f65b6d0f-ad4b-4ae7-b0c1-53bd6374af46

FOOD
PACKAGING
MATERIALS
FOOD
PACKAGING
MATERIALS
Testing & Quality Assurance
Edited by
Preeti Singh • Ali AbasWani •
Horst-Christian Langowski
CRC Press
Taylor & Francis Group
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Library of Congress Cataloging-in-Publication Data
Names: Singh, Preeti (Materials scientist) | Wani, Ali Abas. | Langowski,

Horst-Christian.
Title: Food packaging materials : testing & quality assurance / [edited by]
Preeti Singh, Ali Abas Wani, Horst-Christian Langowski.
Description: Boca Raton : CRC Press, 2017. | Includes bibliographical
references and index.
Identifiers: LCCN 2016059197 | ISBN 9781466559943 (hardback : alk. paper)
Subjects: LCSH: Food containers. | Food–Packaging–Quality control. |
Packaging–Testing.
Classification: LCC TP374 .F687 2017 | DDC 664/.09–dc23
LC record available at https://lccn.loc.gov/2016059197
Visit the Taylor & Francis Web site at

http://www.taylorandfrancis.com
and the CRC Press Web site at

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Contents
Preface......................................................................................................................vii
Editors .......................................................................................................................ix
Contributors ..............................................................................................................xi
Chapter 1
Introduction: Food Packaging Materials....................................................................1
Ali Abas Wani, Preeti Singh, and Horst-Christian Langowski
Chapter 2
Shelf Life of Packed Food and Packaging Functionality ........................................11
Chapter 3
Testing of Physical, Optical, Electrical, Thermal, and Rheological Properties
for Plastic Packaging Materials................................................................................67
Young T. Kim, Hezhong Wang, and Byungjin Min
Chapter 4
Testing of Mechanical Properties for Plastic Packaging Materials........................ 103
Laszlo Horvath, Byungjin Min, and Young T. Kim
Chapter 5
Permeation Testing of Synthetic Polymers ............................................................123
Ayman Abdellatief and Bruce Welt
Chapter 6
Testing Glass as a Food Packaging Material .........................................................139
Khalid Gul, Haroon Maqbool Wani, Preeti Singh,
Idrees Ahmed Wani, and Ali Abas Wani
Chapter 7
Metal Packaging: Testing and Quality Assurance .................................................155
Heinz Grossjohann, Alex Grossjohann, Thomas Duve,
and Maura Marcks
v
vi CONTENTS
Chapter 8
Testing of Paper as Packaging Material for Food Industry ...................................185
Shabir Ahmad Mir, Haroon Maqbool Wani, Idrees Ahmed Wani,
Preeti Singh, and Ali Abas Wani
Chapter 9
Testing and Quality Assurance of Bioplastics ....................................................... 201
Manzoor Ahmad Shah, Markus Schmid, Ankit Aggarwal,
and Ali Abas Wani
Chapter 10
Shock and Vibration Testing of Packaging Materials ...........................................233
Robert Meisner and Dennis Young
Chapter 11
Testing Migration from Food Packaging Materials ...............................................251
Annika Ebert, Roland Franz, Carina Gehring, Diana Kemmer,
and Frank Welle
Chapter 12
Food Package Testing Authorities and Regulations ..............................................303
Angela Störmer and Keun Taik Lee
Index ......................................................................................................................333
Preface
Food packaging is vital for providing physical protection, preventing post process
contamination, extending shelf life, and communicating vital information to the con-
sumer. Food packaging is of paramount significance in preserving the quality of fresh
and processed foods. It would be practically impossible for food processors to distri-
bute food without packaging. Developments in packaging have moved beyond these
basic packaging functions. Introduction of new packaging methods, such as modified
atmosphere packaging, active packaging (oxygen scavenging, antimicrobial activity),
and intelligent technologies, have performed beyond basic functions; have increased
product quality, safety, and shelf life beyond consumer expectations; and have furth-
ered outreach to distant markets. A variety of packaging materials and technologies
are in use to extend the shelf life of food products. Packaging design and material
properties determine the end use of a package and the shelf life of packaged foods.
Glass, paper, metal, and plastics are the most important groups of materials used
for food packaging. Plastic or polymer-based packaging is still the most widely
used in the food industry, but developments in bio-based packaging are gaining
importance in order to reduce pollution and improve environmental sustainability.
Material properties (e.g., mechanical, permeability, sealing, and food contact
material migration) have significant impact on food quality, shelf life, and safety.
Therefore, food packaging materials are tested to ensure that they have correct gas
and water permeability, an appropriate tin or lacquer layer, thickness, and strength.
Furthermore, new regulations for ensuring the safety of packaging material and pro-
ducts in key industries such as food, cosmetics, and pharmaceuticals have resulted in
increasingly complex legislation that varies by region and country. Additional risks
due to additives in coatings, inks, or adhesives and the use of recycled fibers and plas-
tics, epoxy resins such as bisphenol A in cans, and the reuse of plastic containers all
cause safety concerns. Therefore, food packaging needs to be rigorously tested, and
potential risks mitigated before market entry.
There is a limited number of books on food package testing; therefore, this book
has been designed to shed light on food packaging material testing, shelf life, and
regulations on package testing. This comprehensive handbook, written by a team
of specialists in the specific areas of food packaging, package testing, and food
regulations, will broaden knowledge dealing with problems in package testing in
a series of well-defined chapters on plastics, metal, glass, and paper, so that all
those involved with the production or use of this significant knowledge may obtain
reliable information. This book also covers the areas of vibration, permeation, and
material migration tests and will benefit students, scientists, and professionals in the
area of food packaging.
We are thankful to our contributors for their cooperation and support of this book
project. We also thank the families of our contributors for their support and encour-
agement throughout this project. Our special thanks go to Stephan Zollo, senior editor,
CRC Press/Taylor & Francis Group, for his encouragement and professional advice.
vii
Editors
Preeti Singh has obtained her master’s degree (food technology) and PhD (dairy
technology) from leading institutions in India. She has worked as a scientist at Defence
Food Research Laboratory in Mysore, India, for 2 years. In 2008, she joined the chair of
Food Packaging Technology, Technical University of Munich (TUM), as a research
scientist. Later, she joined the Fraunhofer Institute for Food Process Engineering and
Packaging IVV, Freising, Germany. She has been actively publishing on food packa-
ging, contributing 28 international papers and 15 technical papers, and is currently
coeditor of two forthcoming books on packaging. She is also managing editor of
Food Packaging & Shelf Life, published by Elsevier Science, UK.
Ali Abas Wani is a senior researcher at the Fraunhofer Institute for Process Engi-
neering and Packaging, Freising, Germany. Born and educated in India, he
received his master’s degree (food technology) and PhD (food technology)
from leading Indian universities. Since 2006, he has been a senior assistant pro-
fessor at the Islamic University of Science and Technology, Awantipora, India,
where he was responsible for establishing the Department of Food Technology
and also initiated several key food science programs in the region. Additionally,
he is establishing a food testing center at the Islamic University of Science and Tech-
nology, Awantipora. Dr. Wani is also a cochair for the European Hygienic Engineer-
ing Design Group (EHEDG) representing the Indian regional section. He is the
cofounder and editor-in-chief of Food Packaging & Shelf Life, published by Elsevier
Science, UK. Dr. Wani has published numerous international papers, book chapters,
coedited books, and conference papers. His research focus is on the development of
functional ingredients and measurement of food quality. In addition to close associa-
tion with many scientific organizations in the area of food science and technology, he
is an active reviewer for Carbohydrate Polymers, Food Chemistry, LWT–Food
Science and Technology, Journal of Agricultural Food Chemistry, and many other
scientific journals of repute.
Horst-Christian Langowski is a professor and the chair of Food Packaging Tech-

