remote break, the plastic film breaks after applying the
force due to the defects in the film or due to the very high strength of the seal. Based on
the test results, sealing can be divided into two main groups of peelable and lock seal.
Peelable seals are those that show peeling behavior (adhesive or cohesive) during test,
while lock seals do not show peeling behavior. Therefore, based on this categorization,
seal area showing adhesive peeling, cohesive peeling, and peeling with elongation be-
havior can be labeled as peelable seals. On the other hand, seals that show delamina-
tion, break, remote break, elongation, and tear are categorized as lock seals. Figure
3.13 shows images of the samples with these three types of sealing behavior.
Both samples (a) and (b) show adhesive peeling behavior but sample (a) shows poor
hot tack strength and no considerable change in the film appearance after seal opening,
while sample (b) shows adhesive peeling behavior with higher seal strength and whiten-
ing of the sealed area after peeling. This whitening has been shown to be due to forma-
tion of elongated filaments at the seal area during testing [15]. It should be mentioned
that distinguishing adhesive and cohesive peel could be challenging in some cases and
may require microscopy analysis to determine where peeling occurred. Sample (c) shows
very high hot tack strength and tears from sealed area during testing. Based on these re-
sults, samples (a) and (b) can be categorized as peelable with adhesive peeling mecha-
nisms and sample (c) as lock seal with tear in sealed area. As hot tack strength depends
on the peeling rate [16], it is recommended to examine it at both high (about 12 in/min or
42 Chapter 3 Seal quality and performance evaluation methods

Adhesive Peeling

Cohesive Peeling

Delamination
Figure 3.11: Different modes of seal separation. The
dashed lines show the interface between two sealant
layers. The dark layers in the last row represent the
abuse layer.

5 mm/s) and low (1 in/min or 0.43 mm/s) peeling rates for materials when hot tack
strength change considerably with peeling rate. However, in packaging industry, compa-
nies use the peeling rate for hot tack test according to their final application. This results
in a wide range of peeling rate used in packaging industry, which can result in discrepan-
cies in hot tack strengths of the same sample measured by two different companies.

3.2.2 Seal strength measurement

The typical sample widths for seal strength measurements are 15 and 25 mm. The
sealed area length is determined based on the sealer configuration. For example, in
heat bar sealing, it is the same as the width of the heated bars/jaws. Seal strength
measurements can be done based on ASTM F88 [17] using three different sample sup-
porting options: (i) technique A: unsupported sample, (ii) technique B: supported 90°
by hand and (iii) technique C: supported 180°. These three techniques are shown sche-
matically in Figure 3.14.
In technique A, both films are secured in the grips with 90° angle with respect to
the unsupported seal area (also referred to as the tail). Due to the unsupported nature
of the seal area in this technique, this angle changes during the test. In technique B,
the seal area is fixed during the test and remains in 90° angle with respect to the films.
 3.2 Seal performance tests 43

Break Elongation

Remote Peeling
break and elongation

Figure 3.12: Possible failure modes during seal test.

(a)

(b)

(c)

Figure 3.13: Samples showing different modes of separation: (a) adhesive peel (very low seal strength)
and (b) adhesive peeling (higher seal strength), (c) tear.
44 Chapter 3 Seal quality and performance evaluation methods

(i) (ii) (iii)

Figure 3.14: Three different techniques used for seal strength test based on ASTM F88: (i) technique
A: unsupported, (ii) technique B: supported 90°, and (iii) technique C: unsupported 180°. The pointers
show the direction of applied force.

Finally, in technique C, the sealed area is parallel to the films during the test. Technique
C is used mostly to evaluate the seal strength of a flexible film to a rigid substrate or
sheet. For example, technique C is commonly used to examine the seal strength of lid-
ding films to cups/trays. Methods A and B are commonly used to examine film samples
with similar flexibility. It is worth noting that according to ASTM F88, a flexible film is
defined as a material for which its flexural strength and thickness allow a turn back to
approximately 180°. The steps of the heat seal test are the same as hot tack test shown in
Figure 3.9. During the heat seal test, two sides of the sealed area are pulled apart and
the applied force opens the sealed area. Seal strength test can be done using a tensile
machine or an automated heat seal tester [18, 19]. The result obtained from seal strength
test is in the form of the peeling force per width of the sealed area versus the peeled
distance (similar to the one shown in Figure 3.10). According to ASTM F88, the reported
seal strength should be determined by averaging the force in the plateau region of the
curve. However, in practical applications, maximum seal strength is mostly reported,
which is defined as the maximum of the seal strength in the plateau region. It is also a
common practice in industry to report the maximum strength when the grips traveled a
distance equal to the half of the sealed area.

3.2.3 Internal pressurization failure resistance

In this type of testing, the ability of a package to withstand internal pressure is exam-
ined. ASTM F1140 [20] discusses three types of testing in this category. In burst test
method, the internal pressure is increased continuously until the package fails. The
 3.2 Seal performance tests 45

result of this test is the maximum pressure that the package could withstand before
failure. Figure 3.15 shows the testing machine to measure burst pressure and Figure 3.16
shows the test result for the shown package. At the early stages of the test, the inside
pressure does not change considerably as the introduced air results in inflation of the
package. When the package is completely inflated, the pressure increases rapidly until
the package fails. The failure should occur in the package walls (such as the one shown
in Figure 3.15(c)) and not in the seal area.

(a) (b)

Air tube

(c)

Grip Lock Package

Mechanism

Package
Grip

Burst Area

Figure 3.15: (a) Internal pressurization test machine with open package testing, (b) inflated package
under the protection cover, and (c) an example of the burst package.

In the creep test method, the pressure is increased to a specific level and then main-
tained for a certain time. If the package does not fail in the examined time period, it
is considered to pass the test. In the third method that is called creep to failure
method, the pressure is increased to a specific point and kept constant until the pack-
age fails. The result of this test is the time that the package failure is observed.
These types of test can be done for two package types: (i) open package test and
(ii) closed packages. The first type is useful to examine seal performance by convert-
ing companies that produce pouches for downstream companies that fill the pouch
with the product. The second type is mostly used for companies that fill the pouches
with products. The instrument that is used for all these tests is the same as the one
shown in Figure 3.15(a). However, the configuration for gas inlet is different. In the
46 Chapter 3 Seal quality and performance evaluation methods

10 Burst

8
Pressure (psi)

0 2 4 6 8 10
t (s)

Figure 3.16: Evolution of pressure inside the package during the burst test for the package shown in
Figure 3.15.

case of open package testing, gas is introduced from the open side of the package,
while in the closed package testing, gas is introduced using a needle inserted in the
pouch wall.

References

[1] Kirsch, L.E., Package Integrity Testing, in Guide to Microbiological Control in Pharmaceuticals and Medical
Devices, S.P. Denyer and R.M. Baird, Editors. 2006, CRC Press.
[2] Akers, M.K., D. Larrimore, and D. Guazzo, Package Integrity Testing, in Parenteral Quality Control:
Sterility, Pyrogen, Particulate, and Package Integrity Testing. 2002, CRC Press.
[3] Patrício, T., et al., Fabrication and characterisation of PCL and PCL/PLA scaffolds for tissue engineering.
Rapid Prototyping Journal, 2014.
[4] Thadavirul, N., P. Pavasant, and P. Supaphol, Development of polycaprolactone porous scaffolds by
combining solvent casting, particulate leaching, and polymer leaching techniques for bone tissue
engineering. Journal of Biomedical Materials Research Part A, 2014. 102(10): p. 3379–3392.
[5] Standard Test Method for Determination of Leaks in Flexible Packaging by Bubble Emission. 2013.
[6] Harris, L.D., B.S. Kim, and D.J. Mooney, Open pore biodegradable matrices formed with gas foaming.
Journal of Biomedical Materials Research: An Official Journal of the Society for Biomaterials, the
Japanese Society for Biomaterials, and the Australian Society for Biomaterials, 1998. 42(3):
p. 396–402.
[7] Standard Test Methods for Pressure Decay Leak Test for Flexible Packages with and without Restraining
Plates. 2013.
[8] Standard Test Method for Nondestructive Detection of Leaks in Packages by Vacuum Decay Method. 2013.
[9] Sai, H., et al., Hierarchical porous polymer scaffolds from block copolymers. Science, 2013. 341(6145):
p. 530–534.
 References 47

[10] Huang, Y., et al., Preparation and properties of poly (lactide-co-glycolide)(PLGA)/nano-hydroxyapatite

(NHA) scaffolds by thermally induced phase separation and rabbit MSCs culture on scaffolds. Journal of
Biomaterials Applications, 2008. 22(5): p. 409–432.
[11] Shekhar, A., A model for hot tack behaiveior in Ethylen Acid co-polymer films. Tappi, 1994. 77(1):
p. 97–104.
[12] Standard Practice for Conditioning and Testing Flexible Barrier Packaging. 2015.
[13] Standard Test Methods for Hot Seal Strength (Hot Tack) of Thermoplastic Polymers and Blends Comprising
the Sealing Surfaces of Flexible Webs. 2018.
[14] Kurobe, H., et al., Concise review: Tissue-engineered vascular grafts for cardiac surgery: Past, present,
and future. Stem Cells Translational Medicine, 2012. 1(7): p. 566–571.
[15] Najarzadeh, Z. and A. Ajji, Role of molecular architecture in interfacial self-adhesion of polyethylene
films. Journal of Plastic Film & Sheeting, 2017. 33(3): p. 235–261.
[16] Theller, H.W., Heatsealability of flexible web materials in hot-bar sealing applications. Plastic Film and
Sheeting, 1989. 5: p. 66–93.
[17] Giannico, S., et al., Clinical outcome of 193 extracardiac fontan patients: The first 15 years. Journal of the
American College of Cardiology, 2006. 47(10): p. 2065–2073.
[18] Fiesser, F.H. and R.V. Jeral, Transverse heat-sealing apparatus for continuous shrink film packaging,
US5475964 A, 1995.
[19] Montano, L.M., J.M. Montano, and W.J. Witzler, Method and apparatus for testing the quality of
crimped seals, US7179344 B1, 2007.
[20] Kim, T.K., et al., Gas foamed open porous biodegradable polymeric microspheres. Biomaterials, 2006.
27(2): p. 152–159.
Chapter 4
Sealant layer materials

This chapter is dedicated to a summary of the most common sealant materials that are
used in plastic packaging. It is worth mentioning that only pure materials are reviewed
here and multiphase sealant materials are presented in Chapter 7 as some theoretical
concepts need to be introduced first.

4.1 Polyethylene

Polyethylene is the most common sealant layer material used in plastic packaging in-
dustry due to its low cost, availability, ease of processing, good seal performance, high
moisture barrier, high thermal stability, and chemical resistance. The repeat unit for
polyethylene is shown in Figure 4.1.

H H

C C

H H
n Figure 4.1: Repeat unit of polyethylene.

As can be seen, polyethylene has a saturated structure without any functional group
which can explain its high chemical and thermal stability [1]. Polyethylene can only be
dissolved in non-polar solvents such as cyclohexane at high temperatures [2]. This indi-
cates the significant potential of polyethylene as the inner layer in contact with chemi-
cals or acidic foods. It is worth mentioning that the chemical resistance and barrier
properties should not be confused here. Chemical resistance indicates how much a sol-
vent can change the nature of the material by dissolution or degradation, while barrier
properties indicate the resistance of the material against permeation of a substance. For
example, polyethylene has good resistance against chemicals and is one of the best
choices for the sealant for detergent applications, but its barrier properties are not
enough to ensure inhibiting chemicals permeation out of the package. Therefore, a high
barrier layer or coating is usually used within these multilayer structures to prevent mi-
gration of the substances in these products. In addition, the lack of functional groups in
polyethylene structure results in a nonpolar hydrophobic surface [2], which is suitable
for applications where low adhesion to polar liquids is desired. Figure 4.2 shows sche-
matically the most common categorization of different polyethylene types based on their
molecular architecture.

https://doi.org/10.1515/9781501524592-004
50 Chapter 4 Sealant layer materials

(i)

(ii)
Figure 4.2: Different molecular architectures of polyethylene:
(i) linear chain with no or very few side groups, (ii) long-chain
(iii)
branched, and (iii) linear chain with side groups.

4.1.1 High-density polyethylene (HDPE)

Polyethylene with linear chain structure (Figure 4.2(a)) is known as the high-density poly-
ethylene or HDPE. The linear molecular structure of HDPE allows high level of molecular
arrangement and leads to a highly crystalline material. Due to the high crystallinity of
HDPE, it commonly has the highest density (0.945–0.97 g/cm), melting temperature
(130–140 °C), water vapor barrier, oxygen barrier, and mechanical strength among differ-
ent types of polyethylene. On the other hand, the high crystallinity of HDPE dramatically
reduces its clarity. Previous studies showed that the low clarity of HDPE film is mainly
originated from light reflection at the film surface due to film surface asperities [3]. HDPE
is commonly used in plastic packaging to provide mechanical strength and thermal resis-
tance. Due to its high melting temperature, HDPE is not a common material for the seal-
ant layer in packaging applications. However, HDPE liners are commonly used as the
interior layer of multiwall paper bags to provide moisture barrier and allow sealing of
the bags. In those applications, ultrasonic sealing is a very common sealing method that
allows quick sealing without burning of the exterior kraft paper layers. Figure 4.3 shows
the typical footprint peaks of a polyethylene film in Fourier transform infrared (FTIR). A
small peak observed at 1,735–1,750 cm−1 is assigned to stretching of the C＝O band of anti-
oxidants that are commonly added to commercial polyethylene during pelletizing process
in petrochemical plants.
The peak at 720 cm−1 is assigned to CH2 rocking and is observed for CH2 sequences
with a length greater than 4. The peaks at 1,465, 2,850, and 2,920 cm−1 are related to
CH2 bending, CH2 symmetric stretch, and CH2 asymmetric stretch, respectively [4].

4.1.2 Low-density polyethylene (LDPE)

Low-density polyethylene (LDPE) is produced by free radical polymerization of ethylene

in high-pressure tubular reactors [5]. This process results in a polymer with very long
chain branches (LCB, Figure 4.2(ii)) that can have sizes comparable to the backbone length.
It should be noted that in the classification of side-chain branches, branches with more
than 100 repeat units are referred to as LCB which can form entanglement themselves [6].
The presence of LCB results in poor molecular order and reduces the melting temperature,
crystallinity, and density of LDPE compared to HDPE. Consequently, LDPE typically shows
 4.1 Polyethylene 51

4000 3500 3000 2500 2000 1500 1000 500

Wave Number (cm–1)

Figure 4.3: Typical FTIR spectrum of polyethylene.

a melting temperature in the range of 100–115 °C and a density of 0.91–0.925 g/cm3. In addi-
tion, LCB in LDPE structure suppress its molecular interdiffusion and results in high seal-
ing temperature and poor seal performance [6]. On the other hand, the presence of LCB
enhances significantly the melt strength and stability of LDPE in film processing, especially
in blown film applications [7]. Therefore, optimizing LCB density in order to achieve a bal-
ance between processing and sealing is essential in LDPE.

4.1.3 Linear low-density polyethylene (LLDPE)

Figure 4.4 shows the molecular structure of linear low-density polyethylene (LLDPE) re-
peat unit. The side-chain groups in LLDPE, which are referred to as short-chain branches
(SCB) in some literature, are produced by random copolymerization of ethylene and

H H H H

C C C C

H H H (CH2)x
m n
Figure 4.4: Molecular structure of LLDPE with ethylene (left) and
CH3 alpha olefin (right) sequences.
52 Chapter 4 Sealant layer materials

another alpha olefin comonomer. Comonomers of 1-butene, 1-hexane, and 1-octene are
the most common alpha olefin comonomers used in polymerization of LLDPE.
The presence of side groups in LLDPE repeat unit results in the appearance of a
small methyl deformation band peak in the range of 1,378–1,383 cm−1 in FTIR spec-
trum of LLDPE. This is very close to the small CH2 wagging peak located at 1,368 cm−1
in the amorphous phase of polyethylene homopolymer. The side groups in LLDPE pre-
vent high level of chain order and reduce its melting temperature and crystallinity
compared with HDPE. Consequently, density (0.91–0.93 g/cm) and melting tempera-
ture of LLDPE (120–125 °C) are lower than HDPE. Figure 4.5 shows a typical dynamic
scanning calorimetry (DSC) heating curve of an LLDPE resin.
Heat Flux
Exo.

25 50 75 100 125
Temperature (°C)

Figure 4.5: DSC heating curve of an LLDPE showing peaks at 109, 119, and 122 °C.

The DSC results show three distinct melting peaks 109, 119, and 122 °C. Although this
result may imply that LLDPE has three types of crystals that melt at different temper-
atures, but previous works used temperature-modulated DSC and showed that the
three peaks are observed due to the overlap of multiple exothermic crystal perfection
phenomena with endothermic crystal melting [5].
The lower crystallinity of LLDPE results in high clarity and toughness and makes
LLDPE a great candidate for many film applications. The presence of side groups in
LLDPE delays molecular diffusion but due to their small sizes, the effect is much less
pronounced compared to that of LCB in LDPE [8]. The effect of side chains and molec-
ular architecture on seal performance is discussed later in detail in Chapter 5. How-
ever, the lack of LCB and low melt strength lead to instabilites in LLDPE blown film
production and it is a common practice to blend 10–20 wt% of LDPE with LLDPE to
enhance their melt strength and processing. The effect of addition of LDPE on thermal
properties of LLDPE was examined by Prasad [9], who showed that the addition of
 4.1 Polyethylene 53

LDPE to Bu-LLDPE and Oct-LLDPE increases crystal perfection at high temperature

but did not have a significant effect on Hex-LLDPE. At the same time, addition of
LDPE can delay seal initiation when LLDPE is the sealant material.

4.1.4 Metallocene polyethylene (mPE)

Metallocene polyethylene (mPE) resins are a family of polyethylene that are produced
using metallocene catalyst family and can offer interesting properties due to the much
higher control on the chain microstructure compared to the conventional Ziegler–Natta
polymerization. This leads to much narrower molecular weight distribution (MWD) in
mPE and allows tailoring properties to achieve high toughness and puncture resistance
and superior heat sealing performance with high hot tack strength. Figure 4.6 shows
schematically the difference between LLDPE produced by metallocene catalysts and
conventional Ziegler–Natta catalysts. As can be seen, chains produced by metallocene
catalysts have almost identical lengths with an even distribution of side groups within
each chain and similar side group density among different chains. However, chains pro-
duced by Ziegler–Natta catalysts have a broad MWD with an uneven side group distri-
bution within each chain and different side group density among different chains.

(i)

(ii)

Figure 4.6: Different molecular structures of LLDPE chains produced by (i) metallocene catalyst
and (ii) Ziegler–Natta catalyst.

Different types of polyethylene can be produced by metallocene polymerization but

the most interesting category of mPE in flexible packaging is that of copolymers of eth-
ylene and alpha olefins or m-LLDPE. Among alpha olefins, 1-hexane and 1-octane are
the most common types of mPE that exist in the market. mPE with different densities
from <0.9 to 0.935 g/cm3 can be found in the market where their melting temperature
54 Chapter 4 Sealant layer materials

increases with density. Despite their interesting properties, mPE resins are more ex-
pensive compared to conventional Ziegler–Natta LLDPE resins. In order to achieve a
balance between properties and costs, mPE resins are used as a thin sealant layer or
are blended with regular LLDPE resins. The effect of blending m-LLDPE with conven-
tional LLDPE is discussed in detail in Chapter 7.

4.1.5 Plastomers

Plastomer is a group of ethylene and alpha olefins copolymers having a unique molec-
ular structure that allows them to have the performance of rubber-like materials
while they can be processed as thermoplastics. The recent advances in catalyst tech-
nology allowed producing LLDPE resins with a combination of LCB and SCB in their
microstructure. The presence of LCB enhances melt strength and blown film process-
ing while SCB leads to lower crystallinity, higher toughness, and more sticky material
and ensures enhanced molecular mobility and interdiffusion. The ratio of LCB/SCB in
plastomer resins dictates their final properties and processing. For example, resins
with low level of LCB have much higher toughness and good sealing properties but
are more difficult for processing. On the other hand, resins with high level of LCB
have good processing but lack good sealing and toughness. A detailed discussion on
the effect of molecular architecture on seal performance is presented in Chapter 5.

4.2 Polypropylene (PP)

Polypropylene (PP) is produced by polymerization of propylene using Ziegler–Natta or

metallocene catalysts in gas phase or slurry reactors [10]. The molecular structure of PP
is shown in Figure 4.7. Similar to polyethylene, PP does not have any functional group
and has a hydrophobic nature. However, the presence of a tertiary carbon in PP struc-
ture reduces its resistance against photo and thermal oxidation compared to PE [11].

H H

C C

H CH3
n Figure 4.7: Molecular structure of polypropylene.

FTIR spectrum of PP (Figure 4.8) is known for its finger-like peaks in 2,800–3,100 cm−1
range.
 4.2 Polypropylene (PP) 55

4000 3500 3000 2500 2000 1500 1000 500

Wave Number (cm–1)

Figure 4.8: FTIR spectrum of polypropylene.

PP can be categorized into three different types based on their tacticity: (i) isotac-
tic (i-PP), (ii) syndiotactic (s-PP), and (iii) atactic PP (a-PP). Figure 4.9 shows schemati-
cally the difference between tacticity of these structures.

CH3 CH3 CH3 CH3 CH3 CH3 CH3

i-PP
n

CH3 CH3 CH3 CH3 CH3 CH3 CH3

s-PP
n

CH3 CH3 CH3 CH3 CH3 CH3 CH3

a-PP
n
Figure 4.9: Different types of polypropylene based on their tacticity.