nology, Dean of Studies, at the TUM School of Life Sciences Weihenstephan,
Technical University of Munich (TUM), and the director of the Fraunhofer Institute
for Process Engineering and Packaging, Fraunhofer IVV, Freising, Germany.
He received his diploma degree in physics in 1980 and PhD in 1989, both from
the University of Hannover, Germany. He worked with the Philips Group from
1981 to 1991 as a development engineer and project manager before joining
Fraunhofer IVV in 1991. Since then, he has been deeply involved in food packaging
and shelf-life research at both TUM and Fraunhofer IVV. Professor Langowski has
received numerous research grants and presented his work at several international
conferences. He has published many research papers, technical papers, patents, and
book chapters, and has supervised many master’s and doctoral theses. Among other
ix
x EDITORS
functions, he is a member of the management board of the Bayerische

Staatsbrauerei Weihenstephan and a member of the advisory board of the group
on extrusion technology within the Verein Deutscher Ingenieure (VDI). He is
also the cofounder and editor-in-chief of Food Packaging and Shelf Life, which
is published by Elsevier Science, UK.
Contributors
Ayman Abdellatief Laszlo Horvath
Packaging Engineering Program Department of Sustainable
Department of Agricultural and Biomaterials, Packaging Systems
Biological Engineering and Design
University of Florida Virginia Polytechnic Institute and
Gainesville, Florida State University
Blacksburg, Virginia
Ankit Aggarwal
Fraunhofer Institute for Process Diana Kemmer
Engineering and Packaging IVV Fraunhofer Institute for Process
Freising, Germany Engineering and Packaging IVV
Freising, Germany
Thomas Duve
CMC-KUHNKE GmbH
Young T. Kim
Berlin, Germany
Department of Sustainable
Annika Ebert Biomaterials, Packaging Systems
Fraunhofer Institute for Process and Design
Engineering and Packaging IVV Virginia Polytechnic Institute and
Freising, Germany State University
Roland Franz
Fraunhofer Institute for Process Horst-Christian Langowski
Engineering and Packaging IVV Chair of Food Packaging Technology
Freising, Germany TUM School of Life Sciences
Weihenstephan
Carina Gehring Technical University of Munich
Fraunhofer Institute for Process Freising, Germany
Engineering and Packaging IVV
Freising, Germany Keun Taik Lee
Department of Food Processing and
Alex Grossjohann
Distribution
CMC-KUHNKE GmbH
Gangneung-Wonju National University
Berlin, Germany
Gangneung, Republic of Korea
Heinz Grossjohann
CMC-KUHNKE GmbH Maura Marcks
Berlin, Germany CMC-KUHNKE GmbH
Berlin, Germany
Khalid Gul
Department of Food Technology Robert Meisner
Islamic University of Science and Packaging Programme
Technology University of Wisconsin Stout
Awantipora, India Menomie, Wisconsin
xi
xii CONTRIBUTORS
Byungjin Min Ali Abas Wani

Department of Food and Nutritional Fraunhofer Institute for Process
Sciences Engineering and Packaging IVV
Tuskegee University Freising, Germany
Tuskegee, Alabama
Haroon Maqbool Wani
Shabir Ahmad Mir Department of Food Technology
Department of Food Technology Amity University
Islamic University of Science and Jaipur, India
Technology,
Awantipora, India Idrees Ahmed Wani
Department of Food Science and
Technology
Markus Schmid
University of Kashmir
Fraunhofer Institute for Process Srinagar, India
Freising, Germany
Frank Welle
Fraunhofer Institute for Process
Manzoor Ahmad Shah Engineering and Packaging IVV
Department of Food Science and Freising, Germany
Technology
Pondicherry University Bruce Welt
Puducherry, India Packaging Engineering Program
Department of Agricultural and
Preeti Singh Biological Engineering
Fraunhofer Institute for Process University of Florida
Engineering and Packaging IVV Gainesville, Florida
Freising, Germany
Dennis Young
School of Packaging
Angela Störmer Michigan State University
Fraunhofer Institute for Process
East Lansing, Michigan
Freising, Germany
Hezhong Wang
Department of Sustainable Biomaterials,
Packaging Systems and Design
Virginia Polytechnic Institute and
State University
CHAPTER 1
Introduction
Food Packaging Materials
Ali Abas Wani, Preeti Singh, and Horst-Christian Langowski
CONTENTS
1.1 Introduction.......................................................................................................1
1.2 Packaging Materials for Food Applications ..................................................... 3
1.3 Properties of Packaging Materials ....................................................................4
1.3.1 Barrier Properties ..................................................................................7
1.3.2 Physical and Mechanical Properties .....................................................8
1.3.3 Migration Aspects of Packaging Materials...........................................8
References .................................................................................................................. 9
1.1 INTRODUCTION
Food packaging is not only indispensable in the distribution chain but is designed
to prevent the spoilage of food products throughout the supply chain. Diversity
in food composition and product structure in fresh and processed food products
demands unique packaging solutions for each product category. However, the pri-
mary function of packaging remains similar in order to preserve the freshness as
well as to prevent spoilage and pathogenicity and to extend the shelf life. Before
we proceed to the packaging material properties, it would be appropriate to review
basic functions of food packaging—that is, protection, containment, communication,
and convenience (Figure 1.1) (Wani et al., 2014).
Protection: Each package is intended to protect the food from physical, chemi-
cal, and biological changes. Therefore, the product type determines the pack-
age requirements in order to prevent the food from any physical changes such
as shrinkage arising from moisture loss due to dehydration, loss of texture due
to moisture gain (e.g. potato chips), and/or a tissue injury during transporta-
tion or handling (such as damage to fresh produce). Proper packaging also
1
2 FOOD PACKAGING MATERIALS: TESTING & QUALITY ASSURANCE
reduces chemical changes such as light- or oxygen-induced oxidation and