As in i-PP all methyl groups are located on one side of the polymer chain, a high level
of molecular order and crystallinity can be achieved, which leads to the highest crys-
tallinity and melting temperature compared to s-PP and a-PP. Due to the higher crystal-
linity and mechanical strength, i-PP is the most commonly used type of PP, particularly
in rigid plastic packaging. Industrial grades of i-PP have usually melting temperatures
56 Chapter 4 Sealant layer materials

around 155–160 °C. The high melting temperature of i-PP makes it a great candidate for
applications where the film needs to withstand high temperatures such as retort appli-
cations or microwavable packages. However, high crystallinity of i-PP leads to low clar-
ity of the film. Clarifiers are commonly added to i-PP to improve its clarity. These
additives act as nucleating agent and reduce the size of the spherulites in i-PP leading
to much clearer films. In s-PP, methyl groups are alternatively located on each side of
the chain, resulting in a higher steric hindrance compared to i-PP and therefore lower
crystallinity. s-PP has usually melting point around 130 °C and exhibits poor mechanical
strength. In a-PP structure, methyl groups are randomly located on either side of the
chain which imposes a significant steric hindrance against molecular arrangement.
Consequently, a-PP is an amorphous polymer soluble in a great number of aliphatic
and aromatic hydrocarbons, esters, and other solvents [12]. The level of tacticity in PP is
represented by isotactic index which is determined as the insoluble fraction of PP in
boiling heptane. The commercial grades of PP have an isotactic index between 85% and
95%.
PP films that are commonly used in packaging industry are classified based on
their orientation level as cast PP (cPP), monoaxially oriented PP (MOPP), and biaxially
oriented PP (BOPP) with their level of molecular orientation following the order: cPP <
MOPP < BOPP. In fact, cPP represents PP films that did not undergo any postprocessing
stretching while MOPP and BOPP went through postprocessing stretching in uniaxial
and biaxial directions, respectively. These processes increase considerably the level of
molecular orientation in the films. Previous studies showed that increasing molecular
orientation reduces the seal strength in PP films [13]. In order to achieve both good
strength and sealability, BOPP films usually have three-layer structure of A/B/A, where
the A layer is the copolymer of PP and polyethylene and the B layer is PP homopolymer.
Due to their low orientation potential and melting temperature, the skin layers provide
sealability, while the core homopolymer layer provides strength.

4.3 Ethylene vinyl acetate (EVA)

Ethylene vinyl acetate (EVA) is a random copolymer of ethylene and vinyl acetate (VA)
produced by radical polymerization in tubular or continuous stirred reactors. Figure 4.10
shows the molecular structure of EVA.
The presence of VA groups in EVA disrupts crystallinity of ethylene chains and
results in a less crystalline material. This increases tackiness, toughness, and clarity
while reduces the mechanical strength [14]. In addition, the presence of VA in the
structure allows better adhesion and interaction with polar components and surfaces.
VA monomer can act as transfer agent in the polymerization reaction which leads to
reduced MW of EVA at higher VA contents. EVA is characterized by the amount of VA
used in the copolymer. The most common VA contents in plastic packaging are 9% and
18% but higher VA contents also exist and used in some other applications such as hot
 4.3 Ethylene vinyl acetate (EVA) 57

H H H H

C C C C

H H H O
n m
C O

CH3 Figure 4.10: Molecular structure of EVA.

melt adhesives. The higher VA content in EVA results in larger fingerprint peaks at
wave numbers of 1,020 (C–O band), 1,235 (C–O band), and 1,735 (C＝O band). Figure 4.11
shows the FTIR spectrum of an EVA with 9% VA content. It is worth mentioning that
the peak around 3,400 cm−1 is due to humidity absorption.

4000 3500 3000 2500 2000 1500 1000 500

Wave Number (cm–1)

Figure 4.11: FTIR spectrum of EVA with 9% VA content.

In contrast with polyethylene, the density of EVA is controlled by its VA content and
increases linearly with an increase in the VA content. For example, Henderson [14]
reported the following equation for the variation of density of EVA with VA content:
 
Density g=cm3 = 125 × 10−5 × VA content ð% Þ + 0.915

For example, this equation leads to a density of 0.937 g/cm3 for EVA with 18% VA con-
tent. Increasing VA content also reduces dramatically the stiffness of EVA and results
in transition from thermoplastic behavior at 5% VA content to elastomeric behavior
at 17% VA content [14].
58 Chapter 4 Sealant layer materials

EVA has been used in plastic packaging for two main reasons: its elastic properties
and low sealing temperature. EVA used to be the main option for sealing of heat sensi-
tive materials like cheese and chocolates. Blending of EVA and conventional PE has been
considered as an effective approach to reduce sealing temperature of conventional PE
sealants. An example of the effect of blending EVA with PE on seal properties is pre-
sented in Chapter 7. The invention of mPE, plastomers, acid copolymers, and ionomers
reduced considerably the applications of EVA as a sealant material due to their better
seal properties, less challenging processing, and their competitive cost (especially mPE
and plastomers).

4.4 Acid copolymers

Copolymers of ethylene and methyl acrylic acid (EMA) or ethylene and acrylic acid
(EAA) are the most well-known acid copolymers used in packaging industry. The mo-
lecular structure of these copolymers is shown in Figure 4.12.

H H H R

C C C C

H H H C
n m
HO
O

H H H OH
O

C C C C Figure 4.12: Molecular structure of acid copolymers, R is hydrogen

in ethylene-acrylic acid (EAA) copolymer, while R is CH3 in
H H H R ethylene–methacrylic acid (EMA) copolymer. The red lines show the
n m possible hydrogen bonding between acid moieties.

Copolymerization of ethylene with acid copolymers allows combining water resistance

and chemical resistance of ethylene with adhesion and polarity of acid segments. The
presence of acid comonomers increases density and improves low temperature sealing
and hot tack strength. Figure 4.13 shows the FTIR spectra of EMA (10% MA) and EAA
(6.9%AA).
The peak at 1,705 cm−1 is assigned to the C＝O stretch in dimerized acid and the
peak at 940 cm−1 is related to the O–H bending in the dimer structure. The peak at
940 cm−1 is used commonly to examine relative acid comonomer content in EMA and
EAA copolymers. The presence of acid comonomers allows the formation of hydrogen
bonding between acid moieties (Figure 4.12), which leads to the appearance of a shoul-
der-like peak at 2,650 cm−1. This strong intermolecular interaction allows high melt
 4.5 Ionomers 59

EMA, 10% MA

EAA, 7% AA

3600 3100 2600 2100 1600 1100 600

Figure 4.13: FTIR spectra of acid copolymers: EMA with 10% MA and EAA with 7% AA.

strength and high hot tack strength. It has been shown that increasing acid comono-
mer increases modulus by increasing the glass transition temperature of the amor-
phous phase [15].
Acid copolymers, especially EAA copolymers, are known for their great adhesion
to aluminum foil which makes them a great bonding layer between polyolefin layers
and aluminum foil in extrusion coating processes. But processing of acid copolymers
has its own challenges as it requires corrosion-protected extrusion equipments. Acid
copolymers are tacky materials which makes working with them challenging espe-
cially in blown film extrusion processes. In addition, they need to be purged after
extrusion at shutdown as they can be cross-linked if exposed to heat for long period
of time.

4.5 Ionomers

Ionomers are ion-containing polymers that exhibit interesting properties due to the
presence of the ionic group in their structure. Ionomers can be categorized based on
the nature of the ion group: (i) anionomers (ionomers with anionic group), (ii) catiom-
ers (ionomers with cationic group), and (iii) polyampholytes and zwitterionomers
(ionomers with both anionic and cationic moieties). The majority of ionomers in pack-
aging are anionomers and more specifically anionomers with carboxylate groups that
are partially or completely neutralized with alkali metals or zinc. Figure 4.14 shows
schematically the structure of zinc ionomers based on polyethylene.
60 Chapter 4 Sealant layer materials

H H H R

C C C C

H H H C
n m
–O

O
Zn++
H H H O–
O
C C C C

H H H R
n m Figure 4.14: Molecular structure of zinc ionomer.

As ionomers are composed of a nonpolar (e.g., ethylene or styrene) segment and

a polar (ion) segment, their morphology has been the subject of many studies, and
different models have been proposed for their microstructure. It has been shown that
incorporation of ionic group changes the molecular morphology in different scales
from nano- to microscales [16]. The transition in structures of ionomers below and
above melting temperature of their semicrystalline matrix (e.g., ethylene segments) is
shown schematically in Figure 4.15.

Crystalline Domains

Melting

Crytallization

Figure 4.15: Structural transition in ionomers at melting temperature of their semicrystalline matrix.

By increasing temperature, crystalline domains of the polyethylene phase melt but the
ionic domains remain intact. These ionic domains act as cross-links points and hinder
chain movement which results in increasing melt strength in ionomers. It is worth men-
tioning that some previous studies considered another order–disorder transition within
the ionic domains at temperatures below melting of the semicrystalline matrix [17]
which has been debated by some other researchers [18]. Previous studies showed that
the rheological behavior of ionomers does not obey the Cox–Merz law. This confirms
the presence of two-phase structural model where ionic domains are embedded in a
matrix of hydrocarbons [19]. In FTIR spectra of anionomers with carboxylate group, the
 References 61

peak around 1,560 cm−1 is assigned to carboxylate ions and its intensity increases by
increasing the extent of neutralization [20].
In plastic packaging, ionomers are known for their fat and grease resistance,
their low seal temperature, their superior hot tack, and their seal through properties
[21]. All these features have made ionomers an interesting candidate where high-
quality hermetic sealing is necessary such as in pharmaceutical applications. How-
ever, ionomers are known to be relatively expensive, moisture sensitive, and their
processing is challenging due to their tackiness and temperature sensitivity.

4.6 Polyethylene terephthalate (PET)

The molecular structure of polyethylene terephthalate (PET) is shown in Figure 4.16.

The presence of the aromatic ring in the backbone of PET increases considerably the
chain stiffness and strength of PET. In addition, the stiff backbone of PET allows achiev-
ing high level of molecular orientation upon stretching. The presence of polar groups in
the microstructure of PET provides good interfacial adhesion with inks and good print-
ability. All these properties make PET a promising option for the external abuse layer
that provides mechanical strength and printability. The most common form of PET
used in the abuse layer in flexible packaging is biaxially oriented PET or BOPET.

O O

O C C O
H2 H2
Figure 4.16: Molecular structure of PET.

PET is industrially produced by condensation polymerization of ethylene glycol and

terephthalic acid in the presence of a catalyst [22]. Due to its high melting tempera-
ture, crystalline PET is not used as a sealant layer; however, amorphous PET (A-PET)
is commonly used for lidding of trays made of either cast PET or A-PET. Transparent
PET-based film for lidding applications are two-layer films with a thicker BOPET layer
as an abuse layer and a thinner A-PET layer on the sealing side. The seal initiation
temperature for PET lidding films is commonly 90–100 °C.

References

[1] Woishnis, W. and S. Ebnesajjad, Chemical Resistance of Thermoplastics. 2011, William Andrew.
[2] Jalali Dil, E. and B.D. Favis, Localization of micro and nano- silica particles in a high interfacial tension
poly(lactic acid)/low density polyethylene system. Polymer, 2015. 77: p. 156–166.
62 Chapter 4 Sealant layer materials

[3] Ashizawa, H., J.E. Spruiell, and J.L. White, An investigation of optical clarity and crystalline orientation in
polyethylene tubular film. Polymer Engineering & Science, 1984. 24(13): p. 1035–1042.
[4] Noda, I., et al., Group Frequency Assignments for Major Infrared Bands Observed in Common Synthetic
Polymers, in Physical Properties of Polymers Handbook, J.E. Mark, Editor. 2007, Springer: New York, NY.
p. 395–406.
[5] Peacock, A., Handbook of Polyethylene: Structures: Properties, and Applications. 2000, CRC press.
[6] Najarzadeh, Z. and A. Ajji, Role of molecular architecture in interfacial self-adhesion of polyethylene
films. Journal of Plastic Film & Sheeting, 2017. 33(3): p. 235–261.
[7] Liang, J.-Z., Melt strength and drawability of HDPE, LDPE and HDPE/LDPE blends. Polymer Testing, 2019.
73: p. 433–438.
[8] Bartels, C.R., et al., Self-diffusion in branched polymer melts. Macromolecules, 1986. 19(3): p. 785–793.
[9] Prasad, A., A quantitative analysis of low density polyethylene and linear low density polyethylene blends
by differential scanning calorimetery and fourier transform infrared spectroscopy methods. Polymer
Engineering & Science, 1998. 38(10): p. 1716–1728.
[10] Karian, H., Handbook of Polypropylene and Polypropylene Composites, Revised and Expanded. 2003, CRC
press.
[11] Bertin, D., et al., Polypropylene degradation: Theoretical and experimental investigations. Polymer
Degradation and Stability, 2010. 95(5): p. 782–791.
[12] Karger-Kocsis, J., Amorphous or Atactic Polypropylene, in Polypropylene: An A-Z Reference, J. Karger-
Kocsis, Editor. 1999, Springer Netherlands: Dordrecht. p. 7–12.
[13] Yamada, K., et al., Molecular orientation effect of heat-sealed PP film on peel strength and structure.
Advances in Materials Physics and Chemistry, 2015. 5(11): p. 8.
[14] Henderson, A.M., Ethylene-vinyl acetate (EVA) copolymers: A general review. IEEE Electrical Insulation
Magazine, 1993. 9(1): p. 30–38.
[15] Wakabayashi, K. and R.A. Register, Micromechanical interpretation of the modulus of
ethylene–(meth)acrylic acid copolymers. Polymer, 2005. 46(20): p. 8838–8845.
[16] Grady, B.P., Review and critical analysis of the morphology of random ionomers across many length
scales. Polymer Engineering & Science, 2008. 48(6): p. 1029–1051.
[17] Tadano, K., et al., Order-disorder transition of ionic clusters in ionomers. Macromolecules, 1989. 22(1):
p. 226–233.
[18] Farrell, K.V., Effects of temperature on aggregate local structure in a zinc-neutralized carboxylate
ionomer. Macromolecules, 2000. 33(19): p. 7122–7126.
[19] Sakamoto, K., W.J. MacKnight, and R.S. Porter, Dynamic and steady-shear melt rheology of and
ethylene-methacrylic acid copolymer and its salts. Journal of Polymer Science Part A-2: Polymer Physics,
1970. 8(2): p. 277–287.
[20] MacKnight, W., L. McKenna, and B. Read, Properties of ethylene‐methacrylic acid copolymers and their
sodium salts: Mechanical relaxations. Journal of Applied Physics, 1967. 38(11): p. 4208–4212.
[21] Morris, B.A. and J.M. Scherer, Modeling and experimental analysis of squeeze flow of sealant during hot
bar sealing and methods of preventing squeeze-out. Journal of Plastic Film & Sheeting, 2015. 32(1):
p. 34–55.
[22] Ma, Y., et al., Solid-state polymerization of PET: Influence of nitrogen sweep and high vacuum. Polymer,
2003. 44(15): p. 4085–4096.
Chapter 5
Effect of processing and material properties
on seal performance

Understanding the effects of different processing and material parameters on heat

sealing is essential in controlling heat sealing properties of sealant films. In this chap-
ter, a review of previous works that studied the effects of sealant material character-
istics and heat sealing condition on seal and hot tack strength will be presented. The
main sealing process parameters that affect seal performance are sealing tempera-
ture, dwell time, sealing pressure, and delay time or cooling time.

5.1 Sealing temperature

Sealing temperature is a critical parameter in heat sealing and needs to be adjusted

carefully to ensure achieving the desired seal properties. Flexible packaging experien-
ces a thermal shock once they are sandwiched between two heated jaws during heat
sealing. For instance, if we assume that a film at room temperature is placed between
two heated jaws at 150 °C and reaches jaw temperature after 0.5 s, the film experien-
ces a heating rate of 300 °C/s or 18,000 °C/min. Such high heating rate during heat seal-
ing process and the thin thickness of films make measuring temperature at the
interface between seal sides very challenging. Therefore, in most previous studies, ef-
fects of jaw temperature on the seal performance were investigated instead of the ef-
fect of the interface temperature. Theller [1] examined heat sealing of cast coextruded
low-density polyethylene (LDPE) films and blown coextruded high-density polyethyl-
ene (HDPE)/ethylene vinyl acetate (EVA)-PB films and showed that increasing jaw tem-
perature increased the seal strength (SS). He also found that the highest peelable SS
could be obtained around the melting temperature of the sealant material which is in
agreement with the results of other researches [2]. Tetsuya et al. [3] showed a very
low SS for oriented polypropylene (OPP)/cast polypropylene (CPP) laminate films
sealed below ~110 °C. The maximum SS in this system achieved by increasing temper-
ature to 120 °C but further increase in temperature reduced the SS. Similar results
were reported by other researchers [4]. Morris [5] reported that high SS could only be
achieved at temperatures higher than melting point of sealants. Najarzadeh and Ajji
[6] also studied the effect of temperature on seal properties and concluded that a gen-
eral optimum temperature cannot be defined as other process parameters and mate-
rial characteristics also play a role in SS.
Muller and coworkers [7] observed a rapid increase in the SS by increasing the
temperature from 115 to 125 °C in linear LDPE (LLDPE) sealant films. When they stud-
ied the morphology of the peeled surfaces at different temperatures, they found a

https://doi.org/10.1515/9781501524592-005
64 Chapter 5 Effect of processing and material properties on seal performance

shift in the surface morphology from small, isolated fractured fibrils for the samples
sealed below 115 °C to a membrane-like connected pattern in the samples sealed at
120 and 125 °C. They also found that increasing temperature up to 115 °C, increased
the fibril density which was related to increasing chain diffusion across the interface.
Increasing temperature above 115 °C led to a significant increase in the diffusion
across the interface which increased the number and size of fibrils. Najarzadeh and
Ajji [6] also studied the topography of the peeled surfaces of LLDPE films sealed at
different temperatures using AFM and SEM and found that increasing sealing temper-
ature increased the number of microfibrils or bridges between the surfaces which led
to an increase in SS (Figure 5.1).

300.0 nm 300.0 nm
0.0 nm 0.0 nm
30 um 30 um
30 um 30 um
10 20 10 20
20 10 20 10
30 um 30 um

300.0 nm
Seal Strength

0.0 nm
30 um
30 um
10 20
20 10
30 um

300.0 nm 300.0 nm
0.0 nm 0.0 nm
30 um
30 um
30 um 30 um
10 10 20
20
20 20 10
10
30 um 30 um

Temperature

Figure 5.1: AFM images showing the effect of sealing temperature on the morphology of peeled surfaces
that were sealed at dwell time= 0.5 s and pressure = 0.5 N/mm2 [6].

These results point to the increase in the energy level of chain ends and the free vol-
ume that enhanced the chain end diffusion across the interface. When the tempera-
ture at the interface between seal sides reached the melting temperature of the
sealant material, molecular diffusion across the interface was enhanced considerably.
This increased the number and strength of the links created across the interfaces.
When pulled apart, these links will be stretched into fibrils and finally break. Increas-
ing temperature increases the number and strength of these links which increases the
SS. Finally, the number of links increases so that it covers the majority of the surface
 5.1 Sealing temperature 65

and lock-seal behavior is observed. A similar trend can be seen in the previous studies
on the effects of sealing temperature in which increasing sealing temperature in-
creases the SS followed by reaching a plateau at higher temperatures and finally
decay in SS at very high temperatures [2, 3, 6, 8–14]. Figure 5.2 shows an example of
this behavior with the following important aspects:
– The seal initiation temperature (Tsi or SIT): an onset temperature where the SS
begins to increase rapidly with temperature.
– The plateau initiation temperature (Tpi): the temperature where the SS reaches a
plateau and does not change considerably by further increase in temperature.
– Plateau SS (SSp): the SS in the plateau region.
– The final plateau temperature (Tpf): the temperature in which the SS begins to
decay rapidly, and extensive seal distortion is observed.

Tpi Tpf
2 3
Seal strength

4
SSp

Figure 5.2: Example of seal strength variation with

Tsi sealing temperature. The arrows show important
1 points in the curve. Tsi, seal initiation temperature;
Tpi, seal plateau initiation temperature; SSp, seal
Jaw temperature strength plateau; Tpf, seal strength decay [15, 16].

The definition of SIT depends on determining the SS threshold in which sealing be-
gins. The value of this threshold varies between industries and different values from
100 to 500 g/in can be seen in literature. It should be noted that in some cases SIT is
confused with Tpi. As a common role of thumb for comparing SIT of different materials,
SIT follows the melting temperature of the sealant. For example in the case of polyeth-
ylene, the following order for SIT order is observed: very LDPE (vLDPE), LLDPE, and
HDPE follow their melting temperature: SIT(vLDPE) < SIT(LLDPE) < SIT(HDPE), which
matches with their melting temperatures.
Tpi indicates the temperature in which the seal reached its maximum strength. This
temperature is important in determining sealing temperature where lock seal property
is expected. The SS at plateau (SSP) is important in designing the package where lock
seal behavior is expected. In those applications, this value should be at least equal to
the yield strength of the film to ensure that seal failure does not occur before film de-
formation. At Tpf, seal distortion and sealant squeeze out causes the decay in SS [6].
The sealing window or sealing range is defined as the temperature range between SIT
and Tpf. From industrial viewpoint, a broad sealing window is an important parameter
as it allows changing temperature to achieve optimum performance/cost balance or to
66 Chapter 5 Effect of processing and material properties on seal performance

compensate the variation of processing conditions such as temperature of jaws, hu-

midity, or food contaminations [17].
The effect of sealing temperature on hot tack of sealants has also been studied in
the literature and a general trend has been observed in which increasing temperature
increases hot tack strength up to a maximum strength and further increase in temper-
ature reduces it, as illustrated in Figure 5.3 [6, 18–27]. While increase in hot tack at
temperatures below the maximum is attributed to the increase to the molecular diffu-
sion, the observed decrease at higher temperature has been attributed to the easy
pull out of polymer chains [14].
The different effect of temperature on seal and hot tack can be understood by
considering the fact that seal test is done at room temperature where polymer is solid
and therefore chain pull-out is much difficult. Therefore, failure mechanism in seal
test is due to craze formation followed by stretching of fibrils. On the other hand, hot
tack is done in the molten or hot polymer melt where chain pull-out requires much
lower force. This makes chain pull-out the main failure mechanism in hot tack test.