flavor loss, and it prevents postprocessing microbial contamination of foods.
Therefore, the package’s primary function is to protect the food from undesirable
changes emanating from interaction with environment and to maintain the quality
and safety of fresh or processed foods.
Containment: The function of containment of food products in specific packages is
to facilitate transportation and distribution throughout the supply chain. Packa-
ging prevents huge product losses from several environmental factors, such as
damage due to friction of loose materials, contamination from air-suspended
particles, and so on. Containment also prevents the mixing of some foods
while giving shape to others. Mixing of different solid foods is possible during
transportation due to shock and vibration, while it is practically impossible to
move liquid products without packaging.
Convenience: Packaging brings convenience to foods through innovative
containment solutions with features such as easy-to-open containers, aseptic
packaging, microwavable packaging, product visibility, oven safe trays,
boil-in-bags, resealability, and so on. This has enabled the consumer to pre-
pare food in the shortest possible time and has increased the global demand
for fresh, processed, and fast foods.
Containment
Protection
(prevents mixing and bruising,
(oxygen, moisture,
acts as transportation
microorganisms, dirt,
medium for liquid foods to
chemical contaminants,
prevent vibration and
toxins, etc.)
mechanical shock)
Convenience Communication
(easy lid opening, (nutrition labeling,
microwave and price, product
retortable pouch ingredients, product life,
processing) and storage conditions)
Figure 1.1 Major functions of food packaging.

INTRODUCTION 3
Communication: The purpose of package labeling is to inform the consumer about

a product’s contents, brand, shelf life, storage conditions, and price. Consumers
are keen to know about product quality, proper handling instructions, and nutri-
tional composition. Package labeling provides product information (nutrients,
weight, brand labels, certification, ingredient labeling, barcodes, etc.) in order
to satisfy legal requirements and to promote product branding, storage, cooking
instructions, price, and shelf life.
1.2 PACKAGING MATERIALS FOR FOOD APPLICATIONS
Approved packaging materials for food use are mainly glass, metal, paper,
plastic, and biobased materials. The material properties determine the end use
of a packaging material, and the shelf life is product specific (Robertson
2006). Plastic, metal, glass, and paper are commonly used as packaging materials
to preserve the freshness and quality of different food products. However, bio-
based packaging is a focus of current research in order to avoid the environmen-
tal impact of polymeric packaging materials. Several books have highlighted
specific packaging materials in detail. Following is a brief overview of packaging
materials for food use.
Glass: This inert packaging material provides an absolute barrier to gases and
moisture, making it suitable for flavor retention and freshness of food products
such as beer and wine. Glass can withstand high thermal-processing condi-
tions, provides good insulation, and can be formed into different shapes—either
transparent or opaque. Aluminum oxide coatings improve its barrier properties,
especially from chemical attack (Marsh & Bugusu 2007). Recycling glass to
preserve our fragile environment from pollution is an additional advantage.
Heavy weight and fragility when exposed to internal pressure, impact, and
thermal shock are some of the disadvantages for extensive use of glass as a
packaging material.
Paper: Paper is modified with additives (lacquers, waxes, resins, etc.) or coex-
truded with other polymers to improve its barrier properties. Paper and paper
boards are used in different forms (corrugated boxes, cartons, bags, sacks,
and wrapping paper) for several packaging levels in food and allied products.
Different forms of paper include:
1. Kraft paper: Natural brown, unbleached, bleached white, and heavy duty,
this paper is used to fabricate bags and wrappings. It is the strongest paper
and is used for packaging flour, sugar, and dried fruits and vegetables.
2. Sulfite paper: This paper is glazed to improve its appearance, wet strength,
and oil resistance. Sulfite paper is relatively lighter and weaker than kraft
paper but has high print quality. It is often used with plastic or foil lami-
nates to prepare packaging materials for biscuits and confectionery.
3. Greaseproof paper: Offering resistance to oil but allowing moisture
migration, greaseproof paper is commonly used to pack cookies, butter,
oily foods, candies, and so forth.
4. Glassine: This greaseproof paper has a high degree of smoothness and a