0.025
LDPE
Normalized Adhesion Strength

Zn-LLDPE
0.020 HDPE
(N.m–1/g.mol–1)

0.015

0.010

0.005

0.000
100 120 140 160
Temperature (°C)

Figure 5.3: Examples of hot tack curved of LDPE, conventional LLDPE, and HDPE normalized to the
molecular weight of the sealant [28].

5.2 Dwell time

During the dwell time, two phenomena should occur to achieve good seal or hot tack
strength [1]: (i) the interface between seal layers should reach the temperature that
allows chain ends to diffuse across the interface and (ii) Brownian motion of the
chain ends across the interface should occur with a length scale large enough to cre-
ate entanglement. Increasing dwell time increases the seal or hot tack strength by in-
creasing both the interface temperature and diffusion depth of the polymer chain
ends [27].
 5.3 Sealing pressure 67

On the other hand, increasing dwell time above certain time does not improve
considerably the SS as the interface temperature approaches the jaw temperature
and the diffusion length becomes comparable to critical length scale required for en-
tanglement [4]. Therefore, an optimum dwell time that ensures strong seal while al-
lowing high production rate needs to be determined for any desired application. It
has been well established in literature that increasing the sealing temperature re-
duces the required dwell time to reach high SS through increasing heating rate and
improved molecular diffusion [3, 4, 6, 15, 16, 29].
Yuan et al. [4] showed that in two layers laminated films of OPP/CPP, increasing
dwell time at temperatures below seal initiation temperature (Tsi = 122 °C) did not
have a considerable effect but above this temperature, the effect of dwell time was
considerable. They also found that the effect of dwell time became negligible (even at
temperatures above Tsi) after reaching plateau SS. Based on the reptation model, Mu-
eller et al. [7] proposed a linear relation between SS and square root of dwell time.
This relation was confirmed later by Qureshi et al. [30] and Najarzadeh and Ajji [6].
Najarzadeh and Ajji [6] plotted a 3D diagram (Figure 5.4) to show the combination
effects of dwell time and jaw temperature on SS and found a strong dependency of SS
on both parameters. They found that there is an optimum region of dwell time and
temperature which results in the highest SS (the orange regions in Figure 5.4).
Dwell time has been shown to have a similar effect on hot tack, due to its effects
on molecular diffusion of chains across the interface [14, 31, 32]. This indicates that
the combination of sealing temperature and dwell time provides a powerful design
tool to control and optimize seal properties. Generally, in flexible packaging industry,
dwell time is of the order of fractions of a second, or in some cases 1–2 s for thick
samples. The optimum dwell time ensures that no excessive time is lost to keep up the
production rate.

5.3 Sealing pressure

Sealing pressure is needed to bring seal layers to close contact and overcome micro-
roughness between surfaces to enhance wetting and eventually molecular diffusion
across the interface [1]. For example, Theller [1] observed that increasing pressure
from 0.27 to 2.75 MPa changed slightly the SS of HDPE films but did not have a consid-
erable effect on the SS of LDPE films. Accordingly, the effects of dwell time and sealing
temperature are much important than sealing pressure. This conclusion has also been
reported by many researchers [4, 6, 9, 15, 16, 33]. It has been mentioned that excessive
pressure may squeeze out the molten fraction of material from the seal area and dis-
tort the seal [6]. A minimum required pressure has also been reported which below
that, no SS could be attained. It should be mentioned that this minimum pressure
limit depends on the material, film thickness, and surface roughness of the films and
a general limit cannot be presented [33].
 68

135
Breakage Zone Seal Strength
(g/25.4mm)
130
0
500
125
1000

m)
1500 3000
120 2000 2500
2500

/25.4m
2000
115 3000 3.0
1500
2.5

Temperature (°C)
1000

ength (g
2.0
s)

110 500
e(

1.5
im

0
ll t

Seal Str
105 130
e

1.0
125
Dw

120
115 0.5
100 Temp 110
0.5 1.0 1.5 2.0 2.5 3.0
eratur
e (°C) 105
100
Dwell time (s)

Figure 5.4: 2D (left) and 3D (right) plot of seal strength versus different temperatures and dwell times [6].
Chapter 5 Effect of processing and material properties on seal performance
 5.4 Effect of material characteristics 69

Najarzadeh and Ajji [6] presented a 3D diagram that shows the relation between
pressure, temperature, and SS of metallocene PE films. The orange region in Figure 5.5
shows the optimum pressure and temperature that resulted in the highest SS. They
found that a minimum pressure of 0.2 MPa at temperatures below 125 °C was needed to
achieve good SS while at higher sealing temperatures, this limit disappeared. They also
found that increasing pressure to a high value of 3 MPa allowed a reduction in the
temperature range in which they could observe the high SS. The observed reduction
in SS at high seal pressure was attributed to the squeeze out flow of the film at high
pressures. Similar effect of sealing pressure has been reported for hot tack [31, 34–36]
with a minimum pressure required to ensure the contact between the films during heat
sealing.
Some defects such as channeling or wrinkles due to contamination and three-
point junctions threaten the sealing functionality. Their effect can also be minimized
by selecting sealants with good caulkability [37–39]. Caulkability is the ability of a
sealant material to flow and fill gaps in the wrinkles and junctions or encapsulate
contaminations in the seal area. This property is especially needed for packaging of
powder grainy or shredded products such as coffee powder or shredded/powdered
cheese. Considering the physics of heat sealing process, caulkability can be seen as
the ability of a sealant to flow under the squeezing sealing pressure during heat seal-
ing process. Therefore, selecting the optimum sealing pressure beside the good tem-
perature and dwell time could help to overcome these issues [40]. It should be noted
that caulkability also depends on material properties that should be considered as
well.

5.4 Effect of material characteristics

5.4.1 Effect of crystallinity

During the heating stage of heat sealing cycle, polymer crystals have to be melted to
allow molecular diffusion across the interface. In addition, after opening the heated
jaws at the end of dwell time, the sealed area begins to cool down due to the heat
transfer to the surrounding environment. Cooling of the sealed area in semicrystalline
polymers can be considered as a nonisothermal crystallization process. In semicrys-
talline polymers, crystallization can occur mainly between melt temperature (Tm) and
glass transition temperature (Tg) [41].
Crystallinity of sealants affects both seal and hot tack properties as increasing
their crystallinity increases their melting temperature and retards chain diffusion.
After sealing, recrystallization of diffused chains during delay time increases seal and
hot tack strength. For example, Stehling and Meka [16] studied sealing behavior of 42
different types of sealants including m-LLDPE, ZN-LLDPE, HDPE, LDPE, VLDPE, PP, and
 70

135
Seal Strength
Breakage Zone (g/25.4mm)
130
0
125 500
1000

m)
1500 3000
120 2000 2500

/25.4m
2500
3000 2000
115 3.5
1500

Temperature (°C)
3.0

ength (g
1000
)

110 2.5
m2

500 2.0
/m

Seal Str
N

0 1.5
e(

105
r

130
1.0
ssu

125
120
Pre

Temp 115 0.5

100 eratu 110
0.5 1.0 1.5 2.0 2.5 3.0 3.5
re (°C
) 105
100
Pressure (N/mm2)

Figure 5.5: 2D countour (left) and 3D plot (right) of seal strength at different sealing pressure and temperature for metallocene PE films. Sealing was
done at dwell time of 0.5 s [6].
Chapter 5 Effect of processing and material properties on seal performance
 5.4 Effect of material characteristics 71

EVA. They estimated the amorphous fraction at any temperature, fa (T), using dynamic
scanning calorimetry (DSC) and the following equation:
 
ΔHS − ΔHT
fa ðT Þ = 1 − (5:1)
ΔHU

where ΔHT, ΔHS, and ΔHU are the cumulative heat of fusion at temperature T, the total
heat of fusion of the sample, and the heat of fusion of 100% crystalline polymer,
which is 293 J/g for polyethylene [42]. They found that for semicrystalline polymers,
amorphous fraction at sealing temperature has a significant effect on SS and con-
cluded that seal initiation temperature occurs when amorphous fraction reaches 77%.
In addition, a broader distribution of fa as a function of temperature results in
broader transition region between seal initiation temperature and seal plateau. Simi-
lar results and conclusions were reported by Najarzadeh and Ajji [6]. Stehling and
Meka [16] concluded that the shape of the seal curve between SIT and seal plateau
depends on distribution of the melting peak.
The addition of high molecular weight (HMW) fractions to increase amorphous
fraction of sealant materials has been examined by some researchers as a method to
improve seal properties of highly crystalline polymers. For example, Miyata et al. [43]
compared the wide-angle X-ray scattering pattern and DSC scans of HDPE blends with
different amounts of HMW HDPE before and after heat sealing. Their results showed
that the addition of less than 10% of HMW HDPE reduced crystallinity and crystalline
orientation and enhanced SS. Some researchers also showed that the addition of low
crystalline ethylene-based copolymers such as EVA or plastomers reduced seal initia-
tion temperature and increased SS by reducing the crystallinity of polyethylene matri-
ces [44–47]. Moreira et al. [27] attempted to establish a relation between Avrami
crystallization rate and seal properties and concluded that good seal properties could
be obtained when the Avrami crystallization rate at the sealing temperature was
greater than 0.2. Nicastro et al. [48] studied the crystallinity of PP during heat sealing
and its effect on SS. By comparing the crystallinity of films before and after heat seal-
ing, they found that crystallinity of PP films increased from 38% for the film before
heat sealing to 50–56% after cooling of the sealed area. By comparing SS of film sam-
ples with different crystallinity, they claimed that they found a linear relation be-
tween SS and crystallinity of the film, although the linear behavior is not clear from
their results.
The observed different effect of crystallinity in the previous studies can be related
to the complex effect of crystallinity on the seal properties of polymer films. Low crys-
tallinity level enhances melting and diffusion during sealing while high crystallinity
can provide higher SS after cooling of the seal.
72 Chapter 5 Effect of processing and material properties on seal performance

5.4.2 Effect of molecular architecture

Previous studies showed that increasing molecular weight (MW) of the sealant ma-
terial increased the plateau SS, but also increased the seal initiation temperature
(Tsi) [7, 14, 16, 24, 44]. Najarzadeh [14] compared seal properties of three metallocene
LLDPE (m-LLDPE) with different MWs, narrow molecular weight distribution (MWD),
and almost identical branch densities. She found that increasing MW increased both
hot tack strength and seal initiation temperature (Figure 5.6, left). She also reported a
linear relation between the maximum hot tack strength and MW (Figure 5.6, right).
They observed that the effect of MW on seal properties can be attributed to higher en-
tanglements of polymer chains by increasing their MW [49].

7000 7000
mSC3

Adhesion Strength (N.m–1)

Adhesion Strength (N.m–1)

6000 mSC4 6000

mSC5
5000
5000
4000
4000
3000
3000
2000
mSC5
1000 2000 mSC4
mSC3
0 1000
90 100 110 120 130 140 70 80 90 100 110 120 130
Temperature (°C) Mw (kg.mol–1)

Figure 5.6: (Left) The effect of molecular weight on hot tack or adhesion strength of metallocene short
chain branched linear low-density polyethylene. (Right) Linear relationship between maximum hot tack
strength and MW. MW of mSC3, mSC4, and mSC5 are 123, 96, and 73 kg/mol, respectively [14].

5.4.3 Chain branching

There are two types of chain branching: long chain branches (LCB) and short chain
branches (SCB). If MW of branches is greater than critical entanglement MW (Me)
(which is for example around 2,800 g/mol for PE or 100 c–c bond length [41]), the
branch is considered as an LCB [6]. Branches with lower MW than this critical value
are considered as SCB. Najarzadeh and Ajji [14, 46] studied the effect of branching on
hot tack of a conventional polyethylene with broad MWD and two metallocene long-
chain branched ethylene α-olefin copolymers with narrow MWD.
Table 5.1 summarizes the molecular characteristics of the materials studied in
their work. Their hot tack results are also shown in Figure 5.7.
 5.4 Effect of material characteristics 73

Table 5.1: Molecular characteristics of branched PEs studied by Najarzadeh and Ajji [28].

Type Code Mw (kg/mol) MWD LCB density SCB density

(/ C atoms) (/ C atoms)

Conventional LDPE LDPE  . . –

Metallocene LLDPE mLC  . . .
Metallocene LLDPE mLC  . . .

0.05 0.07

Normalized Adhesion Strength

Normalized Adhesion Strength

LDPE mLc2
mLC2 0.06 mLc1
0.04 mLC1 mLc3

(N.m–1/g.mol–1)
(N.m–1/g.mol–1)

0.05
0.03 0.04

0.02 0.03
0.02
0.01
0.01
0.00 0.00
100 120 140 160 100 120 140 160 180
Temperature (°C) Temperature (°C)

Figure 5.7: Left: Adhesion strength or hot tack normalized by Mw versus seal temperature for a
conventional LDPE and two metallocene LLDPE. Right: Comparing normalized adhesion strength of LCB
metallocene LLDPEs with SCB metallocene LLDPEs (mLC3 had an Mw of 123 kg/mol and SCB density of 2.5
(1/10,000 C atom)) [14].

As shown in Figure 5.7 (left), increasing the density of LCBs from 0.19 to 0.3 (per
104 C atoms) reduced significantly hot tack strength. Further increase in LCB density
to 5.2 (in conventional LDPE) dramatically reduced hot tack properties. These results
indicate that the presence of LCB increases seal initiation temperature and reduces sig-
nificantly hot tack strength. Similar effects of LCB on hot tack were reported by Mor-
eira et al. [27] for metallocene polyethylene. The effect of LCB on seal and hot tack
strength can be attributed to much difficult chain diffusion in the presence of LCB due
to the increased entanglement density with the surrounding chains [50]. As shown in
Table 5.1, the SCB branching densities of mLC1 and mLC2 are different; therefore, Na-
jarzadeh and Ajji [28] also compared their hot tack results with the hot tack results of
a short-chain branched polyethylene and their results are presented in Figure 5.7
(right). As the SCB densities of mLC3 and mLC1 are almost identical, comparing the re-
sults of these two samples can clearly show that LCB retarded the diffusion due to an
increased hindrance of LCB on molecular motion.
The observed differences between seal performance of metallocene PE and conven-
tional PE have motivated some researchers to investigate the origin of these differences.
Previous researchers reported surface segregation in conventional polyethylene films
in which an amorphous layer composed of highly branched and low MW chains exist
at the surface [30, 51–54]. The observed segregation at the surface is attributed to the
74 Chapter 5 Effect of processing and material properties on seal performance

entropic gain due to the presence of low MW chains at the surface. Moreover, the pres-
ence of highly branched copolymers increases significantly the chain end density at the
surface which reduces the surface energy by increasing surface entropy [30]. During
heat sealing of conventional PE films, the low MW fraction in the segregated layer can
diffuse rapidly but they cannot provide SS due to the lack of entanglement formation.
The highly branched fraction of the segregated layer requires long dwell times to dif-
fuse. Both phenomena believed to cause the poor seal properties observed for conven-
tional PE films. On the other hand, the much narrower MW in metallocene PE leads to
the formation of much uniform chain size and branching distribution through the film.
These results clearly highlight the importance of high degree of control of MW and
branching density distribution in achieving high seal properties.

5.4.4 Monomer sequence

In addition to the effect of branching and MW on seal performance, few works studied
the effect of monomer sequences in ethylene alpha olefin copolymers. Moreira et al.
[27] tried to find a relation between ethylene sequence in LLDPE and seal properties by
defining a new parameter which they called the welding power. They ran hot tack tests
at dwell times between 0.2 and 2 s and then plotted force/25 mm as a function of the
dwell time. The welding power was then defined as the initial slope of this curve at
dwell times between 0.2 and 0.5 s. They reported that increasing the ethylene dispersity
(which means shorter ethylene sequences in LLDPE chains) decreased the seal initiation
temperature by reducing the melting temperature.

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[22] Philippe Mesnil, et al., Seal through contamination performance of metallocene plastomers. In TAPPI
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[26] Shekhar, A., A model for hot tack behavior in Ethylene Acid co-polymer films. Tappi, 1994. 77(1):
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[27] Moreira, A.C.F., P.C. Dartora, and F. Paulo dos Santos, Polyethylenes in blown films: Effect of molecular
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Sheeting, 1989. 5: p. 66–93.
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[44] Morris, B.A., Predicting the performance of ionomer films in heat-seal processes. Paper, Film and Foil
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[45] Poisson, C., et al., Optimization of PE/binder/PA extrusion blow-molded films. II. Adhesion properties
improvement using binder/EVA blends. Journal of Applied Polymer Science, 2006. 101(1): p. 118–127.
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[47] Chen, Y., et al., Melting and crystallization behavior of partially miscible high density polyethylene/
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[48] L. C. Nicastro, et al., Change in crystallinity during heat sealing of cast polypropylene film. Plastic
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[51] Qureshi, N.Z., et al., Self-adhesion of polyethylene in the Melt. 2. Comparison of heterogeneous and
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[52] David T. Wu and G.H. Fredrickson, Effect of architecture in the surface segregation of polymer blends.
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[53] Schuman, T., et al., Solid state structure and melting behavior of interdiffused polyethylenes in
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[54] Schuman, T., et al., Interdiffusion of linear and branched polyethylene in microlayers studied via melting
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Chapter 6
Modeling of heat sealing process

Optimization of heat sealing process parameters to obtain a desired seal strength at

shorter dwell times and lower jaw temperatures is an approach for increasing produc-
tion rate and reducing final product cost. Optimization of heat sealing lines in packag-
ing industry is commonly done using experimental trial and error which requires
considerable amount of time, material, and energy. As a result, heat sealing machines
are usually run at much higher temperatures than melting temperatures of sealant
layers to ensure sealing at short dwell times. In order to show the importance of optimi-
zation in an industrial heat sealing process, a heat sealing machine with line speed of
100 packages per minute and dwell time of 0.4 s can seal more than 52 million packages
per year. The production capacity of this line can be increased to more than 63 million
packages by only reducing 0.1 s of the dwell time. This will also increase the profit and
reduce the final cost and result in a more competitive final price for the product. It
should be noted that reducing the dwell time reduces the power consumption of the
heaters used in the jaws as well.
Considering the mentioned drawbacks and limitations of experimental optimiza-
tion technique of the heat sealing process, optimization based on mathematical
modeling and simulation software has been introduced as an promising strategy to
reduce optimization time and cost [1, 2]. A comprehensive model of heat sealing pro-
cess should consider (i) heat transfer from the jaws toward the interface between two
seal sides, (ii) molecular interdiffusion at the interface, (iii) squeeze-out flow, (iv) crys-
tallization after sealing, and (v) estimation of seal strength development. Due to the
complexity of presenting a model with all components, a comprehensive predictive
heat sealing model is lacking in the literature. As shown in Chapter 5, interface tem-
perature has a critical role in determining the final seal performance. Therefore, first,
previous studies on modeling or simulation of the interface temperature in the heat
sealing process will be reviewed in this chapter. It should be noted that theories of
molecular interdiffusion and crystallization from the melt were thoroughly discussed
in Chapter 2 and, therefore, will not be reviewed here. Previous studies attempted to
model the squeeze-out flow will also be reviewed later in this chapter. Finally, differ-
ent mathematical models proposed for estimation of seal strength development dur-
ing heat sealing will be reviewed at the end of this chapter.

6.1 Modeling of the interface temperature

Modeling of the interface temperature using material characteristics and processing

condition is an interesting approach to predict the interface temperature in a heat
sealing process. Figure 6.1 shows the configuration of a multilayer film between

https://doi.org/10.1515/9781501524592-006
78 Chapter 6 Modeling of heat sealing process

heated jaws in a heat sealing process. In most cases, heated jaws are at the same tem-
perature (symmetric heating) and heat transfer is from the heated jaws toward the
interface. In some cases, only one jaw is heated (asymmetric heating) and the heat
transfer in these cases is from the heated jaw toward the cold jaw.
Kanani Aghkand et al. [3] measured interface temperature variations in different
directions in the sealed area. Their results are shown in Figure 6.2. They found that only
the temperature gradient in the thickness direction is considerable. Therefore, the heat
sealing process can be considered as a one-dimensional heat transfer problem in the
thickness direction.

Jaw

Heat & Pressure

When Jaws and Film come together
PA Layer
Tie layer Jaw
Sealant Layer

Sealant Layer
PA Layer
Tie layer Tie Layer
PA Layer
Sealant Layer
Heat & Pressure
Jaw

a b c

Figure 6.1: (a) Geometry of a multilayer film in contact with a heated jaw in a heat sealing process and
(b) microstructure of the contact area between jaw and the outermost layer of the film [3].

L
L W L
Seal Area
Ar eal

Seal Area 1 Seal Area

S
ea

H H 2
W

1 2 3 H 1 2 3 W
L

H 3
a b c d

120 120 120

e f g
100 100 100
Temperature (°C)
Temperature (°C)

Temperature (°C)

80 80 80 1
1
1 2
2 60
60 60 2 3
3 3
40 40 40

20 20 20

0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Time (s) Time (s) Time (s)

Figure 6.2: Variations of temperature in different directions in the sealed area: (a) seal area dimensions;
(b) location of thermocouples in longitudinal direction; (c) width direction; and (d) thickness direction; (e),
(f), and (g) show the recorded temperature profiles for thermocouples in (b), (c), and (d), respectively [3].
 6.1 Modeling of the interface temperature 79

By considering constant thermal conductivity (k), density (ρ), and specific heat
(Cp), one-dimensional transient heat transfer equation can be written as

dT d2 T
ρCp = −k 2 −Q (6:1)
dt dx
where T, t, x, and Q are temperature, time, coordinate in thickness direction, and the
heat absorbed by melting of polymer(s). Figure 6.3 shows schematically the solution
of equation (6.1) in two cases of symmetric heating and asymmetric heating.

(a) (b)
Tjaw Tjaw
t

t
Troom Troom

X = h/2 X=0 X = –h/2 X = h/2 X=0 X = –h/2

Figure 6.3: Schematics of temperature profile (gray lines) within two single-layer films with thickness of
h/2 in a heat sealing process: (a) both jaws are heated (symmetric heating) and (b) only one jaw is heated
(asymmetric heating) and the other jaw is assumed as an insulator.

Based on equation (6.1), heat absorbed during melting of sealant or other layers shifts
the temperature profiles shown in Figure 6.3 toward lower temperatures and results
in longer time required for the interface temperature to reach the jaw temperature.
In order to model heat transfer in a heat sealing process, heat transfer at contact sur-
face between two seal sides and heat transfer within the bulk of the films need to be
discussed.

6.1.1 Heat transfer in contact areas

Heat transfer between surfaces at contact points has been the subject of many stud-
ies [4–8]. The main surface contact areas in a heat sealing process are (i) the contact
between jaws and the films and (ii) the contact between two sides of the seal before
their melting. The second contact area will be important only when asymmetric heating
is applied, and in the case of symmetric heating, the surface contact between sides of
the seal does not play a considerable role on heat transfer. This is due to the fact that in
symmetric heating, heat transfer occurs from both jaws toward the interface between
80 Chapter 6 Modeling of heat sealing process

films and therefore the interface between two film is located at the symmetry boundary
condition line and does not affect the heat transfer. As symmetric heating is used in
most heat sealing processes especially in flexible packaging, the main focus in this part
of the chapter is dedicated to the heat transfer from jaw to the film. It should be noted
that the same concept can be used to model polymer/polymer contact between two
sides of the seal in asymmetric heating sealing. Meka and Stehling [9] considered heat
convection as the heat transfer mechanism from the heated jaws to the film:
 
Q = h Tjaw − Tfilm (6:2)

where Q and h are the heat transferred from the jaw and the heat transfer coefficient
(h), respectively. The authors used h as a fitting parameter to fit their model on exper-
imental data of interface temperature. Their results showed that changing the heat
transfer coefficient significantly affected simulation predictions. They found the best
agreement between experimental and simulation results by using a heat transfer co-
efficient of 3,910 W/m2 K. Mihindukulasuriya and Lim [10] used COMSOL and exam-
ined asymmetric heat sealing of two LLDPE films. They considered a heat transfer
coefficient between coated jaw and the film and between two sides of the film. Similar
to Meka and Stehling [9], they determined the heat transfer coefficients by fitting
their model on the experimental results. The main disadvantage of finding heat trans-
fer coefficients by fitting the model on experimental results is the fact that the ob-
tained model cannot be used as a predictive model for other cases. In addition, using
this approach may mask other phenomena occurring in the film such as variation of
material properties and introduces error in the model results.
As heat sealing is usually done below melting temperature of the abuse layer, this
layer remains in solid state during the heat sealing process. Figure 6.1(b) shows a mi-
croscale schematic of the contact area between the surface of the jaw and the abuse
layer. The presence of microroughness on the film surface and the jaw surface pre-
vents a complete contact between two surfaces. The presence of air pockets trapped
between surfaces results in heat transfer through two simultaneous mechanisms: (i)
heat conduction in the direct contact points and (ii) heat transfer through trapped air
pockets. The resistance against heat transfer due to the presence of surface roughness
is known as thermal contact resistance (TCR) and is considered in heat transfer mod-
els using an overall heat transfer coefficient (h). Heat transfer at the contact of two
surfaces has been extensively studied in thermal contact theory. Based on this theory,
the overall heat transfer coefficient (h) is defined as the sum of the gap conductance
(hg) and the heat transfer coefficient between contact surfaces (hc). It should be noted
that hg and hc indicate the contributions of heat transfer through trapped air and the
contribution of heat transfer in the direct contact points, respectively. Gap conduc-
tance is defined as [6, 8]

hg = kg =δ (6:3)
 6.1 Modeling of the interface temperature 81

where kg is the gas conductivity and δ is the effective gap thickness which is related
to the surface roughness, microhardness, and contact pressure. Different models for
prediction of the effective gap thickness were reviewed by Song et al. [11].
Existing models for estimation of hc can be categorized into elastic, plastic, and
elastoplastic models based on the type of deformation of surface asperities [4–7, 12].
When the applied contact pressure by the jaws is greater than the microhardness of
the softer surface, asperities on the softer surface undergo a plastic deformation. On
the other hand, when the contact pressure is lower than the surface microhardness,
only an elastic deformation occurs in surface asperities. Elastoplastic models consider
a combination of the plastic and elastic deformations for surface asperities. Determin-
ing type of the deformation of surface asperities is important in estimation of hc and,
consequently, TCR as it directly affects the direct contact area between surfaces.
As heat sealing process is commonly done at temperatures above the glass transi-
tion temperature (Tg) of the commonly used abuse layers (PET or PA), Kanani Agh-
kand et al. [3, 13] recommended to use plastic Cooper−Mikic−Yovanovich (CMY) model
in simulation of heat sealing process. CMY model uses the following equation for pre-
diction of hc:


masp P 0.95
hc = 1.25Kcontact (6:4)
σ asp Hc

where P, Hc, masp, and σasp are the contact pressure, microhardness of the abuse layer
surface, surface roughness (σasp), and asperity average slope (masp). In addition, the
thermal conductivity between two contact surfaces (Kcontact) is defined as
2K1 K2
Kcontact = (6:5)
K1 + K2

where K1 and K2 are conductivities of the two surfaces. Kanani Aghkand et al. [3, 13]
used COMSOL multiphysics software to model symmetric heat sealing process of a PA/
tie/LLDPE film sample between two stainless steel jaws. They estimated TCR by CMY
model using the measured surface microhardness, surface roughness, and thermal
conductivity of the abuse layer. Figure 6.4 compares their simulation results and ex-
perimental data with and without TCR boundary condition.
The simulation results without TCR boundary condition are much different from
the experimental result which emphasizes on the important role of considering TCR
boundary condition in prediction of the interface temperature at early stages of the
process (short dwell times). As most industrial heat sealing machines work at short
dwell times (0.3–0.5 s), these results indicate the critical role of considering TCR in the
simulation of heat sealing.
82 Chapter 6 Modeling of heat sealing process

120

100
Interface Temperature (°C)

80 Experimental data
Simulation without TCR
60 Simulation with TCR

40

20

0.0 0.2 0.4 0.6 0.8 1.0

Dwell Time(s)

Figure 6.4: Comparing experimental data for the interface temperature and the simulation results with
and without TCR boundary condition (experimental data from Kanani Aghkand et al. [3]).

6.1.2 Heat transfer within the film

Heat transfer within film structure can be described by the Fourier’s law of heat
conduction:

q = −kT (6:6)

where q is the heat flux, k is the thermal conductivity, and T is the temperature gradi-
ent. Meka and Stehling [9] modeled heat transfer in a single-layer sealant using finite
element method (FEM) and compared the model predictions with experimental meas-
urements of the interface temperature. They assumed isotropic and constant thermal
conductivity, constant specific heat, and variable density in their model. In order to
consider heat absorbed during melting of polymers, they also considered heat of fu-
sion in some samples. Based on the comparison of their model predictions and experi-
mental data, they found that their model predictions were satisfactory below melting
temperature of the sealant layer. However, at temperatures above melting tempera-
ture of the sealant, model predictions were always lower than the measured interface
temperatures. The authors attributed these results to the thinning of the sealant layer
under sealing pressure at temperatures above sealant melting temperature. Mihindu-
kulasuriya and Lim [10] used COMSOL multiphysics software to model heat transfer
in heat sealing of two single-layer LLDPE films. During heat sealing, only the upper
jaw was heated and a silicon rubber jaw was used for the bottom side as an insulator.
They also applied Kapton® tape to the upper jaw to avoid sticking of the film to the
jaw. Similar to Meka and Stehling [9], they did not consider variations of density, spe-
cific heat, and thermal conductivity with temperature.
 6.1 Modeling of the interface temperature 83

As temperature of polymer film changes significantly during the heat sealing pro-
cess [14], considering temperature dependency of the materials property is very impor-
tant to achieve a reliable model. Kanani Aghkand et al. [3] used COMSOL multiphysics
to model the heat sealing of film samples with PA/PE-g-MA/mLLDPE structure. They
considered dependency of material properties by measuring temperature variations of
density (ρ), specific heat (Cp), and thermal conductivity (k). Their results are shown in
Figures 6.5–6.7.

1.05 1.05
1.00 mLLDPE 1.00
Density (g/cm3)

Density (g/cm3)
HDPE
0.95 0.95
0.90 0.90
0.85 0.85
0.80 0.80
0.75 0.75
40 60 80 100 120 140 160 40 60 80 100 120 140 160
Temperature (°C) Temperature (°C)
1.05 1.05
1.00 PE-g-MA 1.00
Density (g/cm3)

Density (g/cm3)

0.95 0.95
0.90 PA
0.90
0.85 0.85
0.80 0.80
0.75 0.75
40 60 80 100 120 140 160 40 60 80 100 120 140 160
Temperature (°C) Temperature (°C)

Figure 6.5: Variations of density of typical mLLDPE, HDPE, PE-g-MA, and PA.

As shown in Figure 6.5, density of polyethylene-based sealant materials and tie (PE-g-
MA) decreased considerably after melting. This is attributed to the melting of ordered
crystalline regions which increases free volume and reduces density. On the other
hand, density variation of PA (the abuse layer) was within the range of experimental
error and can be considered as constant.
Figure 6.6 shows that increasing temperature increased thermal conductivity of
mLLDPE and PE-g-MA but reduced thermal conductivity of HDPE. Variations of thermal
conductivity by increasing temperature can be explained by considering two opposing
involved mechanisms [15–17]: (i) increasing the free volume by increasing temperature
which reduces thermal conductivity; (ii) increasing segmental mobility which increases
thermal conductivity. In highly crystalline HDPE, free volume increases significantly by
84 Chapter 6 Modeling of heat sealing process

0.32

Thermal Conductivity (W/(m.K))

Thermal Conductivity (W/(m.K))
0.32 HDPE
mLLDPE 0.28
0.28
0.24
0.24
0.20 0.20

0.16 0.16

0.12 0.12

0.08 0.08
20 40 60 80 100 120 140 160 20 40 60 80 100 120 140 160
Temperature (ºC) Temperature (ºC)
0.32

Thermal Conductivity (W/(m.K))

0.32
Thermal Conductivity (W/(m.K))

PE-g-MA PA
0.28 0.28

0.24 0.24

0.20 0.20

0.16 0.16

0.12 0.12

0.08 0.08
20 40 60 80 100 120 140 160 20 40 60 80 100 120 140 160
Temperature (ºC) Temperature (ºC)

Figure 6.6: Variations of thermal conductivity of mLLDPE, HDPE, PE-g-MA, and PA by temperature.

25 25

20 mLLDPE
20 PA
HDPE
Cp (J/(g.°C))

Cp (J/(g.°C))

15 PE-g-MA
15
10
10
5
5
0
0
30 60 90 120 150 20 40 60 80 100 120 140 160
Temperature (°C) Temperature (°C)

Figure 6.7: Temperature-modulated DSC (TMDSC) results showing the variations of specific heat of
mLLDPE, HDPE, PE-g-MA, and PA.

melting crystals, and as a result, the first mechanism becomes dominant and re-
duces the thermal conductivity with temperature. On the other hand, in lower crys-
tallinity mLLDPE and PE-g-MA, the change in the segmental mobility is dominant
and, therefore, thermal conductivity of these materials increases by increasing
temperature.
 6.2 Modeling of squeeze-out flow 85

Specific heat measured by temperature-modulated DSC (TMDSC), Figure 6.7 shows

a peak with a maximum at melting temperature. It should be noted that as DSC deter-
mines Cp based on the difference between the heat applied to the sample and the refer-
ence pans [18, 19], the change in Cp in the phase transition region indicates the heat
absorbed by the material due to the phase transition. However, Kanani Aghkand et al.
[3] showed that using the obtained values of Cp from TMDSC in the phase transition
region allows considering the heat absorbed by the material during phase transition
and, consequently, the difference between melting behavior of materials. This can be
clearly seen in Figure 6.8 by comparing interface temperature of HDPE film at different
jaw temperatures below and above HDPE melting temperature.

180
160
Interface Temperature (ºC)

140
120
100
Ex. 160ºC
80 Sim. 160ºC
60 Ex. 140ºC
Sim. 140ºC
40 Ex. 105ºC
20 Sim. 105ºC
0.0 0.5 1.0 1.5 2.0
Dwell Time (s)

Figure 6.8: Comparison of experimental (Ex.) and simulation (Sim.) results for the interface temperature
in heat sealing of HDPE at different jaw temperatures. Melting temperature of HDPE was 132 °C [3].

It can be seen that melting of HDPE causes a delay in heat transfer and results in lon-
ger times required for the interface temperature to reach jaw temperature. In the
case of variation of Cp of PA with temperature, as the heat sealing is done at much
lower temperature than its melting temperature, only a smooth linear increase in Cp
of PA can be seen in the studied temperature range.

6.2 Modeling of squeeze-out flow

Channeling in the seal area is a common defect which can be due to nonoptimized sealing
conditions such as temperature, pressure, or dwell time [20–22]. Channeling can occur in
the wrinkled area, three-point junctions, or in the presence of contaminations in the seal
area. Selecting sealants with good caulkability is a promising approach in eliminating
channeling in wrinkles, junctions, or in the presence of contaminations [20, 22]. Caulkabil-
ity is defined as the ability of a sealant to flow under the sealing pressure [22]. This phe-
nomenon is also known as the squeeze-out flow or in short, SOF [21–23]. Caulkability is a
86 Chapter 6 Modeling of heat sealing process

necessary characteristic especially in the packaging of powders, grainy or shredded prod-

ucts such as coffee powder or shredded cheese that have a high chance of seal area con-
tamination due to product residues [24, 25]. Despite the significant importance of SOF in
heat sealing, few works have been done on the effects of sealant material properties and
sealing condition on SOF in heat sealing process. Ward and Li [20] examined SOF in a
wide range of different sealant materials but could not find a relation between SOF and
zero-shear viscosity of sealant materials. Some previous works have also examined caulk-
ability by attempting to correlate it to seal strength [24]; however, as the seal strength is
affected by many material properties and sealing conditions, this approach cannot provide
a reliable tool in examining the caulkability of sealants.
The high cost of industrial trials and the importance of SOF indicate the significant
importance of modeling SOF during heat sealing. Squeeze flow of liquids between solid
surfaces has been studied extensively due to its wide range of applications [21, 26–37].
Analytical models have been presented to estimate SOF in different geometries such as
parallel rectangular plates [38], circular disks [34, 39], or even nonparallel surfaces [40]
for both Newtonian and non-Newtonian fluids [41–43]. The previous works on modeling
of SOF in the literature can be categorized into two main groups: (i) constant volume
squeeze mode [31, 39] and (ii) constant contact area squeeze mode [34, 38]. In the first
group, the liquid does not fill the gap between plates and the contact area between
solid surfaces and the liquid increases during squeezing, but liquid is not squeezed out.
This type of SOF is commonly seen in compression molding of polymer melts. In the
constant contact area mode, the liquid always fills completely the gap between plates
and squeezing of the plates leads to squeeze out of the liquid. SOF in heat sealing is an
example of constant contact area mode. Most of the previous studies on squeeze flow in
constant contact area category focused on SOF between two parallel circular disks in
cylindrical coordination with very thick polymeric layer between them. Therefore,
those studies cannot be directly applied to the squeeze flow within sealant layers in
heat sealing. In order to determine the squeeze-out flow, authors commonly model two
parallel plates filled with polymer and separated with an initial distance. The top plate
approaches the bottom one under a pressure equal to the sealing pressure. The models
predict the decrease in the gap between plates to determine the materials pulled out of
the gap. Shuler and Advani [44] modeled transverse squeeze-out flow of a polymeric
liquid between two rectangular plates with length of 2 L and width of W and found that
for a Newtonian fluid with viscosity of η, under an applied force (F), the rate of gap
thickness reduction (h)_ can be estimated as

L3 dh
F = −8 ηW (6:7)
h3 dt
 6.2 Modeling of squeeze-out flow 87

After integration, variation of the gap with time can be determined as

2 −1=2
h Ph0
= t + 1 (6:8)
h0 2L2

Equation (6.8) predicts that the squeeze-out flow depends on time with a power of −1/
2. Morris and Scherer [45, 46] used the same equation for modeling squeeze-out flow
but found considerable error in determining initial and final thickness (h and h0) of
the films. They proposed examining the change in the thickness at the edge of the seal
bar to study squeeze-out flow. They reported that the squeezed-out region had a
shape close to a trapezoid similar to the one schematically shown in Figure 6.9.

Figure 6.9: Schematic showing the method used by Morris and

2h

A B Scherer [45] for the estimation of squeeze-out flow in heat sealing

of two films with thickness of h. B is the squeeze-out area (which
includes A) and A shows a portion of the film cross-section
overlapped with the squeeze-out area (or B).

They proposed that the amount of squeeze out can be determined using the following
equation:

2ðB − AÞ
% Squeeze out = × 100 (6:9)
2h0 W

Finally, they compared experimental data and model predictions and found a poor
agreement between model predictions and experimental results. The observed dis-
crepancy between experimental and their model predictions was attributed to the
simplifications assumptions such as constant temperature (no heat transfer was con-
sidered in their model).
Grewell and Benator [47] proposed that squeeze-out flow can be modeled by con-
sidering melting of surface asperities at the interface of two films. They assumed sur-
face asperities as many small, identical cylinders on the surface of two parallel plates
and considered a Newtonian fluid and constant material properties. Finally they ob-
tained the following equation for the gap reduction by dwell time:

−1=4
h 16Fh3
= t − 1 (6:10)
h0 3αr04

where h0, h, F, r0, and α are initial gap, gap opening at time t, the force applied by the
upper plate, the radius of cylinders (surface asperities), and the thermal diffusivity,
respectively. Equation (6.10) predicts that gap opening variation should be propor-
tional to t−¼. However, this equation does not consider the effect of viscosity of the
88 Chapter 6 Modeling of heat sealing process

liquid. The authors did not present experimental results to examine their model
predictions.
Levy et al. [48] examined the squeeze out of a molten thermoplastic between two
rectangular plates using COMSOL multiphysics and compared their simulation results
with experimental measurements. They used lubricating assumption and achieved
the following set of analytical equations to predict the velocity fields:


d du dP
η =− (6:11)
dy dy dx
ð
h=2

u dy = x.Vup (6:12)
− h=2

ð
L=2

P dx = F=W (6:13)
− L=2

where u is the horizontal velocity that varies in the thickness (y) and horizontal (x)
directions, P is the applied pressure to the top plate, Vup is the upper plate velocity, W
is the depth of the sample in the third direction, and F is the applied force. Their sim-
ulation results are shown in Figure 6.10. It can be seen that the experimental values
are always lower than the simulation and analytical model predictions. This can be
attributed to the squeeze-out flow of the material in the third direction that was not
considered in their 2D model. Their result show a dependency of t−0.2, t−0.4, and t−0.7 for
applied forces of 445, 1,334, and 2,222.4 N. Using the surface area of the sample (50 ×
50 mm), the applied pressures can be calculated as 178, 536, and 889.6 kPa, respectively.
These experimental results show that the time dependency of the thickness variation
increases by increasing the applied force (pressure). The effect of pressure on time de-
pendency of squeeze out has not been considered in the previous models in the
literature.
Kanani Aghkand and Ajji [49] examined the effect of sealant material thickness,
sealing condition, and sealant viscosity on SOF in film with a structure similar to the
one shown in Figure 6.11.
They used a new image analysis approach to quantify SOF in which the film thick-
ness was traced back into the sealed area until the traced lines reach each other in
the center (Figure 6.12). These lines reach each other in the center at a point where
sealed area should begin in the absence of SOF.
In the absence of SOF, the traced lines reach each other at the point where the
sealed area begins (Figure 6.12(a1)). When the samples exhibit SOF (b1 and c1 in Figure
6.12), the traced lines reach each other inside of the sealed area. To calculate the
amount of SOF, the area of the highlighted regions between traced lines in Figure 6.12
(b, c) was multiplied by the width of the sealed strips. As SEM measurements were
done at room temperatures, the authors multiplied the calculated volume from image
 6.2 Modeling of squeeze-out flow 89

6.6024×10–5
×10–6

60

50

40

30

20

10

0
0
× 10–3 F = 22240
7

5
Thickness [m]

exp. F = 445N
exp. F = 1334N
3 exp. F = 2224N
FEM F = 445N
FEM F = 1334N
FEM F = 2224N
2
ana. F = 445N
ana. F = 1334N
ana. F = 2224N
1
0 50 100 150
time [s]

Figure 6.10: Simulation of squeeze-out flow of a thermoplastic material from a gap between two parallel
plates. (Top) velocity field at t =150 s with applied force F =1,335 N and (Bottom) comparison of
experimental results (shown as “exp”) with Comsol simulation results (shown as “FEM”) and prediction of
numerical solution of analytical equations (shown as “ana”). F indicates the applied force in each case
(reproduced with the permission of P. Hubert [48]).
90 Chapter 6 Modeling of heat sealing process

F
F
Heated
Jaw
Tie PA y Tie PA y
Sealant x 2ho Sealant x
2h

L L
t=0 t=t1
F F

Figure 6.11: Squeeze flow during heat sealing process: (left) before and (right) after squeeze flow [49].