glossy finish. It is commonly used for packaging biscuits, fats, fast
foods, and so on.
5. Parchment paper: Made from acid-modified cellulose to improve its air
and moisture barrier properties, parchment paper is used for butter, lard,
and fat packaging.
6. Paperboard: Paperboard is available in several forms (white board, solid
board, chip board, fiber board, and paper laminates) and is mainly used in sec-
ondary packaging to improve the handling and distribution of food products.
Metal: The commonly used metals for food packaging are tin, steel, aluminum, and
chromium. They offer excellent barrier properties, physical protection, printability,
consumer acceptance, and recyclability. Tinplate is produced from low carbon steel
that is coated on both sides with a thin layer of tin and then further lacquered with
epoxy phenolic, oleoresins components, or vinyl resins to provide an inert barrier
for food materials. Metal is commonly used in retort processing of fruits, vegeta-
bles, meats, fish, and pulses, as well as in cans for drinks or containers for baby
foods, powders, confectionery, and so on. Aluminum is commonly used to make
foil, laminated paper/plastic films, laminates and metalized films, or cans. It has sev-
eral advantages over other metals such as being light in weight and corrosion resis-
tant, as well as providing a barrier to air, temperature, moisture, and chemical attack.
Aluminum-based packaging materials are used for soft drink cans, seafood, can/
bottle closures, and so forth.
Plastics: Plastics can be classified into thermosets and thermoplastics, which are
often made by the process of condensation or additional polymerization. Ther-
mosets are mainly used in nonfood applications, while thermoplastics consti-
tute the major packaging material used for films, bottles, jugs, and so on for
food industries. Although several plastics are allowed for food use (such as poly-
olefins, polyesters, polyvinyl chloride, polyvinylidene chloride, polystyrene, poly-
amide, ethylene vinyl chloride, laminates, and coextrusions), there is a growing
tendency to replace them with bioplastics to protect the environment. However,
plastic use in food packaging has continuously increased because of the low
cost and other functional advantages such as optical properties, thermosealability,
microwavability, and so on (Lopez-Rubio et al. 2004). Despite these advantages,
there are safety concerns about the use of plastics, especially the migration of plas-
tic additives in food stuffs. Monomer migration is continuously monitored and
regulated by agencies such as the U.S. Food and Drug Administration (FDA),
the European Union (EU), and other regulatory organizations. These concerns
are discussed in detail in Section 1.3.3 of the chapter. Details about properties of
several plastics commonly used in food packaging are listed in Table 1.1.
1.3 PROPERTIES OF PACKAGING MATERIALS
Packaging materials are selected on the basis of characteristics of the food to be

packed for a specific period of time. The basic material properties of packaging
INTRODUCTION
Table 1.1 Properties of the Commonly Used Plastic Packaging Materials for Food Products
Mechanical, Chemical, and

Type Physical Properties Miscellaneous Properties Barrier Properties Food Use
Polyolefins
LDPE Density (910–925 kg m−3), transparency Tough, flexible, resistant to grease High moisture barrier, very Bread and frozen food bags,
(poor–fair), low crystallinity, temperature and chemicals, good sealing low gas barrier flexible lids, squeezable food
range (−50°C to 80°C) properties bottles, etc.
LLDPE Density (910–940 kg m−3), transparency Tough, extensible, good resistance High moisture barrier, very Stretch/cling wrap, heat sealant
(poor–fair), high crystallinity, temperature to grease, good sealing properties low gas barrier coating, etc.
range (−30°C to 100°C)
HDPE Density (945–967 kg m−3), transparency Tough, stiff, strong, resistant to Extremely high moisture Used for bottles of milk, juice, and
(poor), high crystallinity, temperature grease and chemicals, good sealing barrier, very low gas water; cereal box liners,
range (−40 to 120°C) properties, easy to process and barrier margarine tubs; trash and retail
form bags
PP Density (900–915 kg m−3), transparency Moderately stiff, strong, good High moisture and low gas Used for bottles of milk, juice, and
(fair), low crystallinity, temperature range resistance to grease and barrier water; cereal box liners;
(−40°C to 120°C), high meting point of chemicals margarine tubs; hot filled and
160°C microwavable packaging; trash
and retail bags
Polyesters Density (900–915 kg m−3), high High impact-resistance, low High moisture and gas Refillable water bottles, sterilizable
transparency (like glass); temperature scratch-resistance, tough, strong, barrier baby bottles
range (−10°C to 220°C), high meting and resistant to grease and oil
point of >200°C
PETE or PET Density (1380–1410 kg m−3); high Stiff, strong, good resistance to Good barrier to gases and As containers (bottles, jars, and
transparency (good), low crystallinity, grease and chemicals moisture, good grease tubs), semirigid sheets (trays and
temperature range (−60°C to 200°C) resistance blisters), and thin oriented films
(bags and snack food wrappers)
PEN Density (1.36 g cm−3), transparency Stiff, chemical and hydrolytic Good gas and moisture Suitable for hot refills, rewashing,
(good), applicable at both high and low resistance, thermal and thermo- barrier, UV light barrier and recyclable. Suitable for beer
temperatures oxidative resistance and wine bottles to preserve the
flavor
(Continued)
5
6
Table 1.1 (Continued) Properties of the Commonly Used Plastic Packaging Materials for Food Products
Mechanical, Chemical, and

Type Physical Properties Miscellaneous Properties Barrier Properties Food Use
Polycarbonate
PVC Density (1350–1450 kg m−3), Strong, stiff ductile, resistant to High moisture barrier, Used in bottles and packaging
transparency (good), temperature range chemicals, stable electrical moderate oxygen barrier, films. Limited use in food
FOOD PACKAGING MATERIALS: TESTING & QUALITY ASSURANCE

(−2°C to 80°C) properties good resistance to grease applications
and oil
PVdC Density (1600–1700 kg m−3), Strong, stiff ductile, resistant to Excellent oxygen and Suitable for poultry, cured meats,
transparency (good), temperature chemicals, stable electrical moisture barrier cheese, tea and coffee, snack
range (−20°C to 130°C) properties properties, very good foods, and confectionery. May be
grease and oil resistance used in hot filling, low temperature
storage, and modified
atmosphere storage conditions
Polystyrene Density (1030–1100 kg m−3); Hard and brittle with low melting Low moisture and air Used as protective packaging for
transparency (very good), temperature point barrier, fair to good eggs, disposable plastic ware,
range (−20°C to 90°C) resistance to oil and cups, plates, bottles, and trays.
grease Expanded form may be used as
cushioning material
EVOH Density (1140–1210 kg m−3), Stiff, strong, very strong oil and Excellent moisture barrier, Used in coextruded films to avoid
transparency (good), applicable grease resistance high air barrier, very good its contact with water
temperatures (−20°C to 150°C) resistance to grease
and oil
Polyamide Density (1130–1160 kg m−3), Stiff, strong, good resistance to High air and moisture Used for boil-in-bag packaging
transparency (good), applicable grease and chemicals barrier, good resistance to
temperatures (−2°C to 120°C) grease and oil
Source: Marsh, K., Bugusu, B., J. Food Sci., 72, R39–R55, 2007; Lee, D.S., et al., Food Packaging Science & Technology, CRC Press, Boca Raton, FL,
2008.
Note: EVOH, ethyl vinyl alcohol; HDPE, high-density polyethylene; LDPE, low-density polyethylene; LLDPE, linear low-density polyethylene;
PEN, polyethylene naphthalate; PETE, polyethylene terephthalate; PP, polypropylene; PVC, polyvinyl chloride; PVdC, polyvinylidene chloride.
INTRODUCTION 7
materials that influence food quality and safety are barrier properties (light, oxygen,
and water vapor transmission rate), mechanical properties, chemical reactivity, and
migration properties. In order to predict the performance of a package, scientists
and packaging technologists perform an array of tests to ensure that the packaging
material has the desired properties for a selected product to keep it safe throughout
the distribution chain. Some of the critical factors while determining the packaging
materials properties are discussed as follows:
1. Permeability—Should have selective permeability for gases, moisture, and