(a) (b) (c)

Sealed area

(a1) (b1) (c1)

Figure 6.12: Schematic and SEM images of different possible shapes of the cross-section of sealed area
in 130 μm sealants: (a) and (a1): no SOF (P = 0.2 MPa, t = 1 s, T = 140 °C); (b) and (b1) low SOF (P = 0.2 MPa,
t = 2 s, T = 140 °C); (c) and (c1): high SOF or poly ball (P = 3 MPa, t = 3 s, T = 140 °C) [49].

analyses by the ratio of solid/melt densities. The authors presented one-dimensional

models based on power-law fluid and Carreau–Yasuda fluid models based on the coor-
dination system shown in Figure 6.11. Using a quasi-steady-state assumption, they could
achieve the following analytical equation for the power-law model:

1=n !n+1
n
h0 4ðn + 1Þ n1 + 1 2F
= 1+t h (6:14)
h Lð2n + 1Þ 0 mL2 W
 6.2 Modeling of squeeze-out flow 91

where n is the power-law index and m is the consistency index. Using the Carreau–Yasuda
fluid model, they obtained the following nonlinear differential equation:
0 1


 n−1
∂P ∂ @ ∂Vx a a ∂Vx A
= η0 1 + −λ (6:15)
∂x ∂y ∂y ∂y

where P is the pressure inside the molten sealant. Due to the lack of an explicit analyt-
ical solution for equation (6.15), they used finite difference method (FDM) to solve this
model. The authors compared the models prediction with experimental results. They
showed that in a film with thick 130 μm sealant layer, increasing temperature from
105 to 140 °C increased significantly SOF (Figure 6.13).

Experimental data T = 140 °C Experimental data T = 105 °C

50 FDM model 25 FDM model
Power-law model Power-law model
40 20

15
SOF (%)

SOF (%)

30

20 20

15 5

0 0

0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Dwell time (s) Dwell time (s)

Figure 6.13: Comparing SOF at different dwell times with the predictions of the FDM and power-law
models. All samples were sealed at sealing pressure of 3 MPa [49].

They found that the FDM model could predict much better the experimental data but
still required more precision to be considered as a predictive model. The authors
used heat transfer modeling and showed that heat transfer induces a lag in SOF.
Figure 6.14 shows the heat transfer model predictions for temperature distribution
within the sealant layer at different jaw temperatures and dwell times (Figure 6.14
(b, c)). Based on the predicted temperature profiles and by considering peak melt-
ing temperature at the criterion for melting, they could build a melt front versus
heating time curve for each sealing temperature as shown in Figure 6.14(c). They
then considered the time required for complete melting of the sealant layer as a
horizontal shift factor for their FDM model and showed that using this approach,
the FDM model could predict well the SOF experimental data. The authors also ex-
amined the effect of sealing layer thickness and showed that reducing sealant thick-
ness from 130 to 50 μm suppressed SOF. They also examined the effect of sealant
viscosity in a film with 50 μm sealant layer and found that reducing sealant viscosity
could enhance SOF only at high sealing pressure and time. The authors compared the
92 Chapter 6 Modeling of heat sealing process

effect of sealing pressure on SOF in films with 130 and 50 μm sealants and, as shown in
Figure 6.15, found that increasing sealing pressure by 10 times could only improve SOF in
thick sealant and had almost no effect on SOF. As can be seen, their proposed FDM model
could predict the effect of SOF in both thick and thin sealants.

Heat

PA(Solid)
Tie
(a) hm
ho
Sealant
Solid layer
Melt layer PA(Solid)

L
Heat
(b) 150 140 °C 105 °C
100
125
100 0.05 s 75 0.05 s
T (°C)

0.1 s 0.2 s
T (°C)

75 0.15 s 0.3 s
50 0.4 s
0.2 s
50 0.5 s
0.25 s 0.6 s
25
25
Sealant Layer Tie PA Sealant Layer Tie PA
0 0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
y/H y/H

(c) 140 Interface with other sealant side

140 Interface with other sealant side
120 120 105 °C
140 °C 100
100
hm (μm)

hm (μm)

80 80
60 60
40 40
20 20
0 Interface with tie 0 Interface with tie
0.10 0.15 0.20 0.25 0.40 0.45 0.50 0.55 0.60
Time (s) Time (s)

Figure 6.14: (a) Schematic of melt layer thickness evolution during heat sealing and (b) and (c) exact 3,131
melt layer thickness (hm) at different times during heat sealing process at jaw temperatures of 140 and
105 °C. The total thickness of the sealant layer was 130 µm.
 6.3 Modeling seal strength development 93

20 Experimental Thick Sealant

Experimental Thin Sealant
FDM Thick Sealant
15 FDM Thin Sealant
SOF (%)

10

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Sealing Pressure (MPa)

Figure 6.15: Effect of sealing pressure on SOF in films with thick (130 µm) and thin (50 µm) sealants. Heat
sealing was done at 0.5 s and T =140 °C for all samples. The lines show shifted FDM model predictions [49].

In addition, using two-dimensional simulation of SOF in heat sealing using COMSOL

multiphysics software and experimental data, they showed that the pressure profile in-
side the sealant is a nonlinear profile. Using the obtained sealant velocity profile, the
authors estimated the shear rate during SOF and found that it falls within the transition
region between the Newtonian and power-law regions. These results emphasizes on the
importance of considering Carreau–Yasuda fluid model in prediction of SOF in heat
sealing.

6.3 Modeling seal strength development

Predicting seal initiation temperature and final seal strength are two important goals
of any heat sealing model. As mentioned in Chapter 2, both molecular diffusion and
crystal formation after sealing contribute to the final seal strength while hot tack
strength depends mainly on molecular diffusion. Crystallinity in the sealed area de-
pends on molecular characteristics such as Mw, MWD, branching architecture, and
branching density as well as cooling rate of the sealed area after sealing [50]. There-
fore, prediction of seal strength requires much complex analysis compared with the
hot tack strength. However, it should be considered that without enough molecular
interdiffusion at the interface, even highly crystalline materials show poor seal
strength. This indicates that the molecular diffusion is the main important factor, es-
pecially at the early stages of the seal strength development, while crystal formation
enhances the strength by reducing mobility of the diffused chains. This indicates the
significant importance of considering molecular interdiffusion in the prediction of
seal initiation temperature. It should also be noted that, increasing initial crystallinity
94 Chapter 6 Modeling of heat sealing process

of the films can delay considerably the interface temperature by reducing heat trans-
fer through heat absorption due to melting of these crystals. Considering all afore-
mentioned, this section presents literature models for estimation of seal strength
using molecular interdiffusion. These models focus mainly on the relation between
fracture stress or fracture energy and time.
Wool [51] used the following rate law to establish a relation between the damage
or void concentration per unit volume of the interface (C) and time:

dC
− = ktn (6:16)
dt

where k is a temperature-dependent rate constant and n is the order of the healing

process. Using this approach, the following empirical kinetic theory equation for
crack healing was proposed to determine recovery or healing as a function of time:

σ ðt Þ 1 − R0
ffi 1− (6:17)
σ∞ 1
ð1 + KtÞ1−n

where σ∞ is the bulk fracture stress and R0 and K are constants. Equation (6.17) can
predict the general sigmoidal behavior observed in seal strength development; how-
ever, order for damage disappearance (n) is unknown, and therefore, the order of
healing process needs to be determined experimentally. This indicates that equation
(6.17) is a strictly empirical equation that cannot predict the time dependency of the
seal strength without experimental measurements.
Wool et al. [52] proposed the following scaling law, based on the reptation model,
to relate dynamic properties of interfaces to their static (bulk) properties:

r=4
t
H ðtÞ = H∞ (6:18)
τd

In this equation, H(t) and H∞ are any dynamic and static property of the interface,
respectively. Moreover, r can be 1, 2, 3 . . . depending on the molecular property that
is investigated. It has been shown that disentanglement time (t < τd), fracture stress,
and fracture energy of a polymer–polymer interface, in uniaxial tension, vary with
time according to t1/4 and t1/2, respectively [52–56]. Therefore, it is likely to expect a
dependency of t1/2 for seal and tack strength in a heat sealing process.
Wool and O’Connor [57] developed another healing theory based on the molecu-
lar interdiffusion across the interface by considering two contributions for fracture
stress (σ) as

σ = σ0 + σd (6:19)

where σ0 is the stress due to wetting or surface attractions and σd is the stress due to
chain interdiffusion across the interface. They assumed that the fracture stress originated
 6.3 Modeling seal strength development 95

from interdiffusion of polymer chains across the interface (σd) and is proportional to the
number of the new constrains imposed on the diffused chain:

σ d = qn = qn0 X (6:20)

where q, n, n0, and X are a constant, the number of the new constrains, and the total
number of constrains per unit volume of the virgin bulk material and the diffusion
length of polymer chains, respectively. Using this assumption and by considering a
diffusion initiation function ψ_ ðtÞ and a wetting distribution function ϕ_ ðtÞ, they ob-
tained the following general healing function expressions for fracture stress and frac-
ture energy:


σ ðt Þ σ0 qn0
= + ð2DtÞ ψðtÞ ϕ_ ðtÞ
1=4 _
(6:21)
σ∞ σ∞ σ∞

2 2 
EðtÞ E0 q n0
= + ð2DtÞ1=2 ψ_ ðtÞ ϕ_ ðtÞ (6:22)
E∞ Eσ∞ σ∞

where E∞ and D are the bulk fracture energy and the diffusion coefficient, respec-
tively. The following conclusions can be made based on the proposed healing theory
of Wool and O’Connor [57]:
· ·
i. For instant wetting and instantaneous diffusion (ϕðtÞ = ψðtÞ = δ(t), where δ(t) is
the step function):

σ ⁓ t1=4 and E ⁓ t1=2

· ·
ii. For constant wetting rate and diffusion (ϕðtÞ = a.t, ϕðtÞ = δ(t)):

σ ⁓ t + t5=4 and E ⁓ t + t3=2

·
iii. For constant wetting rate and small diffusion rate (ϕðtÞ = at and D→ 0):

σ, E ⁓ t

Considering the timescale in the heat sealing process, instant wetting and diffusion
assumption are likely to be valid, and therefore, the seal strength is expected to obey
t1/2 dependency. It should be noted that the presented healing theory of Wool and
O’Connor can also be used to predict the effect of molecular weight on seal strength
by considering D ~ 1/MW.
Moffitt [58] proposed an integral form equation for evolution of peel strength
with time. By comparing model predictions with literature data, he reported that con-
sidering time dependency of wetting process is necessary in the prediction of seal
strength.
96 Chapter 6 Modeling of heat sealing process

Morris [59] proposed to use the Brownian motion concept and the terminal relax-
ation time to estimate the diffusion length using the following equation [59]:
pffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffi
W 4 Dt t
W✶ = = pffiffiffiffiffiffiffiffiffiffiffiffiffi = (6:23)
Rg 4 Dtd,avg td,avg

where W✶, W, Rg, D, and td,avg are dimensionless penetration distance, penetration
distance at time t, the radius of gyration of the polymer chain, diffusion coefficient,
and the average terminal relaxation time. He used a heat transfer model to estimate
the interface temperature at each time and determined the average terminal relaxa-
tion time using the following equation:

1 1Xi=n
1
= (6:24)
td,avg n i=1 td,i

A critical penetration distance called Wc✶ was defined where the penetration length
corresponds with the onset of the seal strength plateau region. By assuming direct
correlation between dimensionless diffusion length and seal strength, Morris fitted
the variation of plateau initiation temperature with dwell time in two different cases
to determine Wc✶ as the fitting parameter. He found that in both cases, Wc✶ was lower
than 0.1. This indicates that the seal formation was done at much smaller length scale
than Rg of the polymer chain. By comparing experimental results and model predic-
tions, they proposed that a direct relation between Wc✶ and the seal strength could be
established.

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[25] Bamps, B., et al., Evaluation and optimization of seal behaviour through solid contamination of heat‐
sealed films. Packaging Technology and Science, 2019. 32(7): p. 335–344.
[26] Picher-Martel, G.-P., A. Levy, and P. Hubert, Compression moulding of carbon/PEEK randomly-oriented
strands composites: A 2D finite element model to predict the squeeze flow behaviour. Composites Part
A: Applied Science and Manufacturing, 2016. 81: p. 69–77.
[27] Levy, A., G.P. Martel, and P. Hubert, Modeling the Squeeze Flow of a Thermoplastic Composite Tape
during Forming, in COMSOL Conference. 2012, Boston, USA.
[28] Hou, J., et al., An analysis of the squeeze-film lubrication mechanism for articular cartilage. Journal of
Biomechanics, 1992. 25(3): p. 247–259.
[29] Mueller, C., et al., Heat sealing of LLDPE: Relationships to melting and interdiffusion. Journal of Applied
Polymer Science, 1998. 70(10): p. 2021–2030.
[30] Ting, G., Polymer Welding: Strength Through Entanglements. 2012.
[31] Grewell, D. and A. Benatar, Welding of plastics: Fundamentals and new developments. International
Polymer Processing, 2007. 22(1): p. 43–60.
[32] Grewell, D. and A. Benatar, Coupled temperature, diffusion and squeeze flow model for interface healing
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98 Chapter 6 Modeling of heat sealing process

[33] Engmann, J., C. Servais, and A.S. Burbidge, Squeeze flow theory and applications to rheometry: A review.
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[36] Suwonsichon, T. and M. Peleg, Rheological characterisation of almost intact and stirred yogurt by
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Chapter 7
Multicomponent sealant films

Increasing demand for seal layers with wide range of properties and functionality
and the limited capabilities of a single polymer component sealant have increased the
application of multicomponent sealants in packaging industry. These multicomponent
sealants can play various roles in a package including, but not limited to, modifying
sealing, mechanical and rheological properties of sealant. Multicomponent sealant
films are mainly produced from blending of multiple polymer components. Blending
has been shown to be a promising method in achieving high-performance polymer
materials. From sealing point of view, the main goals for using polymer blends as the
multicomponent sealant layer can be summarized as (i) reducing sealing temperature,
(ii) broadening the sealing window, (iii) possibility of asymmetric sealing, (iv) enhanc-
ing caulkability, (v) changing sealing behavior, and (vi) optimizing sealant cost. Before
discussing sealants based on polymer blends, first a short review of thermodynamic
and morphology of polymer blends is presented in the next section.

7.1 Thermodynamics of polymer blends

From the thermodynamic point of view, polymer blends can be categorized into three
groups: miscible, partially miscible, and immiscible blends. Miscible polymer blends
form one-phase mixture that is homogeneous in the molecular scale. Partially misci-
ble blends form two phases in which each phase contains both polymer component
molecules. Each of these phases is homogeneous at the molecular scale but contains
different compositions of polymer components compared to the other one. The two
phases have their boundaries known as the interface and can have different shape
and size or in another word can have different morphology. Immiscible polymer
blends form two phases in which each phase consists of only one polymer component.
Like partially miscible blends, they also have interface between the phases and can
have different morphologies. Figure 7.1 shows schematically the differences between
these types of blends.
The thermodynamic of a polymer blend system can be described using the Gibbs’s
free energy of mixing (ΔGm):

ΔGm = ΔHm − TΔSm (7:1)

In this equation, ΔHm and ΔSm are the enthalpy and entropy of mixing, respectively. A
miscible blend is formed when negative free energy of mixing is achieved (ΔGm < 0).
Different equations for estimation of the enthalpy and the entropy of mixing have
been discussed widely in literature (see reference [1] for example) and will not be dis-
cussed here. The entropy of mixing has been shown to change inversely with the

https://doi.org/10.1515/9781501524592-007
102 Chapter 7 Multicomponent sealant films

Miscible Partially Miscible Immiscible

A
A+B B*+A

A*+B B

Figure 7.1: Different polymer blend types based on their miscibility.

molecular weight of components in binary mixtures [2–4]. Therefore, due to the very
high molecular weights of polymers, the entropy of mixing (ΔSm) in polymeric mix-
tures is typically negligible. In the absence of specific interactions such as hydrogen
bonding [5], it has been shown that polymer mixtures exhibit a positive enthalpy of
mixing (ΔHm > 0) [1]. Therefore, in most cases, mixing of polymer components results
in a positive ΔGm and the formation of an immiscible polymer blend. Miscible blends
of different polyethylene are the most common miscible polymer blend examples
used as sealant material in plastic film. For example, blending of low temperature
sealing metallocene PE (mPE) with conventional PE is a common approach to reduce
S.I.T. and improve seal strength while maintaining reasonable material cost. Najarza-
deh et al. [47] did a systematic study on the effects of the addition of mPE with linear
or long-chain branching (LCB) molecular structures on seal strength of conventional
LLDPE or LDPE and showed that the blending approach is much effective when the
matrix PE has LCB (Figure 7.2). The % shown in the figure indicates the increase in
seal (or adhesion) strength based on the initial PE type, LLDPE (LL) or LDPE (LD).

6000 conventional PE
20wt%metallocene
40wt%metallocene
Adhesion strength (N.m–1)

5000
60wt%metallocene
106% 100wt%metallocene
4000
68% 54%
3000 24% 190%
16% 140% 135%
11%
2000 80%
90%
53%
1000

0
LL/Linear-m LL/LCB-m LD/Linear-m LD/LCB-m

Figure 7.2: Effect of the addition of linear or LCB mPE on seal strength of LLDPE or LDPE [47].
 7.1 Thermodynamics of polymer blends 103

They also studied the effect of addition of mPE with linear or LCB structures on
hot tack of the same blends. Interestingly, they found that the addition of both mPE
types broadened the hot tack window but only the addition of linear mPE could re-
duce hot tack initiation temperature.
As in most cases blending of polymers leads to the formation of immiscible poly-
mer blends, our main focus in this chapter will be dedicated to immiscible polymer
blends. In immiscible polymer blends, the interactions between the two phases occur
at their boundaries or their interface. These interactions indicate the level of compati-
bility of the phases in the system which directly influences final properties. The level
of interactions between two nonreactive phases can be expressed using the work of
adhesion (Wadh) between them. The work of adhesion is the energy required for sepa-
rating a unit area of the interface between two phases [6]. Wu [7] showed that Wadh
can be estimated using the following two approaches:

(i) Harmonic mean

!
p p
γd γd γ γ
Wadh = 4 d 1 2 d + p 1 2 p (7:2)
γ1 + γ2 γ1 + γ2

(ii) Geometric mean

qffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffi
p p
Wadh = 2 γd1 γd2 + γ1 γ2 (7:3)

where γd and γp are the contributions of dispersive and polar components in the sur-
face tension of components 1 and 2, respectively.
The harmonic mean approach should be used for the estimation of the work of
adhesion between two phases with similar polarities such as between polymeric ma-
terials. On the other hand, the geometric mean equation should be used for the esti-
mation of the work of adhesion between two phases with significantly different
polarities such as mixtures of polymers and inorganic solid materials.
Another important parameter in immiscible polymer blends is the interfacial ten-
sion between phases (γ12) which is defined as the work required to increase the inter-
facial area between phases by a unit of area [6–8]. The interfacial tension between
two polymer melts can be estimated using their surface tensions (γ1 and γ2) and the
work of adhesion between them (Wadh) using the following equation [6, 7]:

γ12 = γ1 + γ2 − Wadh (7:4)

A high level of compatibility between phases results in a greater work of adhesion and,
consequently, a lower interfacial tension. Different techniques have been used to mea-
sure experimentally the interfacial tension between polymers such as the breaking
thread method [9], the fiber retraction method [10, 11], the pendant droplet method [12],
 5000
104

(a) 100wt%Zn-LLDPE (b) 100wt%Zn-LLDPE

3000
4000 20wt%Linear-m 20wt%LCB-m
40wt%Linear-m 40wt%LCB-m
60wt%Linear-m 60wt%LCB-m
3000 2000

2000
1000
1000

Adhesion strength (N.m–1)

Adhesion strength (N.m–1)
0 0
110 120 130 140 150 110 120 130 140 150 160
Temperature (°C) Temperature (°C)
3000
(c) 100wt%LDPE 2000 (d) 100wt%LDPE
2500
Chapter 7 Multicomponent sealant films

20wt%Linear-m 20wt%LCB-m
40wt%Linear-m 40wt%LCB-m
2000 1500
60wt%Linear-m 60wt%LCB-m

1500
1000
1000
500

Adhesion strength (N.m–1)

500
Adhesion strength (N.m–1)

0 0
110 120 130 140 150 110 120 130 140 150 160
Temperature (°C) Temperature (°C)

Figure 7.3: Effect of the addition of mPE with linear or long-chain branching (LCB) structures on hot tack of different polyethylene types [47].
 7.2 Morphology of polymer blends 105

and the rheological approach [13, 14]. The details of these techniques will not be re-
viewed here and can be found in the cited references.

7.2 Morphology of polymer blends

The morphology of immiscible polymer blends directly controls their final properties
[15, 16]. It should be noted that the term morphology refers to the shape and size of the
phases in the blend microstructure [17]. Different common morphologies observed in
binary immiscible polymer blends are listed below in Figure 7.4 with their potential
applications.

Matrix-Dispersed
Co-
Spherical Fibrillar Lamellar Continuous
Morphology

Application Toughness Strength Barrier Properties Conductivity

Figure 7.4: Common morphologies in binary immiscible polymer blends with their potential applications.

The final morphology of a polymer blend is the result of a competition between breakup
and coalescence of dispersed phase during melt mixing [17, 18]. Breakup and coalescence
phenomena are controlled by intrinsic properties of polymer phases such as their in-
terfacial tension [19] and viscosity [20] as well as processing conditions such as shear
rate and the flow field [21, 22]. Breakup of a droplet with radius R in a viscous matrix
having a viscosity of η can be evaluated by considering the capillary number (Ca) that
is defined as [23]
·
γ
Ca = γ (7:5)
12
R

The capillary number is the ratio of the viscous forces (ðγ_ Þ) to the interfacial forces
(γ12/R). It is known that viscous forces tend to deform and eventually break up the
dispersed droplets while the interfacial forces withstand droplet deformation. Droplet
deformation and eventually breakup occurs above a certain capillary number known
as the critical capillary number (Cac) where the viscous forces overcome the interfacial
forces and can deform and eventually breakup the dispersed phase droplets. Figure 7.5
106 Chapter 7 Multicomponent sealant films

(i) (ii) (iii) (iv)

Velocity Gradient

Flow Direction

Figure 7.5: The deformation and breakup process of a dispersed phase droplet in a shear flow field:
(i) to (iii) droplet deformation and (iv) droplet breakup and formation of satellite small droplets.

schematically shows deformation and breakup of a dispersed phase droplet in a viscous

matrix under shear flow.
Coalescence of dispersed phase is another important phenomenon that competes
with the droplet breakup. During coalescence, two dispersed phase domains approach
each other and drain a film of the matrix trapped between them under shear forces
applied by the surrounding medium. When the thickness of the film trapped between
dispersed domains reaches a critical value, the film ruptures and two droplets merge
into a larger droplet. According to the Laplace law, the pressure inside each droplet is
inversely related to its radius; therefore, domains with smaller sizes have a higher
internal pressure and are drained into the larger domain during coalescence [24]. The
coalescence process is schematically shown below in Figure 7.6.