flavors as per the product requirements.
2. Light barrier properties—Should protect foods from adverse effects of light.
3. Microbial contamination—Should prevent microbial contamination from the
environment and from the package itself.
4. Tensile strength—Should have sufficient tensile strength to contain the food
during distribution and throughout its entire cycle.
5. Migration aspects—Food package interaction is a serious concern of consumers
mainly with regard to food safety. All packaging Materials should meet migra-
tion limits as per standards and regulations.
These factors will be discussed in subsequent chapters of this book. Following is a

brief overview of the material properties.
1.3.1 Barrier Properties
The barrier properties of packaging materials have significant influence on the

shelf life, safety, and quality of packaged food products. Water vapor, gas, and
light barrier properties are primary considerations when designing a packaging
material for a specific end use.
Water vapor barrier: Food products tend to dry out or gain moisture if they are not
packed appropriately. Dried milk and protein powders tend to agglomerate,
while deep-fried products, cookies, and wafers tend to lose their crispy texture
upon absorption of moisture. Furthermore, fresh produce requires packaging mate-
rials with a certain amount of mass transfer to maintain an optimal level of oxygen
required by the produce to respire and to prevent excessive condensation within
the package. Therefore, water vapor permeability of packaging materials greatly
influences the quality of food products. The water vapor transmission rate, a stan-
dard practice to measure water permeability, determines the ability of a package to
allow water vapor to pass through it. The standard test conditions are 90% relative
humidity at 37.8°C. Several methods are in practice and are discussed in detail in
appropriate sections of this book.
Oxygen barrier: Oxygen may be kept away by appropriate packaging to avoid
many undesirable changes in foods. Oxidation causes discoloration of fresh
and processed meat products, off-flavor development or rancidity in products
rich in oil, and mold growth in cheese and bread, and it accelerates spoilage
in several food products. Therefore, oxygen-sensitive food products require

packaging with adequate oxygen barrier properties. The oxygen transmission
rate is measured as the number of milliliters of oxygen that pass through one
square meter of packaging in 24 hours at one unit of atmospheric pressure.
Packaging materials with values of 10 to 100, 1 to 10, and less than 1 milliliter
are considered as good, very good, and extremely good, respectively. Oxygen
may also find its way inside the package through inappropriate seals, folds,
or through a damaged package. Factors such as temperature and humidity influ-
ence the oxygen barrier properties and must be considered during the selection
of a specific packaging material.
Light barrier: Light-mediated oxidation creates unpleasant odors and taste in a num-
ber of food products. It also causes discoloration of meat products and off-flavor
development. When products are illuminated, components of the food product
become oxidized and this creates unpleasant odors and taste. The food also
loses vitamins A, B, and C, and pigments in the food lose their color. Most vulner-
able are dairy products, meat and meat products, and fats and oils.
1.3.2 Physical and Mechanical Properties
The physical and mechanical properties of packaging materials are important in

determining the physical strength they can withstand under applied stress. Therefore, it
is important to measure and improve the mechanical properties of packaging materials
using a range of mechanical testing methods, such as:
1. Tensile testing
2. Seal and peel testing
3. Testing of tear, flexural, and impact properties
4. Testing of seal strength and puncture resistance
5. Peeling test
6. Edge compression test and box compression test
7. Drop test
1.3.3 Migration Aspects of Packaging Materials
Migration of polymers, additives, and other components from metal and paper packa-
ging has been a serious concern for consumers (Franz, 2000). Several factors such as the
processing, hot filling, pH, and poor processing of polymers increase the migration risk of
packaging constituents into the food stuffs. Liquid products have more serious problems
than solid or semisolid foods. The migration of polymeric compounds, such as vinyl
chloride, acrylonitrile, styrene, plasticizers (phthalate, adipate esters, acetyltributyl
citrate, BHT [butylated hydroxytoulene], BHA [butylhydroxyanisol], odors, etc.), tin,
lead, aluminum, epoxy resin coatings, dioxins, benzophenone, nitrosamines, chlorophe-
nols, and so on, can be evaluated using gas or liquid chromatography to ensure the safety
of food products. Several regulatory authorities (EU, FDA, etc.) have regulations regard-
ing the permissible limits of migrations for these compounds.
INTRODUCTION 9
REFERENCES
Franz, R. (2000). Migration of plastic constituents. In: Piringer, O.-G., & Baner, A.L. (eds.),
Plastic Packaging Materials for Food, Wiley-VCH, New York, pp. 287–358.
Lee, D.S., Yam, K.L., Piergiovanni, L. (2008). Food Packaging Science and Technology,
CRC Press, Boca Raton, FL.
Lopez-Rubio, A., Almenar, E., Hernandez-Munoz, P., Lagaron, J.M., Catala, R., Gavara, R.
(2004). Overview of active polymer based packaging technologies for food applications.
Food Rev Int, 20(4), 357–387.
Marsh, K., Bugusu, B. (2007). Food packaging—Roles, materials, and environmental issues.
Journal of Food Science, 72(3), R39–R55.
Robertson, G.L. (2006). Food Packaging—Principles and Practice, second edition, CRC Press,
Boca Raton, FL.
Wani, A.A., Singh, P., Langowski, H.C. (2014). Food technologies: Packaging. In: Motarjemi, Y.,
Moy, G.G., & Todd, E.C.D. (eds.), Encyclopedia of Food Safety, Elsevier Science, Oxford,
UK, pp. 211–218.
CHAPTER 2
Shelf Life of Packed Food and