(i) (ii) (iii) (iv) (v)

Figure 7.6: Schematic of coalescence process: (i) approaching droplets, (ii) deformation of contact area
between droplets and formation of matrix film between them, (iii) draining of the trapped matrix film,
(iv) matrix film rupture and merging of droplets, and (v) final merged droplets.

Different models have been proposed to explain the effect of different parameters on
coalescence in a polymer blend. The probability of coalescence can be explained by
considering the following equation [25, 26]:
 
tdrain
P ≈ exp − (7:6)
tint
 7.3 Surface morphology of immiscible polymer blend films 107

where tdrain and tint are the draining time of the matrix film between two droplets and the
time that two droplets are in contact before being moved away by the flow field. For exam-
ple, it has been shown that increasing shear rate at low shear rates enhances coalescence
while higher shear rates reduce the coalescence between dispersed phases [27]. It
should be noted that reducing shear rate reduces both tdrain and tint [28]. These results
indicate that, at least in the studied system, the effect of shear rate on tint was much
significant than on tdrain.
In order to better understand the importance of the above-mentioned discussions,
two examples of the importance of the interfacial tension and flow field are discussed
here. Li et al. [19] studied the effect of interfacial tension on the morphology develop-
ment in immiscible polymer blends. To this aim, they compared the morphology of a
high interfacial tension blend of high-density polyethyelene (HDPE)/and polystyrene
and a low interfacial tension blend of HDPE/styrene–ethylene–butylene–styrene. They
found that the morphology of the dispersed phase in the high interfacial tension system
is spherical droplets while in the low interfacial tension the dispersed phase exists in
the form of elongated fiber-like morphology. This indicates easier droplet breakup in
higher interfacial tension systems where interfacial forces are weak. In another study,
Jalali Dil et al. [29] studied the effect of flow field on the morphology of low interfacial
tension poly(lactic acid) and poly(butylene adipate-co-terephthalate) (PLA/PBAT) blends.
They compared the morphology of PLA/PBAT films prepared at different blow-up ratios
(BUR) in film blowing process and found that changing the flow filed from 1D (BUR ~ 1)
to 2D (BUR = 3) changed the morphology of the dispersed PBAT phase from a fibrillar to
a lamellar morphology. It was found that changing the morphology from fibrillar to la-
mellar reduced the seal initiation temperature of the film samples by increasing the
surface area of low sealing temperature phase (PBAT) at the film surface.
These two examples clearly indicate the significant importance of controlling
morphology of polymer blend sealants to achieve the final desired properties includ-
ing sealing performance.

7.3 Surface morphology of immiscible polymer blend films

In addition to bulk properties, controlling the morphology and microstructure of poly-

mer blends is critical in controlling their surface properties [15, 30]. As sealing properties
are directly controlled by the surface morphology, controlling the surface morphology of
a polymer blend is necessary in achieving the desired seal properties. From the thermo-
dynamic view point, the surface morphology of sealant films right after exiting the ex-
trusion die depends on the interactions of the blend components with the metallic inner
surface of the extrusion die. The thermodynamics of the localization of the phases with
respect to the surface of the die can be explained using the Harkins’ equations [31, 32]:

λSAB = γSB − ðγSA + γAB Þ (7:7)

108 Chapter 7 Multicomponent sealant films

λSBA = γSA − ðγSB + γAB Þ (7:8)

where λ, γSB, γSA, and γAB are the spreading coefficients, the interfacial tension between
solid surface and phase B, the interfacial tension between solid surface and phase A, and
the interfacial tension between two polymer phases, respectively. Figure 7.7 shows the
different possible morphology scenarios depending on spreading coefficient values in a
system with dispersed-matrix morphology. It is worth mentioning that when surface
wetting by the minor component is preferred, a minimum amount of minor phase is
needed to form a complete layer. Below such content, discrete domains of the minor
phase are formed at the surface.

Metal Surface
λSAB >0
A
Phase A wets the
λSBA <0 metal surface B

Metal Surface
λSAB <0
Phase B wets the
metal surface A B A
λSBA >0
A

λSAB <0 Metal Surface

Both A and B wet A A A

λSBA <0 the metal surface B A

A A

Figure 7.7: Different surface morphologies of polymer blends in contact with a solid surface based on
Harkin’s equation.

Considering that the inner surfaces of extrusion dies are typically made of hydrophilic
high surface energy stainless steel, it is likely to expect a higher level of interactions be-
tween the surface and the phase with higher polarity. Therefore, from the thermody-
namic stand point, in a two-phase system with different polarities of components, it is
likely to expect that the phase with higher polarity wets the surface of the die and, conse-
quently, covers the surface of the final film. However, considering only thermodynamics
cannot provide a reliable prediction for the localization of the phases at the film surface.
It has been shown that in a two-phase flow, when the viscosity ratio of phases is far from
unity, the phase with lower viscosity migrates and localizes itself close to the wall where
higher shear rates exist [33]. In analyzing the final surface morphology of a polymer
blend film, both thermodynamics and rheological properties as well as flow conditions
(temperature and flow rate) should be considered. Therefore, it is likely to conclude that
 7.4 Sealants based on immiscible polymer blends 109

in a low interfacial tension system where polarity of the phases is similar, the viscosity
ratio can play a much important role in determining the surface morphology while in a
high interfacial tension system, the phase with higher polarity is more likely to wet the
surface. Therefore, a low interfacial tension blend with viscosity ratio close to unity
should be considered if the presence of both phases at the surface is desired.

7.4 Sealants based on immiscible polymer blends

The addition of a polymer with low seal initiation temperature (S.I.T.) to another poly-
mer with higher S.I.T. is a common approach for reducing S.I.T. of a sealant film [34].
In the case of immiscible mixtures, low S.I.T. polymer should be located at the surface
of the sealant film. Figure 7.8 schematically shows the arrangement of low S.I.T. phase
on the surface in the seal area.

High S.I.T. phase

Low S.I.T. phase

Sealing line

Figure 7.8: Seal area between two polymer blend films with low S.I.T. dispersed phase.

At temperatures above S.I.T. of the dispersed phase (but below S.I.T. of the matrix), only the
dispersed phase domain at the surface can be melted and fused together and develop seal
strength. At a low content of the dispersed phase, the effect is not considerable due to the
small number of formed bridges between dispersed phases. By increasing the dispersed
phase content, the effect becomes much pronounced as more bridges can be formed. In
immiscible polymer blends where the S.I.T. of the two phases is at least 20° apart and both
phases exist at the surface, the seal remains peelable between SIT of the phases. By increas-
ing temperature above the S.I.T. of the matrix, matrix regions can also fuse to each other
and contribute to the seal strength development. As a result, an increase in the seal strength
is observed above the S.I.T. of the matrix. Mehta and Chen [35] showed that the addition of
a very low density polyethylene (vLDPE)copolymer to polypropylene (PP) reduced its
S.I.T. and broadened its peelable window (Figure 7.9). Table 7.1 lists common low SIT com-
ponents that are used to reduce sealing temperature of PE-based sealants. The molecular
structure and properties of these materials were discussed in detail in Chapter 4.
As another example, Figure 7.10 shows the effect of addition of 15 and 25 wt% of eth-
ylene vinyl acetate (EVA) on seal strength of PE-based sealant. As can be seen, increasing
EVA content from 0% to 25% reduced the S.I.T. of the sealant from 100 to 85 °C. Moreover,
the addition of EVA broadened the seal curve.
110 Chapter 7 Multicomponent sealant films

HEAT SEAL STRENGTH (LB/IN)

5
4
3
2
1
0
80 90 100 110 120 130 140 150
TEMPERATURE (°C)
4
HEAT SEAL STRENGTH (LB/

3.5
3
2.5
2
1.5
1
0.5
0
80 90 100 110 120 130 140 150
TEMPERATURE (°C) 80/20
60/40
30/70

Figure 7.9: Seal strength of very low density polyethylene (vLDPE) and polypropylene blends at different
blend ratios. The first two digits in the legend show vLDPE content while the second two digits show PP
content [35].

Table 7.1: Common low S.I.T. polymers used in PE-based sealant films.

Low S.I.T. component Peak melting temperature (°C)

Alpha olefin copolymers (plastomers) –

Ethylene vinyl acetate (EVA) –
Ethylene methyl-acrylate (EMA) –
Ethylene-methacrylic acid (EMAA) –
Ethylene-acrylic acid (EAA) –
Ionomer –
Ethylene n-butyl acrylate (EnBA) –

Addition of polybutene-1 (PB-1) to polyethylene is another common strategy to

broaden their peelable seal window [36–40]. Typically PB-1 compositions between 5
and 30 wt% are added to polyethylene for achieving peelable films [41, 42]. Nase et al.
[43] showed that, in a blend of LDPE and PB-1, the peel force decreased exponentially
by increasing the PB-1 content. The morphology of PB-1 in blends with polyethylene
has been studied previously in literature and it was found that PB-1 forms a dispersed
elongated phase in a polyethylene matrix [43, 44]. In addition, it has been shown that
 7.4 Sealants based on immiscible polymer blends 111

Polyethylene
6000 Polyethylene +15wt.%EVA
Polyethylene +25wt.%EVA
5000
Seal Strength (g/25.4 mm)

4000

3000

2000

1000

70 80 90 100 110
T (°C)

Figure 7.10: Effect of the addition of EVA to polyethylene on film seal strength.

cohesive failure within the sealant layer and along the interface of PE and dispersed
PB-1 islands is the peeling mechanism in peelable sealants based on PB-1 [44]. The ad-
dition of polyolefin thermoplastic elastomers such as EPDM, EPM, halogenated butyl
rubber, isoprene rubber, and styrene–butadiene rubber to polyolefin sealants has
also been shown to result in a peelable sealant that can withstand high postprocessing
temperatures such as retort applications [42]. The main disadvantage of using blend
technology for peelable sealant is the fact that peeling properties is directly controlled
with the blend morphology which is affected by the processing condition. Therefore,
the same blend composition can result in different peeling forces when the film is
processed at different conditions. This increases the risk of using this technology espe-
cially in the applications where consistent peel force is needed.
Another application for blending in sealant technology is the modification of the
rheological properties of the sealant layer to enhance its caulkability. It has been
shown that the caulkability of sealant materials increases considerably by reducing
their S.I.T. and viscosity [45, 46]. Blending low S.I.T. and low viscosity sealants such as
plastomers, ionomers, and metallocene polyethylene is typically considered as an ef-
fective approach where caulkability is needed. Forming miscible polymer blends is
the goal in this approach to achieve viscosity reduction at low shear rates where
caulking occurs [48].
112 Chapter 7 Multicomponent sealant films

7.5 Polymer nancomoposites

Polymer nanocomposites have received much attention recently due to their significant
potential in altering different polymer blend properties such as their electrical [49], rhe-
ological [50, 51], and mechanical properties [52]. These materials have also received sig-
nificant attention in polymer packaging due to their unique properties such as gas
barrier, gas absorption, antimicrobial effects, sensing properties, and improved me-
chanical properties [53,54]. Previous studies on the addition of nanoparticles to sealant
materials showed the potential of this approach in altering seal properties. Mohammadi
et al. [62] compared seal properties of PE with organically modified montmorillonite
(oMMT) and nonmodified MMT. They showed that while PE/oMMT nanocomposite ex-
hibited a cohesive peel behavior with a peelable window of about 10 °C, PE film-
containing MMT showed a lock seal performance. They also found a much lower peel
strength with a significantly broad peelable window of 45 °C when PE-grafted-maleic
anhydride (PE-g-MA) was used as a compatibilizer in PE nanocomposite. This was
attributed to the fine distribution of oMMT in the nanocomposite with PE-g-MA that
results in much more zones to form crack initiation during peeling. This mechanism
is schematically shown in Figure 7.11.

Peel propagation path way

Peel through polymer ligament
direction

W
Crack tip

Peel propagation path way

Peel arm through the clay stacks

Figure 7.11: Peeling mechanism of PE/oMMT nanocomposite [61].

The addition of nanoparticles to polymer blends is another new approach in achiev-

ing high performance hybrid systems. Previous studies have shown that controlling
the localization of solid particles in polymer blend is a key parameter in achieving
desired properties. The thermodynamic equilibrium localization of solid particles in a
polymer blend can be predicted by the Young’s model [9]:
γ1s − γ2s
ω= (7:9)
γ12

where ω, γ1s, γ2s, and γ12 are the wetting parameter, the interfacial tensions between
polymer 1 and solid, polymer 2 and solid, and polymer 1 and 2. If ω in equation (7.9) is
greater than 1, then the localization of solid particles in phase 2 is thermodynamically
preferred while for ω < −1, the thermodynamic equilibrium localization of solid particles
 7.5 Polymer nancomoposites 113

should be in phase 1. When −1 < ω < 1, the localization of solid particles at the interface
is thermodynamically preferred. The localization of solid particles is also affected by ki-
netic parameters. Previous studies showed that migration of solid particles from one
phase to another in polymer blends can be considered as a three-step process: (i) migra-
tion from the bulk toward the interface, (ii) draining of matrix film between the particle
and the interface, and (iii) migration at the interface. These steps are schematically
shown in Figure 7.12.

a c b
Solid Solid Solid

A B A B A B

Figure 7.12: Different steps in migration of a solid particle from polymer A to polymer B: (a) bulk
migration within polymer A, (b) film draining of polymer A, and (c) migration at the interface.

In the first step of migration, the particle moves within the initial polymer phase
(polymer A in Figure 7.12). Eckstein et al. [56] studied experimentally the bulk migra-
tion and found that the particle flux in shear-induced migration scales as ðγ_ Þ where
ðγ_ Þ is shear rate. The transitional velocity of spherical solid particles in the direction
of the flow (flow-induced mechanism) has been shown to scale as γ_ × R [57, 58]. These
results indicate that both shear rate and particle size are important in the bulk migra-
tion step. In the film draining step, as the particle approaches the interface, a thin
layer (film) of polymer A between the particle and the interface needs to be drained
out so the particle can reach the interface. The film draining time (td) between a
spherical solid particle with radius R and a deformable liquid/liquid interface can be
estimated as
0 1
3n2 η A2f @ 1 1A
td = − (7:10)
16πFc δ2 δ2
C o

where Fc, η, Af, δC, and δo are the contact force, the viscosity of the polymer A, the surface
area of the polymer A film between the particle and the interface (~2πR2), the critical film
thickness in which the polymer A layer rupture occurs, and the initial polymer A film
thickness where the film draining process begins, respectively. Moreover, n is the num-
ber of immobile interfaces in a system; in this case n = 1 as only the interface between the
particle and polymer A is an immobile interface. In the particle migration theory, each
particle has a limited time to drain the layer between itself and the interface which is
called the contact time (tC). If the draining time from eq. (7.10) is longer that the contact
time, the particle will be moved away from the interface before it can enter the interface.
Although estimating td and tc are challenging, eq. (7.10) still can provide much insight
114 Chapter 7 Multicomponent sealant films

into the effect of different processing conditions on particle migration. For example, in-
creasing the shear rate increases the contact force but at the same time reduces the con-
tact time between the particle and the interface [51]. In the third step, after the rupture of
polymer A layer, the particle is located at the interface and begins migrating across the
interface. Migration at the interface is a complex phenomenon in which interface and
viscous forces compete. Jalali Dil and Favis [51] presented a semiquantitative model to
predict the effect of different thermodynamic and kinetic parameters on particle migra-
tion at the interface.
Polymer hybrid systems where solid particles are added to polymer blends have
also been used as a new approach in sealant technology. Previous studies showed that
the addition of oMMT nanoparticles to PE/EVA blends increased the peelable window
of the blend from 5 to 30 °C [59, 60]. Mohammadi et al. [61] studied the effect of the
addition of oMMT on seal properties of polyethylene methacrylate copolymer (EMA),
ethylene acrylic ester-glycidyl methacrylate terpolymer (EMA–GMA), and their blends
with polyethylene. Using the Young’s equation (eq. (7.9)) and by estimating interfacial
tensions between the components, they found that oMMT nanoparticles should be lo-
cated at the interface of PE/EMA and within EMA–GMA phase in PE/EMA–GMA. Using
transmission electron microscopy and rheological data, they showed that oMMT nano-
particles were located in the predicted localizations.

PE/EMA (a) PE/EMA-GMA (b)

OC/PE/EMA OC/PE/EMA-GMA
1500 1500
Peel Force (N/m)

Peel Force (N/m)

1000 1000

Lock seal
Lock seal
500 500
Easy-open peelable
Easy-open peelable

0 0
100 110 120 130 140 150 160 100 110 120 130 140 150 160
T (ºC) T (ºC)

Figure 7.13: Seal curve of PE/EMA and PE/EMA–-GMA blends and their nanocomposites with oMMT. The
dashed lines show the peelable region [61].

When nanoparticles were located at the interface of PE/EMA, a significant change in

the seal behavior was observed and peelable window was increased from 5 to 35 °C,
Figure 7.13. On the other hand, the addition of oMMT to PE/EMA–GMA did not change
considerably the seal behavior. This was attributed to initiation and growth of crack
at the interface under stress due to the rigid nature of the nanoparticles while locali-
zation within EMA–GMA did not alter the interface crack phenomenon. Figure 7.14
schematically shows these two mechanisms.
 References 115

Seal area
Peel direction Crack propagation

PE EMA Crack tip

organoclay Cohesive peel

Peel arm

Figure 7.14: The effect of the interface localization of oMMT at the interface of PE/EMA on broadening
of its peelable window.

It is worth mentioning that addition of nanoparticles and controlling their locali-

zation can also improve other properties of polymer blend-based packaging, such as
their gas barrier properties. This indicates the multidimensional aspect of this ap-
proach compared to only blending approach and indicates the significant potential of
this approach in improving different aspects of sealant films

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Chapter 8
Bioplastic sealants

Commodity polymers are produced from nonrenewable petroleum resources and are
not biodegradable or compostable. Considering the global capacity of 360 million metric
tons for synthetic polymers, Shinoka et al. [1] indicated their significant environmental
impact. Recently, polymers produced from renewable resources and biodegradable or
compostable polymers have received an increasing amount of attention [2] as solutions
for plastic environmental crisis. Bioplastics can be defined as polymers that are pro-
duced from bio-based resources and/or are biodegradable or compostable [3, 4]. This
definition can be better understood using the schematic in Figure 8.1.

PLA
PHA
Bio-PE
PBS
Bio-Based

PE

PP PBAT

PS

Biodegradability/Compostability

Figure 8.1: Classification of bioplastic materials, except the dark gray zone, other polymers are
considered as bioplastics.

For example, polyethylene (PE) is a nonbiodegradable material but PE produced from

bio-based resources is considered as a part of bioplastic family. This is due to the fact
that bio-based PE is produced from a renewable resource (corn in this case) rather
than nonrenewable petroleum resources.
Bioplastic family also has polymers such as poly(butylene adipate-co-terephthalate)
or PBAT that are petroleum-based but biodegradable. Therefore, it can be seen that the
definition of bioplastics is very broad. Despite such a broad definition of bioplastics, the
majority of polymer materials do not fall within the bioplastic categories.
This has encouraged researchers in industry and academia to focus more on bio-
plastic materials. Despite their environmental advantages, bioplastic materials have not
been able to play a major role in plastic industry. Based on the growth rate of bioplas-
tics in 2010–2012, the annual bioplastic global capacity was expected to reach 6 million

https://doi.org/10.1515/9781501524592-008
120 Chapter 8 Bioplastic sealants

tons at the end of 2017 [5] but the global production capacity of bioplastics in 2017 was
determined as 2.1 million metric tons [6, 7]. This indicates a significantly lower growth
rate than expected in the past decade. Despite the fact that bioplastics were initially pre-
sented as candidates for replacing commodity polymers, their poor mechanical proper-
ties limited significantly their applications in many applications. In addition, bioplastic
materials are more expensive than commodity polymers. Despite the fact that bioplas-
tics could not yet be a key player in plastic market, they still can be an interesting op-
tion to reduce environmental impact of plastic materials in some specific applications.
In this chapter, some bioplastic polymers that are used in flexible packaging are re-
viewed [5].

8.1 Bio-based polyethylene terephthalate (bio-PET)

The molecular structure of polyethylene terephthalate (PET) and its characteristics

were discussed in detail in Chapter 4. PET is industrially produced by condensation po-
lymerization of ethylene glycol and terephthalic acid in the presence of a catalyst [8].
The main difference between the conventional PET and bio-PET is that ethylene glycol
used in the production of bio-PET is obtained from sugarcane or sugar beets. Consider-
ing the molecular structure of PET, ethylene glycol comprises 30 wt% of PET, which in-
dicates that bio-PET is a 30 wt% bio-based material. Although there have been attempts
from giant beverage companies to commercialize 100% plant-based bio-PET since 2011,
it has not yet reached the commercialization stage and is still in the prototype step. Bio-
PET has been the major player of bioplastics especially in rigid packaging with the
global production capacity of about 25% of global bioplastic production capacity.
Recently and following the announcement of the production of bio-based paraxy-
lene (a key raw material for production of terephthalic acid) from beet sugar by Vir-
ent Inc. [9], producing 100% bio-based PET has become possible. It should be noted
that similar to fossil-based PET, bio-PET is not biodegradable/compostable but can be
recycled to reduce its environmental impact.

8.2 Bio-based Polyethylene (PE) and Ethylene

Vinyl Acetate (EVA)
Braskem in Brazil began production of bio-based polyethylene in 2010. The main dif-
ference of bio-based polyethylene and petroleum-based polyethylene is that in bio-PE
production, ethylene is produced from sugarcane rather than from petroleum resour-
ces. Currently, Braskem produced bio-LDPE, bio-LLDPE, and bio-HDPE. Their LLDPE
portfolio includes both conventional butane and hexane copolymers. It should be
noted that the highest bio-based content in their portfolio is their bio-HDPE with 96%
bio-based material. The properties of bio-based PE are similar to petroleum-based
 8.3 Poly(lactide) 121

ones but its higher price and limited availability have limited its application. Braskem
recently began producing bio-based EVA with two grades having 45% and 80% bio-
based content.

8.3 Poly(lactide)

Among the family of biodegradable/compostable polyesters, polylactide (PLA) has been

the focus of much attention due to the following reasons: (i) it is produced from renew-
able resources such as corn, (ii) is compostable; (iii) has very low or no toxicity, (iv) has
high mechanical stiffness and clarity, and (v) good availability in the market [10]. Figure
8.2 shows different molecular structures of PLA. Properties of PLA are highly related to
the ratio between the two isomers D and L in the PLA molecular structure. Commer-
cially available, we can find 100% L-PLA (called PLLA) with high level of crystallinity
and copolymers of poly(L-lactic acid) and poly(D,L-lactic acid) which are rather amor-
phous. Among compostable bioplastics, PLA has a high mechanical strength and clarity.
This high mechanical strength could be disadvantageous in some application due to
flex cracking of PLA films. Anderson et al. [11] reviewed different strategies to increase
toughness of PLA including variation of mesoform ratio in the polymer, plasticization,
and blending with other polymers. Another challenge with PLA is its difficult film pro-
duction due to its low melt strength and high stiffness. Previous studies emphasized on
the importance of optimizing processing conditions such as extrusion temperature and
line speed to achieve a staple extrusion process [12]. Due to its high clarity and stiffness,
PLA has been considered as a candidate to replace PET.

CH3

O
Poly(L, Lactide) OH H

O n
CH3

O
Poly(D, Lactide) OH H

O n

CH3 O

O H
Poly(L,D Lactide) OH O

O CH3 n

Figure 8.2: Different molecular structure of poly(lactide), PLA.

122 Chapter 8 Bioplastic sealants

In 2015, Natureworks and Bi-AX International announced the development of biaxi-

ally oriented PLA film to replace BoPET. PLA can also be used as a sealant layer specially
when laminated to paper or other compostable substrates to create fully compostable
packaging. Sealing properties of PLA films have been investigated by some researchers.
For example, Yousefzadeh and Ajji [13] examined sealing properties of an amorphous
PDLA film and found a seal initiation temperature at around 80 °C.

8.4 Polycaprolactone

Poly(ε-caprolactone) or PCL is a polyester that is obtained by ring-opening polymeri-

zation of ε-caprolactone in the presence of a catalyst. Figure 8.3 shows the molecular
structure of PCL.

O
O

n Figure 8.3: Molecular structure of PCL.

Biodegradable character of PCL has made it an interesting option for controlled release
of drugs [10]. PCL has a low Tg (~−60 °C) and a low melting point (65–80 °C), which in-
dicates that PCL has a low thermal resistance. Although the soft and biodegradable na-
ture of PCL shows that it could be an interesting option for biodegradable flexible
packaging [14], its low melting temperature has limited its applications. Therefore, PCL is
generally blended or modified (e.g., copolymerization, cross-linking) [15]. For example, Li
and Favis [16] studied the morphology and miscibility of PCL blends with thermoplastic
starch (TPS) as a route to produce higher thermal resistance bioplastic blend. They found
that PCL has the tendency to encapsulate TPS in this blend. In addition, they found the
presence of strong hydrogen bonding interactions between the carbonyl groups of the
PCL and the hydroxyl groups on the starch. Tabasi and Ajji [17, 18] examined using PLA/
PCL blends for flexible film application and found that the addition of PCL reduced hot
tack initiation temperature and increased hot tack plateau seal strength (Figure 8.4).

8.5 Aliphatic polyesters and copolyesters

A large number of aliphatic polyesters and copolyesters are biodegradable polymers

that are produced from petroleum resources. Mochizuki [19] reviewed properties and
applications of aliphatic polyesters in detail. Among them, polybutylene succinate (PBS)
and copolyester of poly(butylene succinate/adipate), PBSA, received much attention.
Some previous studies have shown interesting properties for PBS and PBSA such as
 8.5 Aliphatic polyesters and copolyesters 123

100
1800
Hot-tack Plateau Initiation

Hottack Plateau Stregth

90
Temperature (°C)

1600

(gr/25mm)
80 1400

70 1200

60 1000

800
50
0 20 40 60 80 100
PCL Content (%)

Figure 8.4: The effect of addition of PCL on the hot tack properties of PLA/PCL blends [17].

higher oxygen and water vapor moisture [20]. Figure 8.5 shows the molecular structures
of PBS and PBSA.

O
O
O
O
n

O O
O
O O
O O
n m

Figure 8.5: Molecular structure of PBS (top) and PBSA (bottom).

Due to its copolymer nature, PBSA properties can be tailored by changing the ratio of
comonomers. For example, its melting temperature can vary from 115 °C (almost the
same as PBS) to below room temperature by increasing butylene adipate content [21].
Previous studies also showed that increasing butylene adipate content in PBSA increases
its biodegradation rate [22]. Lai et al. [23] studied the blending of PBS with TPS and
showed that adding glycerol as a compatibilizer/plasticizer is necessary in achieving
good dispersion. They also found a considerable increase in the crystallinity of PBS with
the addition of TPS as it played a nucleating role for PBS. Blends of PBS and PLA have
been shown to form an immiscible polymer blend [24, 25]. Despite its much better gas
barrier, the milky look of PBS films has limited its application especially in many food
packaging where transparency is needed. In addition, due to its high degradation rate,
124 Chapter 8 Bioplastic sealants

cautions have to be made when using PBS or PBSA as a sealant in contact with foods
that contain active bacteria such as yeasts as it can accelerate its degradation and result
in packaging failure [26].

8.6 Aromatic copolyesters

Compared to totally aliphatic copolyesters, aromatic copolyesters are often based on

terephthalic diacid. Among them, PBAT has received much attention. Figure 8.6 shows
the molecular structure of PBAT. It is a random copolymer of butylene adipate and
butylene terephthalate.

O
O O O
O
O
O O
n m

Figure 8.6: Molecular structure of PBAT: left sequence shows butylene adipate and the right segment
shows butylene terephthalate.

BASF commercialized PBAT with Ecoflex® trademark which is still the most known
trademark in the market. Aromatic copolyesters, like aliphatic copolyesters, degrade
completely in the microorganism environment. An increase of terephthalic acid content
tends to decrease the degradation rate [10]. Ecoflex biodegradation has been analyzed by
Witt et al. [27] but they could not find any indication for environmental risk (ecotoxicity)
of the composting residue of PBAT. A detailed review on Ecoflex properties and process-
ing was presented by Yamamoto et al. [28]. The low stiffness of PBAT has limited its use
in some applications. Previous studies showed the potential of blending PBAT with PLA
to achieve a balance between stiffness and toughness [29, 30]. Table 8.1 shows the effect
of different PBAT contents on properties of PLA/PBAT blends.

Table 8.1: Effect of the addition of PBAT on mechanical properties of PLA [29].

Sample composition Tensile Yield strength Elongation at Impact strength

modulus (MPa) (MPa) break (%) (J/m)

PLA , . . 

PLA/PBAT(/) ,   
PLA/PBAT(/) , .  
PLA/PBAT(/)    
 8.7 Polyhydroxyalkanoates (PHA) 125

PLA/PBAT blend was patented and commercialized under the trademark of Eco-
vio by BASF [31]. It has been found that the addition of chain extenders with epoxy
functional group improves processability and final mechanical properties in these
blends. Jalali et al. used different analysis techniques and showed that the PLA/PBAT
blend shows a complex partial miscible behavior [32]. Tabasi and Ajji examined the
heat seal properties of PLA/PBAT blends and showed that the addition of PBAT to PLA
is an effective approach in reducing the seal initiation temperature of the blend [13].
Blending of PBAT with TPS is another approach to improve its stiffness. This blend
was commercialized under the trademark of Mater-Bi by Novamont [33].

8.7 Polyhydroxyalkanoates (PHA)

Polyhydroxyalkanoate (PHA) is a family of bioplastics produced from microbial fermenta-

tion of carbon feed stock. Poly(hydroxybutyrate) (PHB) and poly(3-hydroxybutyrate-co-3-
hydroxyvalerate) (PHBV) are the most known members of the PHA family. Figure 8.7
shows the molecular structures of PHB and PHBV.

CH3 O
n

O O

CH3 O C2H5 O Figure 8.7: Molecular structures of PHB (top) and

n m PHBV (bottom).

PHB has high crystallinity and high melting point (~180 °C), which makes it an interesting
candidate to replace PP for high-temperature applications such as hot beverage or retort
applications. However, its brittle behavior and narrow processing window make the use
of PHB very challenging in flexible packaging [34]. PHBV has lower crystallinity and melt-
ing temperature (~145 °C), which allows easier processing of the resin; however, it does
not provide the same thermal resistance as of PHB.
126 Chapter 8 Bioplastic sealants

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[17] Tabasi, R.Y., Z. Najarzadeh, and A. Ajji, Development of high performance sealable films based on
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[18] Najarzadeh, Z., R.Y. Tabasi, and A. Ajji, Sealability and seal characteristics of PE/EVA and PLA/PCL blends.
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[19] Mochizuki, M. and M. Hirami, Structural effects on the biodegradation of aliphatic polyesters. Polymers
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[20] de Matos Costa, A.R., et al., Properties of biodegradable films based on poly (butylene succinate)(PBS)
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Chapter 9
Case studies

In this chapter, we present some examples of sealant design for different flexible
packaging applications. Some aspects that should be considered during designing
their sealant film in particular are reviewed. Presented equations in this chapter are
based on the following assumptions:
– No patterned jaw is used in the sealing.
– No seal imperfection exists in the package.
– The force that acts on the seal area during packaging is applied within a timescale
comparable to the timescale of the force applied during the seal/hot tack test.

It should be noted that these assumptions are critical to be able to establish a relation
between the seal test results and the required seal force in different applications. The
equations presented in this chapter should be used to provide guidelines for sealant
design and should be combined by considering different aspects related to the prod-
uct, film, and packaging methods.

9.1 Design of a peelable sealant for cereal packaging

You were asked to design a peelable film for packaging of 700 g cereal in a pillow
pouch with the dimensions of 35 × 25. Which of the following sealants can be used for
this application?

Table 9.1: Seal and Hot tack strength of peelable sealant materials for dry food
application.

Sealant material Seal strength (N/ mm) Hot tack strength (N/ mm)
name at jaw temperature at jaw temperature

AX- . .

AX- . .
AX- . 

9.1.1 Solution

Cereals are usually packaged on VFFS machines. The package filling process begins
when the jaws are sealing the bottom seal, but the jaws are opened before the comple-
tion of the filling cycle. This exposes the sealed area to the product weight while the
seal is still hot. This clearly indicates that hot tack strength of the sealant is important

https://doi.org/10.1515/9781501524592-009
130 Chapter 9 Case studies

during the packaging process of cereal and should be considered as the designing
parameter.
The required hot tack strength can be estimated by considering the force balance
around the seal area at the bottom of the package as visualized in Figure 9.1.

a b

Package walls

F F
ɵ

mg

Sealed area

Figure 9.1: (a) Bottom seal area in a filled package and (b) higher magnification of the marked area
around the sealed area in (a) with acting force vectors.

Using force balance at the seal area, we can obtain the following equation for the
force that is applied to the seal area:

0.025 × m.g
F= (9:1)
2W sin θ

where F is the required seal force, W is the package width, and θ is the angle between
the force vectors (F) and the product weight (see Figure 9.1(b)). It is worth mentioning
that the factor of 0.025 was used to obtain hot tack strength with the unit of N/25 mm.
When the package is filled with the product, θ is usually small and challenging to deter-
mine. However, by experience, 10° is very common in many different pillow pouch and
pinched bottom packaging. Using this assumption, equation (9.1) can be simplified as

0.072 × m.g
F= (9:2)
W

The required hot tack strength for packaging of 700 g cereal can then be estimated as
~2 N/25 mm. To ensure seal integrity, it is always recommended to consider a safety
factor in designing sealant materials. This means that selecting AX-01 is a risky choice
but both AX-02 and AX-03 should provide enough hot tack to handle 700 g of cereal.
Cereal packaging is made of films containing high HDPE content to provide high
moisture barrier needed for the product [1] as well as dead fold feature as a reclosure
option. However, high HDPE content in these films leads to a low tear resistance in
the bag length direction due to higher molecular orientation [2]. If the seal strength of
 9.3 Film for heavy-duty shipping sack (HDSS) 131

the sealant is high, such as for AX-03, the risk of package tear and failure during open-
ing by the final consumer is high. Therefore, among the presented options, selecting
AX-02 should provide the best solution for this application.

9.2 Sealant for liquid packaging

A customer asked for a sealant film to package 1.5 L of milk on the VFFS machine. The
package dimensions are 32.5 × 15 cm. Which of the following sealants will be your
recommendation?

Sealant material Seal strength (N/ mm) Hot tack strength (N/ mm)
name at jaw temperature at jaw temperature

BX-  (b) 
BX-  (p) 
BX-  (p) 
BX-  (b) 
✶
p, peelable; b, break.

9.2.1 Solution

Considering a density of ~1 kg/L for milk, the product weight can be estimated as
~1.5 kg. In the VFFS packaging of milk, the filling cycle begins when the jaws are closed
but it continues even after jaw opening. This indicates that the seal will be exposed to
the product weight while it is hot and therefore hot tack strength should be the first
design parameter [3]. Using equation (9.2), the required hot tack strength to withstand
1.5 kg of milk can be estimated as 7.35 N/25 mm. Considering the available options and
safety factor, BX-03 and BX-04 could be interesting options for the sealant.
For packaging of liquids, one should consider that the liquid can move in the
package during transportation and final use which compresses the air in the package
overhead space and can cause high stress on the seal area [4]. As a peelable feature
does not add a value for this application (milk packaging) and just increases the risk
of spillage, selecting BX-04 will be a safe option to ensure seal integrity during packag-
ing, transportation, and handling.

9.3 Film for heavy-duty shipping sack (HDSS)

A customer would like to package 10 kg of salt in a pillow-shaped bag with dimensions

of 46 cm × 30 cm. Which of the following films and what thickness can provide the
required performance?
132 Chapter 9 Case studies

Sealant material Film yield Seal strength (N/ mm) Price

name strength (MPa) at jaw temperature ($/lb)

CX-   (b) 
CX-   (b) .
CX-   (b) .

9.3.1 Solution

As heavy-duty sack (HDSS) bags are mostly premade (sealed and cut from the roll-
stock and then filled with product in the next step) and their bottom is supported dur-
ing and after the filling process, the filling process is not the step where the seal area
is exposed to the product weight. Palletization, transportation, and handling are the
steps where the seal needs to stay intact and protect the product in this application.
Therefore, seal strength should be considered as the main sealant design parameter.
Using equation (9.2), the minimum seal strength required to handle 10 kg of product
in this bag can be estimated as 24 N/25 mm. In HDSS application, the stress in the film
should not exceed its yield strength because of yielding and stretching of the film. In
order to avoid film stretching, the stress in the film should always be kept below 60%
of its yield strength. The stress in bag wall can then be estimated using the following
equation which considers this safety factor:

1.5 × F × W=0.025 1.5 × F

σ= = (9:3)
W ×b 0.025 × t

where b is the film thickness. Using F = 24 N/25 mm and yield strength of the films for σ,
the required thickness of the films can be estimated as 160 μm, 111 μm, and 144 μm for
CX-01, CX-02, and CX-03, respectively. By assuming a similar density for the films, these
results indicate that the quantity of CX-02 film needed to produce a certain number of
bags will be the lowest among the three films, and therefore, this will be the most eco-
nomic and sustainable (as it reduces the amount of plastic use) option for the application.

9.4 Peelable film for over-the-mountain packaging

A customer is looking for a peelable film to package snacks. As it will be shipped to a

destination at the altitude of 3,000 m, the package needs to provide hermetic seal for
over-the-mountain (OTM) packaging. The package is a pillow pouch with the dimen-
sions of 12.5 × 11 × 2.5 cm (Figure 9.2). What seal force do you recommend for the appli-
cation? What would be the seal force if the customer decides to send the package by
airplane?
 9.4 Peelable film for over-the-mountain packaging 133

9.4.1 Solution

In OTM applications, the package experiences high altitude or low outside pressures,
and the bag inflates as is schematically shown in Figure 9.2. Therefore, the objective
here is to evaluate the effect of pressure change on the seal integrity. If we consider
the bag as a tube, then the largest equator (D in Figure 9.2(b)) can be estimated using
the following equation:

2W
D= (9:4)
π

where W is the package width (Figure 9.2(a)). Using the package width of 11 cm, D can
be estimated as 7 cm for this package.

a b
Sealed Area
W
Sealed Area

L/2

D
H

Figure 9.2: (a) The cross section of a pillow pouch at room pressure and (b) the cross section
of the pouch in (a) inflated at high altitude due to the lower outside pressure.

Using the same concept as the hoop stress in the pipes [5] and by considering the
force balance between the applied pressure force to the package cross-sectional area
 2 
μD 4 , and the force induced in the package wall (or the film), we can obtain an
estimation formula for the force applied to the bottom and top-sealed area in the
package due to the pressure difference between outside and inside of the package:

ΔP × πD2 0.025 0.025 × ΔP × D

F= × = (9:5)
8 πD 8
where ΔP is the pressure difference between outside and inside of the package, and D is
the largest equator of the cross section of the inflated bag determined from equation
(9.3). It should be noted that 0.025/πD was multiplied to obtain seal strength with the
unit of N/25 mm.
The air pressure at 3,000 m altitude can be estimated using the Laplace barometric
formula [6] as 70.1 kPa. By assuming that the package was filled at the sea level, a
134 Chapter 9 Case studies

pressure difference of 31.2 kPa between outside and inside of the package can be esti-
mated at the destination. Using equation (9.6), the required seal strength can then be esti-
mated as 6.8 N/25 mm. This should be considered as the minimum required peel force.
When the customer uses airplanes to ship, we should consider that nonpressurized
feeder aircraft typically fly at approximately 4,500 m altitude. The air pressure at this
altitude can be estimated as 57.7 kPa which leads to a pressure difference of ΔP = 43.6 kPa
during shipping. Using equation (9.5), we can estimate the minimum required seal force
as 9.5 N/25 mm. These results clearly point to the importance of the knowledge of package
transportation method when designing a package specially for light weight air-filled
products such as snacks.

9.5 Sealant film with caulkability for spouted pouch application

You were asked to select a sealant material for 90 and 250 mL spouted pouches filled
with apple puree that can provide caulkability around the fitment. Figure 9.3 schemat-
ically shows the pouch. They are made in a form fill seal machine where the three
sides are sealed and then the pouch is filled from the top and finally capped spouts
are inserted and sealed from the top. Figure 9.4 shows the viscosity curves of the
Channelling

Figure 9.3: (Left) Spouted pouch: the spout is shown as the gray area at the top with the twist cap
connected to it. Two arrows show spout corners. (Right) Top view of the spout pouch shown in left with
arrows showing spout corners with channels between the films.
 9.5 Sealant film with caulkability for spouted pouch application 135

SF-1
SF-2
Viscosity (Pa.s)

SF-3

0.1 1 10 100
Shear rate (S–1)

Figure 9.4: Viscosity curves of three sealants available for spouted pouch application.

available options for the sealant materials. Which sealant and at what thickness
would you recommend for this application?

9.5.1 Solution

One of the major week points of spouted pouches is on the edge of the spout part of
the fitment which are shown with arrows in Figure 9.3. In these areas, as the two seal-
ants are joined at the corner of the spout, a high chance of channeling exists that can
result in product spillage after filling. In order to ensure that the sealant material
flows and fills the gap at the corners of the spout, a sealant with high caulkability or
squeeze-out flow (SOF) is needed for this application. As discussed in Chapter 6, pre-
cise comparison of SOF between sealants requires simultaneous simulation of heat
and squeeze flow. However, as was shown by Kanani Aghkand and Ajji [7], the shear
rate of SOF in a wide range of sealing pressure falls between 1 and 10 s−1. Using this
rule of thumb, although SF-2 has a higher zero-shear viscosity, it should provide a bet-
ter caulkability as it has the lowest viscosity in this shear rate range.
As was also shown in Chapter 6, in addition to sealant melt viscosity, increasing
sealant thickness is a very efficient approach in enhancing SOF. Kanani Aghkand and
Ajji [7] showed that while 50 μm sealants showed little SOF (1–2%) even at low viscosi-
ties, increasing sealant thickness to above 100 μm could improve significantly SOF
(~25%). In spouted pouches, the size of the pouch indicates the size of the spout that
should be used; the larger the pouch, the larger will be the spout and more precau-
tions need to be taken when designing the sealant. For small product volumes such as
90 mL, standard spouts of 8.6 mm diameter are very common while for 250 mL
pouches, 10 or even 16 mm spout are used. This indicates that while 50 μm sealant
could be enough to provide reliable sealing around the spout in 90 mL pouches, a
thicker sealant of 75 um should be used for 250 mL format to avoid channeling
around the spout.
136 Chapter 9 Case studies

9.6 Peelable barrier film for dried seeds packaging

A customer asked for a peelable film to package 1 kg of dried round-shaped seeds in a

pillow pouch. The pouch has dimensions of 35 × 25 cm. The seeds have an initial mois-
ture content of 5% and their maximum allowed moisture content is 10%. Determine
which of the following sealants could be a good option for this pouch if one year of
shelf life is needed for this product.