Packaging Functionality
CONTENTS
2.1 Introduction to Food Quality and Shelf Life ..................................................12

2.2 Different Cases for Shelf-Life Investigations .................................................15
2.3 Factors from Product, Package, and Environment .........................................16
2.4 General Classification of Decay Processes
of Packed Food Products ................................................................................18
2.5 Factors Relevant for the Assessment of Quality
Decay (Quality-Related Shelf Life) ................................................................21
2.6 Factors Relevant for Declaration-Related Shelf Life......................................22
2.7 Chemical Mechanisms of Quality Decay .......................................................23
2.7.1 Oxidative Reactions ............................................................................23
2.7.2 Autoxidation .......................................................................................23
2.7.3 Photooxidation ....................................................................................24
2.7.4 Quantification of Oxygen Uptake .......................................................25
2.7.5 Pressure-Dependent Interaction of Oxygen with Food
Constituents: Myoglobin as an Example ............................................26
2.7.6 Other Light-Induced Reactions...........................................................27
2.8 Physical Mechanisms of Quality Decay .........................................................27
2.8.1 Changes in Water Content ..................................................................27
2.8.2 Water-Related Quality Changes: Increase in Water
Content................................................................................................31
2.8.3 Water-Related Quality Changes: Decrease in Water Content
of High-Moisture Foods .....................................................................34
2.8.4 Localized Textural Changes without Overall Changes in
Water Content .....................................................................................35
2.8.5 Loss of Flavors, Uptake of Off-Flavors, or Other Contaminants .......35
2.8.6 Other Physical Limitations of Shelf Life ............................................36
11
2.9 Biotic Mechanisms .........................................................................................37

2.9.1 Microbiological Mechanisms..............................................................37
2.9.2 Different Effects of Packaging on the Growth of Microorganisms....38
2.9.3 Biotic Mechanisms, Relevant for Nonprocessed or Minimally
Processed Food ...................................................................................40
2.10 Classification of Food Types and Their Typical
Mechanisms of Decay.....................................................................................40
2.11 Methods to Correlate Packaging Functionality
and Product Shelf Life ....................................................................................45
2.11.1 Basic Issues of Substance Permeation ..............................................45
2.11.2 Consideration of Substance Transport Rates in All
Compartments of the Package: Packed Products, Package
Head Space, and Packaging Materials..............................................46
2.11.3 Packaging Functionality and Product Shelf Life with Regard to
Flavors, Off-Flavors, and Contaminants...........................................48
2.11.4 Packaging Functionality and Product Shelf Life in the Case of
Oxidative Processes ..........................................................................51
Water Uptake/Losses ........................................................................53
2.11.6 Guidance Values for Oxygen Permeability and Water Vapor
Permeation Rate of Packaging Materials..........................................54
2.11.7 Packaging Functionality and Product Shelf Life for
Respiring Products ............................................................................56
2.12 Conclusions and Outlook................................................................................60
References ................................................................................................................60
2.1 INTRODUCTION TO FOOD QUALITY AND SHELF LIFE
In those countries of the world with industrial food production, the indication of a
certain type of shelf life on packed food is common practice or even mandatory. For
consumers, the indicated shelf life is important in their decision to purchase, to con-
sume, and also possibly to waste food. Overall, packaging has a large influence on
shelf life, and properly selected packaging materials determine the efficiency of the
food supply chain.
Although extensive descriptions of the deterioration mechanisms of many food
products have been reported since the 1960s (see e.g., Heiss 1968; Labuza 1982), it
will always be difficult to establish a quantitative relationship between the properties
of food and the performance of its packaging with regard to shelf life. Because of the
huge variability of the products involved, every combination of a new food product
and its packaging will need an individual analysis and optimization procedure. There-
fore, the aim of this chapter is first to look at different decay reactions in foods from the
point of view of a person searching for the proper technical parameters of a packaging
system for an existing or a new product and then to give guidelines for an initial selec-
tion of packaging materials and for their subsequent optimization.
SHELF LIFE OF PACKED FOOD AND PACKAGING FUNCTIONALITY 13
First, a definition of the term “shelf life” has to be given. As current regulations
concerning food and food packaging are—relatively speaking—most consistent in
the European Union (EU), they will be used as our basis here. In Regulation (EU)
No. 1169/2011 (Regulation 1169/2011), two different cases for establishing a date
for the lifetime of a food product are outlined. A “date of minimum durability of a
food” is defined by the regulation as follows: “The ‘date of minimum durability of
a food’ means the date until which the food retains its specific properties when prop-
erly stored.” Here, “specific properties” stands for the expectations of the consumer,
meaning that this concept represents a quality-based approach. Usually, this “date of
minimum durability of a food” is indicated by a “best before” date. Such a date should
be well predictable, meaning that several samples of the same type of product must
show a high degree of similarity in terms of their decay reactions.
The second case appears when food degradation might create risks for the consu-
mer: “In the case of foods which, from a microbiological point of view, are highly per-
ishable and are therefore likely after a short period to constitute an immediate danger
to human health, the date of minimum durability shall be replaced by the ‘use by’ date.
After the ‘use by’ date a food shall be deemed to be unsafe…” (Regulation 1169/
2011). This second case thus represents a risk-based approach, and the establishment
of the time to be indicated by a “use by” date has to follow a different methodology in
comparison to the “best before” date. Interestingly, the EU’s Regulation 1169/2011
avoids using the term “shelf life” for both cases.
Selected food products, however, are usually exempted from the requirement to
indicate one of the two different types of product lifetime: On the one hand are pro-
ducts intended for ready consumption, which are subject to an evident decay; on the
other are those that may still be used after many years of storage. Examples of short-
lived products, according to European legislation, are noncut fruit or vegetables or
fresh bakery products. Apparently, a shelf life could theoretically also be assigned to
these kinds of products, but it would be more like an a posteriori diagnosis and
would strongly vary with the individual characteristics of every single product
item. Even though there is no requirement to indicate a shelf life, the actual lifetime
of fresh produce is also of high importance in the food trade. In the following, it will
be used synonymously with shelf life.
A more general definition for the term shelf life has been given by the Institute of
Food Science and Technology (IFST 1993), explaining it as “… the period of time
during which the food product will (i) remain safe; (ii) be certain to retain desired
sensory, chemical, physical, and microbiological characteristics; (iii) comply with
any label declaration of nutrition data, when stored under the recommended conditions.”
This definition now separates three different cases: (i) represents the risk-related limita-
tion of a food’s lifetime but does not restrict it to microbiological risks, as does EU
Regulation 1169/2011; (ii) represents the quality-based limitation; whereas (iii) further
adds the compliance of the actual amounts of ingredients with the labeled ones, giving
a declaration-related time limit, which, in its nature, is similar to Case (ii).
The use of the common term shelf life for these three different cases has been criticized
by Nicoli (2012), who asks for a clear separation between safety-related and quality-
related criteria and for the use of the terms “safe life” for the former and “shelf life” for
Arbitrary quality parameter

Fresh products
b
Long-life products
Quality threshold
“Use by” or “best before”– Time/ “Best before”–

date (if required) arbitrary units date
Figure 2.1 Quality decay of fresh and long-life food products, schematic. Straight lines indicate
a steady decay, whereas dotted lines symbolize fast decay after exceeding a
critical limit.
the latter, respectively. Such a stringent separation between “shelf life” and “safe life”
would also be highly desirable for communication in the media, which often misleads
consumers. Still, most people would discard a product bearing a “best before” date on
the next day after the indicated shelf life (Figure 2.1).
Summarizing, we can discriminate among three different groups of reasons as
listed here for establishing a specific limited lifetime of a food. As a property common
to all of them, one or more specific parameters—be they relevant for product quality,
for consumer information, or for the health of the consumer—exceed or fall below a
given threshold, as shown very schematically in Figure 2.1 (e.g., the quality of decay).
Here, fresh products are shown whose quality either (a) may still increase, as in the
case of climacteric fruit, or (b) start to decrease from the beginning. Sometimes, the
quality may suddenly decrease after a critical concentration has been reached (e.g., that
of microorganisms in the case of fresh products or that of reacted oxygen in the case of
autoxidation of fatty acids). These cases are symbolized by dotted lines. The three differ-
ent groups of reasons for the limited lifetime of a food are as follows:
• Quality-related reasons, which require a “best before” date that, in turn, represents
the shelf life in a narrower sense. Here, a gradual decay of quality will occur with-
out creating health risks for consumers, and the term “specific properties” of a
food product (as used in EU’s Regulation 1169/2011) should be correlated to
measurable parameters. In common practice, the assessment of food quality
will be made via a sensory analysis, as outlined, for example, in the related Ger-
man standard (DIN 10968 2003). It is up to the discretion of the food manufac-
turer to select quality attributes and to decide at which quality level his product
can be seen as being acceptable for the consumer. In all cases, the establishment
of a “best before” date implicitly involves a quantitative description of a quality
decay process over time and the definition of an appropriate quality threshold.
• Declaration-related reasons where the quantifiable amount of an ingredient (e.g.,

a vitamin or, even simpler, of the whole contents) may fall below its specified
value in the course of time. Related processes also show a gradual mechanism
of decay but allow for the setting of unambiguous threshold values for the
shelf life. The decay is also not linked to direct health risks for the consumer.
• Safety-related reasons, which require a “use by” date that represents the safe life.
Current regulations (such as the EU’s Regulation 178/2002 and Commission
Regulation [CR] 2073/2005) and related guidelines (see e.g., Ireland’s FSAI
2011 and CFA 2010 in the United States) address microbiological hazards,
and quantitative thresholds are given for different types of highly pathogenic
microorganisms.
Chemical hazards that may originate from the packaging are treated by a differ-
ent approach within the framework of EU regulations: Regulation (EC) 1935/2004
gives the general requirements for food packaging whereas CR 10/2011 specifies
migration limits from plastic materials for a list of some 900 substances. These limits
are implicitly related to the shelf life of food products via Annex V, Chapter 2 of CR
10/2011, which indicates actual test conditions, especially contact time and tem-
perature, in view of the “contact time in worst foreseeable use.” It is noteworthy
that this approach asks for proof that the packaging remains safe for the whole
intended shelf life as a prerequisite for its use in conformity with legal requirements.
(This subject will be treated in detail in Chapter 12 of this book, “Food Package
Testing Authorities and Regulations.”)
2.2 DIFFERENT CASES FOR SHELF-LIFE INVESTIGATIONS
As an important prerequisite, we cannot test an isolated product without packaging—