Table 9.1: Different sealant options for packaging round seeds products.

Sealant Seal strength Yield strength Water vapor permeability✶ Price

(N/ mm) (MPa) (g μm/(m day atm)) ($/lb)

B- .   $

B-    $$$
B- .   $$
✶
At 38 °C and 90% relative humidity (RH).

9.6.1 Solution

In the case of barrier films, two main possible scenarios could happen and are shown
in Figure 9.5. The first scenario (Figure 9.5(a)) is where the humidity inside of the
package is higher than the outside. Packaging of moist products or freezer applica-
tions are examples of this scenario. Here, the goal for barrier packaging is to avoid
moisture loss from the package. The second scenario (Figure 9.5(b)) is where the hu-
midity inside the package is lower than the outside. In this case, the goal is to prevent
moisture penetration into the package. Cereal, dried seeds and dried fruits, flours,
and sugar are some examples of this scenario.
Similar to example 1 in this chapter, the required seal force for 1 kg of product
can be estimated as 2.9 N/25 mm using equation (9.2). This indicates that B-01 could
not be a reliable option as its average seal strength is close to the minimum seal re-
quirement. Reformulating equation (9.3) and by using the yield strength of different
film options listed in Table 9.1, the required thickness to withstand the force applied
by the product weight can be estimated by
1.5 × F
t= (9:6)
0.025 × σ

This results in film thicknesses of 17.4 μm and 15.8 μm for B-02 and B-03 films,
respectively.
In order to verify moisture barrier requirements, we can use the transmission
rate formula [8]:
 9.6 Peelable barrier film for dried seeds packaging 137

(a) (b)
Polymer film Polymer film

H 2O
H2O

Oxygen Oxygen

Figure 9.5: (a) Moist products where moisture or other atmospheric gases permeate out of the package
and oxygen permeates toward inside the package; (b) dried products where moisture and oxygen
permeate toward inside of the product. The color gradients represent schematically the concentration
gradients.

q
TR = (9:7)
t × A × Δp

where TR is the transmission rate (g/(m2 day atm)), q is the quantity of permeant, t is
the permeation time, A is the package surface area, and Δp is the partial pressure differ-
ence between outside and inside of the package. As the allowed moisture intake is 5%
of the product weight, the quantity of the allowed moisture intake can be calculated as
50 g. To achieve a precise design, the average temperature and humidity that the pack-
age experiences during its life cycle should be considered in permeation calculations
but as the water vapor transmission rate (WVTR) measurements are commonly done
by ASTM F1249 or ASTM E96 at 38 °C and 90% RH, we will use these conditions to deter-
mine the shelf life. Considering 50 mmHg or 0.0655 atm for the saturation water vapor
pressure at 38 °C [9], the partial water vapor pressure at RH = 90% can be estimated as
0.059. Then the maximum allowed transmission rate for 365 days for the package with
0.175 m2 surface area can be calculated as 13.2 g/(m2 day atm).
Transmission rate and permeability can be related by the following equation:
Pr
TR = (9:8)
thickness

where Pr is the permeability of the film. Considering the water vapor permeability
of B-02 and B-03 and the estimated film thickness, we achieve WVTR of 7.2 and
17.5 g/(m2 day atm), respectively. These results may imply that B-03 is not a good option
for this application. However, as mentioned in the beginning of this chapter, these
138 Chapter 9 Case studies

calculations should be used as guideline and should not be solely used to design without
considering technology limitations and application considerations. For example, most
peelable technologies require a minimum of 5–10 μm of the peelable layer thickness to
perform as expected. Considering a three-layer structure with 25% peelable layer ratio,
this leads to a minimum thickness requirement of 20–40 μm. Considering an average
thickness of 30 μm, both B-02 and B-03 can provide enough moisture barrier for the
application. By comparing their prices, it can be concluded that B-03 is actually a better
choice for this application.

9.7 Oxygen barrier sealant for cheese packaging

A customer would like to package 2.3 kg of grated parmesan cheese in a pillow pouch
format with dimensions of 40 × 30 cm. The package is filled on a VFFS machine and
should provide 120 days of shelf-life. Which of the following films could be the choice
for this application by considering a maximum of 5 ppm allowed oxygen intake before
spoilage?

Hot tack Yield strength Oxygen permeability Price

(N/ mm) (MPa) (cc.  μm/(day m atm)) ($/lb)

BO-   . $
BO-   . $$
BO-   . $$

9.7.1 Solution

As mentioned in the previous examples where the product is packaged by VFFS, the hot
tack strength should be considered as the sealant design parameter. Using equation (9.2),
the required hot tack to handle 2.3 kg of the product can be estimated as 5.75 N/25 mm.
Using equation (9.6), the minimum film thickness required for the three above options to
handle this force can be estimated as 34.5, 28.7, and 31.3 μm for BO2-1, BO2-2, and BO2-3,
respectively.
In order to examine oxygen permeation to achieve the desired shelf-life, we first
need to determine the volume of oxygen gas intake. Considering the maximum al-
lowed oxygen intake of 5 ppm and by assuming no oxygen presence inside the pack-
age initially, the volume of the allowed oxygen can be determined using the following
equation:
 9.8 Film for frozen vegetables 139

 
Allowed O2 intakeðppmÞ × 10−6 × product weight ðgÞ × gas molar volume L
q=  g  mol
Gas molecular weight mol

5 × 10−6 × 2,300 × 22,400

q= = 8.05 cc (9:9)
32

Now by considering the package surface area of 0.24 m2, the transmission rate can be
calculated as follows:
8.05 cc cc
TR = = 1.33 2
120 days × 0.24 m2 × 0.21 atm m day atm

Using equation (9.8), the transmission rate of the available film options with the thickness
cc
determined earlier can be estimated as 2.3, 1.4, and 1.04 m2 day atm
for BO2-1, BO2-2, and
BO2-3, respectively. These results indicate that BO2-2 at ~30 μm should provide both me-
chanical strength and oxygen barrier properties needed for the application.

9.8 Film for frozen vegetables

You were asked to design a 50 μm film for packaging of 2.5 kg of frozen vegetable mix.
The package is a pillow pouch with the dimensions of 37 × 23 cm.

9.8.1 Solution

Using the film thickness and the package dimensions, the force that is applied to the
seal area can be estimated using equation (9.2):
0.072 × 2.5 × 9.8 N
F= = 7.67
0.23 25 mm

Then using equation (9.3), we can determine the yield strength needed from the film:
1.5 × 7.67
σ= = 9.2 MPa
0.025 × 50 × 10−6

It should be considered that this is the required yield strength of the film at the appli-
cation temperature (−18 °C). As reducing temperature increases the yield strength of
plastic materials [10], a lower yield strength at room temperature would be enough to
handle the product weight. The variation of the yield strength by temperature has not
been formulated due to the effects of different parameters such as chain microstruc-
ture, molecular weight, and molecular weight distribution.
Another aspect that needs to be verified for this application is the bag drop test. In
this test, the product is taken out of the fridge and dropped from 3 to 5 ft height to ensure
140 Chapter 9 Case studies

package integrity. Although designing frozen packaging might not be straightforward be-
cause of temperature, as a rule of thumb, PE-based packages for frozen food should be
composed of major phases of low-density PE with the density of 0.910–0.92 g/cm3. There-
fore, the proposed film for the application in question could be any available low density
film with seal force above 7.7 N/25 mm and yield strength of 9.2 MPa.

References

[1] Ebnesajjad, S., Plastic Films in Food Packaging: Materials, Technology and Applications. 2012, William
Andrew.
[2] Tabatabaei, S.H., et al., Effect of machine direction orientation conditions on properties of HDPE films.
Journal of Plastic Film & Sheeting, 2009. 25(3–4): p. 235–249.
[3] Clark, T.A., and J.R. Wagner Jr, Film properties for good performance on vertical form-fill-seal packaging
machines. Journal of Plastic Film & Sheeting, 2002. 18(3): p. 145–156.
[4] Umezaki, E., Y. Shinoda, and K. Futase. Liquid behavior in containers with a liquid-packing bag for
liquid products subjected to drop impact. In Key Engineering Materials. 2006, Trans Tech Publ.
[5] Chasis, D.A., Plastic Piping Systems. 1988, Industrial Press Inc.
[6] Mechtly, E., The International System of Units: Physical Constants and Conversion Factors. Vol. 7012.
1964, Scientific and Technical Information Division, National Aeronautics and . . . .
[7] Kanani Aghkand, Z., and A. Ajji, Squeeze flow in multilayer polymeric films: Effect of material
characteristics and process conditions. Journal of Applied Polymer Science, 2022. 139(13): p. 51852.
[8] Koros, W.J., Barrier polymers and structures: Overview. In Barrier Polymers and Structures, 1990,
American Chemical Society. p. 1–21.
[9] Thomson, G.W., The Antoine equation for vapor-pressure data. Chemical Reviews, 1946. 38(1): p. 1–39.
[10] Landel, R.F., and L.E. Nielsen, Mechanical Properties of Polymers and Composites. 1993: CRC press.
Index
1-Butene 52 Cellulose 1
1-Hexane 52, 53 Cereal Packaging 129
1-Octene 52, 53 Chain Diffusion 14
Chain Dynamics 18
Abuse Layer 41, 80, 81 Chain Extender 125
Acid Copolymer 58 Chain Mobility 17
Acidic Foods 49 Chain Pull-Out 66
Adhesive Peeling 40, 43 Cheese Packaging 138
Adjacent Reentry 23, 25 Chemical Resistance 49, 58
Airborne Ultrasound 37 Clarity 15, 25, 26, 39, 50, 52, 56, 121
Aliphatic Polyesters 122 Coalescence 105–107
Alox 1 Coating 1
Alpha Olefin Copolymer 52, 53, 54, 74 Cohesive Peeling 40, 43, 111, 112
Aluminum 4 Compatibility 103
Aluminum Foil 59 Compostable 119–121
Amorphous 15, 26, 52, 56, 71 Comsol 80–83, 88, 93
Amorphous PET, aPET 61 Consistency Index 91
Antioxidant 50 Cooling Rate 26
Aromatic Copolyesters 124 Cooper−Mikic−Yovanovich Model, CMY model 81
Atactcic PP, aPP 55, 56 Cox–Merz Law 60
Crack Healing 94
Barrier 1, 49 Creep Test 45
Belt Pick-Up 7 Creep To Failure 45
Biaxially Oriented PP, BoPP 56 Critical Capillary Number 105
Bio-Based PE, Bio-PE 120 Critical Nucleus 24
Bio-Based Polyethylene Terephthalate, Bio-PET 120 Cross-Linking 15
Biodegradable 119–122 Crystal Growth 23, 25
Bioplastics 119, 120, 125 Crystal Nuclei 23
Blending 54, 58, 101, 121–124 Crystal Structure 15, 23
Block Bottom 7 Crystallinity 50, 52, 53, 55, 56, 69, 71, 84, 93, 121,
Bopet 61, 122 123, 125
Bottom Seal 6 Crystallization 15, 23, 25, 39, 77
Breakup 105
Brittle Sealing 31 Dancer Arm 6,7
Brownian Motion 95 Degradation 49
Bubble Test 34 Delamination 41
Bu-LLDPE 53 Delay Time 40
Burst Test 44, 46 Detergent 49
Diffusion Coefficient 19, 21, 95, 96
Cap Sealing 4 Disentanglement Time 20, 94
Capillary Number 105 Dwell Time 5, 14, 18, 40, 63, 66–69, 77, 81, 85,
Carreau–Yasuda Fluid Model 90, 91, 93 87, 96
Cast Polypropylene, cPP 56 Dye Penetration Test 36
Caulkability 69, 85, 86, 101, 111, 134, 135 Dynamic Scanning Calorimetry, DSC 16, 17, 25,
Cellophane 1 52, 71

https://doi.org/10.1515/9781501524592-010
142 Index

Ecoflex 124 Heat Conduction 80

Ecovio 125 Heat Convection 80
Entanglement 15, 19, 39, 50, 66, 67, 72–74 Heat Flux 82
Entanglement Time 20 Heat Of Fusion 16, 17, 71, 82
Enthalpy 15 Heat Sensitive 58
Enthalpy Of Crystallization 24 Heat Transfer 14, 15, 23, 82, 85, 87, 91, 96
Enthalpy Of Mixing 101, 102 Heat Transfer Coefficient 80
Entropy 15 Heavy-Duty Sack, HDSS 131, 132
Entropy Of Mixing 101, 102 Heterogeneous Nucleation 24, 25
Ethylene Vinyl Acetate, EVA 1, 56–58, 63, 71, Hex-LLDPE 53
109, 113 HFFS Pouch Machine 7,8,9
Ethylene-Acrylic Acid, EAA 58, 59 High-Density Polyethylene, HDPE 50, 63, 65, 67, 69,
Ethylene–Methacrylic Acid, EMA 58, 59, 113 71, 85, 107, 129
Exothermic 25 High-Pressure Tubular Reactor 50
Extrusion Coating 59 Homogeneous Nucleation 23, 24, 25
Hookean Springs 19, 20
Failure Mode 40 Horizontal Form Fill And Seal, HFFS 5,7,8, 39
Fibrillar Morphology 105, 107 Hot Air 5
Fin Seal 5,6 Hot Tack 15, 22, 38, 39, 53, 58, 59, 61, 63, 66, 67,
Final Plateau Temperature, Tpf 65 69, 72, 73, 93, 94, 103, 104, 122, 129, 130, 138
Finite Difference Method, FDM 91 Hydrogen Bonding 58, 102, 122
Finite Element Method, FEM 82 Hydrophobic 49
Flat Bar Test 33
Flexural Strength 43 Immiscible Polymer Blends 101, 102, 107, 109, 123
Flow Wrapper 7,8,9 Impulse Sealing 9
Folded Chain Model 23 Induction Chamber 4
Forming Collar 6 Induction Sealing 4
Forming Tube 5,7 Interdiffusion 13–15, 17, 18, 22, 51, 54, 77, 93–95
Fourier Transform Infrared, FTIR 50, 54, 57, 58, 60 Interdigitation Time 22
Fourier’S Law 82 Interface Healing 18
Fracture Energy 94, 95 Interface Temperature 14,15, 63, 77–80, 82, 85,
Fracture Stress 94, 95 94, 96
Free Volume 22, 64, 83 Interfacial Tension 103, 105–109, 112
Intermittent VFFS 7
Gap Conductance 80 Intermolecular Interactions 15
Gas Conductivity 81 Internal Pressurization Failure Resistance 44
Gaussian Chain 19, 20 Iodopovidone 36
Geometric Mean 103 Ionomer 59–61, 111
Gibbs Free Energy 15 Isotactic PP, iPP 55, 56
Gibbs’S Free Energy Of Mixing 101
Glass Transition Temperature, Tg 59, 69, 81, 122 Jaw Draw-Off 7
Grease Resistance 61
Gross Leak 34 Knife 7
Gusset 8, 9, 33, 36
Lamellar Morphology 105, 107
Harkins’ Equations 107 Lap Seal 5,6
Harmonic Mean 103 Laplace Law 106
Headspace Gas 34 Leakage 32, 36
Heat Bar Sealing 4 Lidding 4
 Index 143

Linear Low-Density Polyethylene, LLDPE 51, 63–65, Nucleating Agent 56

69, 80–82, 102 Nucleation 23
Liquid Packaging 130
Lock Seal 41, 65, 112 Oct-LLDPE 53
Long Chain Branches, LCB 50, 72, 73, Optimization 77
102, 103 Organically Modified Montmorillonite, oMMT 112
Low-Density Polyethylene, LDPE 50, 65, 67, 69, Orientation 17, 56, 61, 129
102, 110 Oversealed Area 31
Lubricating Assumption 88 Over-The-Mountain, OTM 132, 133
Oxygen Barrier 50, 139
Mater-Bi 125
Mean Square Displacement 19 Partially Miscible Polymer Blends 101, 125
Mechanical Sealing 2 Peelable 41, 63, 110–112, 129, 132, 133, 136
Mechanical Strength 50, 56, 61, 121 PE-g-MA 83, 84, 112
Melt Strength 51, 52, 60, 121 Permeation 49, 137
Metallocene Catalyst 54 Pharmaceutical 61
Metallocene Polyethylene, mPE 53, 58, 69, 72. 73, Pinholes 32
102, 103, 111 Plastomers 54, 71, 111
Microbial Ingress 31 Plateau Initiation Temperature, Tpi 65, 71, 96
Microbubbles 32 Plateau Seal Strength 65
Microchannels 31 Poly(3-Hydroxybutyrate-Co-3- Hydroxyvalerate),
Microhardness 81 PHBV 125
Micro-Roughness 13, 67, 80 Poly(Butylene Adipate-Co-Terephthalate),
Migration 49 PBAT 107, 119, 124
Minimum Inflation Pressure 34 Poly(Butylene Succinate/Adipate), PBSA 122
Misalignment 31 Poly(Ethylene Terephthalate), PET 1, 17, 61, 120
Miscible Polymer Blends 101, 102 Poly(Hydroxybutyrate), PHB 125
Modeling 77 Poly(Lactic Acid), PLA 107, 121–125
Moisture Barrier 1, 49, 50 Polyamide, PA 1, 81, 83
Moisture Sensitive 61 Polybutene-1, PB-1 110
Molecular Architecture 49, 52, 54, 72 Polybutylene Succinate, PBS 122
Molecular Mobility 14, 15, 25, 54 Polycaprolactone, PCL 122
Molecular Weight Distribution, MMD 16, 17, 21, 53, Polyethylene, PE 1, 17, 49, 109, 110, 119
72, 93, 139 Polyhydroxyalkanoates, PHA 125
Molecular Weight, Mw 16, 17, 19, 20, 21, 56, 72–74, Polymer Blends 101
93, 102, 139 Polymer Hardness 14
Monoaxially Oriented PP, MoPP 56 Polypropylene, PP 1, 17, 54, 56, 69, 71, 109, 125
Morphology 60, 63, 101, 104, 107, 111, 122 Polystyrene, PS 17, 107
Multicomponent Sealant 101 Polyvinyl Chloride, PVC 1
Multiwall Paper Bags, MWPB 3, 50 Polyvinylidene Chloride, PVDC 1
Power-Law Index 91
Nanocomposite 112 Power-Law Model 90
Narrow Seals 31 Pressure Decay Leak Test 35
Newtonian Fluid 86, 87, 93 Pressure-Assisted Dye Penetration Test 37
Niche Distance 25 Primary Crystals 23
Nichrome 9 Printability 61
Nitrocellulose 1
Nonisothermal Crystallization 23 Radical Polymerization 50, 56
Non-Newtonian Fluid 86 Radius Of Gyration 22, 96
144 Index

Random Copolymerization 51, 124 Surface Tension 103

Recrystallization 13 Surface Wetting 17, 67, 94
Relaxation Time 19, 20 Switchboard Model 23, 25
Reptation Model 20, 21, 67, 94 Syndiotactic PP, sPP 55, 56
Rigid Containers 4
Rotating Heated Seal Bar 9 Tacticity 55, 56
Rouse Model 18, 19, 20, 21 Temperature Gradient 78, 82
Rouse Relaxation Time 20 Temperature-Modulated DSC, TMDSC 52, 84
Temperature-Sensitive Materials 3
Scaling Law 94 Tensile Machine 44
Seal Initiation 53 Terminal Relaxation Time 96
Seal Initiation Temperature, Tsi, SIT 65, 67, 71–74, Thermal Conductivity 15, 79, 82–84
93, 102, 107, 109, 111, 122, 125 Thermal Contact Resistance, TCR 80, 81
Seal Performance Test 31, 38 Thermal Contact Theory 80
Seal Quality Tests 31 Thermal Diffusivity 87
Seal Strength 23, 39, 42, 56, 63, 93–96, 102, 109, Thermal Oxidation 54
122, 129, 132 Thermal Stability 49
Seal Through 61 Thermodynamics 15, 23, 101, 107, 108, 112
Sealant Materials 49 Thermoplastic Starch, TPS 122, 123, 125
Sealing Pressure 5, 14, 63, 67, 82, 85, 92 Transport Belts 6
Sealing Temperature 5, 63, 66, 67, 69 Twin-Jaw Continuous Motion 7
Sealing Window 65, 101
Serrated Jaws 5 Ultrasonic Anvil 2,3
Shear Rate 105 Ultrasonic Horn 2,3
Short Chain Branches, SCB 51, 72, 73 Ultrasonic Sealing 2, 50
Side-Chain Groups 51, 53 Unsealed Area 31
Simulation 77, 81, 88
SiOx 1 Vacuum Decay Leak Test 36
Sonotrode 3 Vacuum Packing 34
Specific Heat 79, 82, 83, 85 Vacuum Transport Belts 7
Specific Volume 16 Vertical Form Fill And Seal, VFFS 5,6,7, 39, 129,
Spherulites 56 130, 138
Spouted Pouch 134, 135 Vertical Sealer 5
Spreading Coefficients 108 Very Low Density Polyethylene (vLDPE) 69, 109
Springback Force 39 Viscosity 19, 20, 87, 88, 105, 108, 111, 113
Squeeze Out Flow, SOF 65, 67, 69, 77, 85–93, 135 Visual Inspection 33
Statistical Segment 19
Steric Hindrance 56 Water Vapor Transmission, WVTR 137
Sterilization 31 Welding 2, 22
Subcritical Nuclei 24 Work Of Adhesion 103
Supercooling 23, 25
Supercritical Nuclei 25 Young’S Model 112, 113
Surface Asperities 15, 17,50, 81, 87
Surface Impurities 18 Zero Shear Viscosity 21, 85
Surface Rearrangement 15, 17, 18 Ziegler–Natta 53, 54
Surface Roughness 17, 81 Zipper 9