whether the package is realistic or a model—because there is a large difference between
open storage and storage in a package, even for the simplest type of packaging. Even if
we just want to investigate a product under a controlled atmosphere (CA), we need a
package for it in the form of an appropriate container. The three different main reasons
for an assessment of the shelf life of a packed product are distinguished by the different
consequences from the sequence of measurements and the methodology to be applied.
The first reason is the development of a new food product, which calls for parallel
development of the food and its packaging. There will always be a step, which is called
the initial shelf-life study (IFST 1993), in which the relevant degradation mechanisms of
the food have to be identified. Because the vast majority of “new” food products are not
completely new but are derived from common types of food, general knowledge already
exists about the expected degradation mechanisms and the order of magnitude of their
rate. Such facts may serve as a basis for an initial selection of appropriate packaging
materials and will be discussed shortly. Experience shows, however, that the majority
of food producers follow a much simpler principle. They look for similar products on
the market, study their package type and indicated shelf life, and start in on a first attempt
based on these facts. A storage test follows that is undertaken under realistic conditions
for the duration of the indicated shelf life. The process is finalized by an acceptance test
(described later in this chapter), which is based on whether a product will be labeled with
a “best before” date or a “use by” date—the latter determined by a microbiological
assessment. Such trial-and-error approaches will probably be successful in most
cases, but their outcome will not really support further optimization strategies and
will not be helpful in cases of unexpected problems.
Preferably, at the very least, the aforementioned process should be used to estab-
lish qualitative and more quantitative relations among influencing factors and degra-
dation mechanisms. A wide but reasonable selection of packaging materials with
different known properties should already have been evaluated. An optimization
phase then follows, in which more detailed information is be gathered about the actual
behavior of the food in combination with the package via a systematic variation of
packaging parameters under realistic conditions.
The second reason for shelf-life assessment, which occurs similarly in industrial
practices, is that an alternative package has to be designed for an existing food product.
Here, the basic mechanisms of the product degradation are already known, thus elimi-
nating the need for the initial shelf-life study. But because the properties of the new
package will probably be different from those of the original one, the study will be simi-
lar to the optimization phase for testing a new product that was mentioned earlier.
The third type of assessment takes place in the production routine, where storage
tests of packed food are performed at regular intervals as an element of quality control.
Here, the usual properties of both the food product and the packaging are known, and
the test is usually applied to verify proper production performance over longer time
periods. If, in continuous monitoring, the consistency of the properties of the food pro-
duct and its packaging is to be ensured, routines for accelerated storage tests may be
developed, for example, at elevated temperatures (Mizrahi et al. 1970; Labuza 1982;
IFST 1993; DIN 10968 2003; Hough et al. 2006). It should be noted here that the use
of accelerated tests with respect to the first two cases shown here is questionable and
may often be totally misleading (Robertson 2005; Lawless and Heymann 2010).
2.3 FACTORS FROM PRODUCT, PACKAGE, AND ENVIRONMENT
In all cases, a specific food product’s intrinsic properties (such as sensitivity to oxi-
dation or initial microbial population) should be considered. The product is exposed to
external conditions, such as climate, illumination, or the presence of contaminants. The
exposure is not immediate because the packaging more or less separates the food from
the environment. Although the intrinsic properties are responsible for the nature of the
decay mechanisms, as described in the next section, the external conditions determine
the reaction rates of the decay processes. Depending on its properties for substance per-
meation and light transmission, the package acts as a mediator or separator between the
packed product and its environment, as schematically shown in Figure 2.2. One special
component found in most packages that cannot be assigned to a product’s external con-
ditions or to its intrinsic properties is a gas-filled space, called the head space. Its com-
position may change over time. At the time a package is filled, the head space is
Package
Headspace Environment
Gases Permeation Temperature
Humidity Humidity
Flavors and off- Atmospheric gases
Absorption
flavors Contaminants
Desorption
Illumination
Respiration
Degradative Light
reactions ingress
Product
Absorption
Incredients
(dyes, vitamins,
fats, flavors, ...) Migration
Water
Microorganisms
Other living cells
Figure 2.2 Schematics of interactions among packed product, headspace, package, and envir-
onment (processes/reactions in italics).
determined by the gas mixture fed into it. In the course of its shelf life, the product’s
intrinsic properties (e.g., its gas consumption or metabolism), external conditions,
and packaging (e.g., its permeability for different substances) determine the gas compo-
sition of the head space. In the case of active packaging, the composition of the head
space also depends on sorption or on the release properties of the packaging system.
As such, the head space can be regarded as an additional element of the packaging sys-
tem, with properties that change over time (Figure 2.2).
The external conditions consist of constant and variable conditions. Virtually con-
stant conditions are given by the atmospheric composition of permanent gases as fol-
lows (in volume fraction percent): nitrogen: 78.08, oxygen: 20.95, argon: 0.93, carbon
dioxide: 0.04, and total trace gases: below 0.003 (Air 2015, Dlugokencky and Tans
2015). Variable climatic conditions are the actual atmospheric pressure, the tempera-
ture, and the water vapor partial pressure. Depending on the storage conditions, illu-
mination with light will occur as another variable showing different intensities over
the spectrum ranging from ultraviolet (UV) over visible to near infrared.
External climatic conditions may be classified as follows (see e.g., Ellis and
Man 2000):
• Temperate conditions, with a maximum temperature of 25°C and a maximum

relative humidity of 75%. These are normal indoor conditions valid for indus-
trialized countries. Typical testing conditions to simulate them are a tempera-
ture of 23°C and case-adapted values up to 85% of relative humidity
• Tropical conditions, with a maximum temperature of 37°C and a maximum

relative humidity of 95%, with corresponding testing conditions of 38°C and
up to 100% of relative humidity
• Frozen conditions, with a controlled average temperature of −18°C and a rela-
tive humidity close to 100%
• Refrigerated conditions, with temperatures from 0°C to +8°C, with a relative
humidity close to 100%
For a given packed food, the conditions of illumination may vary from sunlight to
shop floor illumination to domestic lighting. Because an increasing number of light
sources with different spectral outputs are used, well-adapted conditions are needed
for tests simulating light exposure.
Substances leading to off-odors or contamination may accidentally be present in the
surroundings of the packed product. Because such cases are usually not regarded as
proper storage conditions, they are normally excluded from shelf-life considerations.
Specific provisions, however, have to be taken if the sources of such substances belong
to the packaging system itself. A well-known example is the contamination by mineral
oil components of food packed in boxes from recycled cardboard. Such cases, however,
are subject to food contact regulations (Regulation 1935/2004) and will be addressed in
Chapter 12 of this book (“Food Package Testing Authorities and Regulations”).
2.4 GENERAL CLASSIFICATION OF DECAY PROCESSES

OF PACKED FOOD PRODUCTS
If we want to understand the potential effects of packaging on shelf life, we need a

proper classification of a food product’s relevant decay processes. The basic decay
mechanisms can be separated into chemical, physical, and biotic. The latter will not
only be of microbiological origin, but may also be quality-related processes that occur
due to the cell metabolism of the product itself, such as for fresh produce and fresh meat.
Table 2.1 presents an overview of the mechanisms of product deterioration and
their determining factors. The most important factors are located inside the product
(i.e., its intrinsic properties). Often, important factors are also found in the composi-
tion of the headspace atmosphere, which is determined by the initial conditions, the
activity of the product, and the exchange of substances with the outside, as noted ear-
lier. In most cases, the transfer of substances or energy through the package wall is a
decisive factor and is determined by the properties of the packaging material, by the
gas composition of the headspace, and by the external conditions from the surround-
ing environment.
As a result of all these factors, a qualitative estimation of the overall influence of an
appropriate type of packaging on the related mechanisms is also presented in Table 2.1.
From this table, we see that the package has great importance in many areas and that no
mechanism can be found where the package’s role can be totally neglected. On the other
hand, it can also be observed that microbiological safety issues only have a weak rela-
tion to packaging. Thus, in packaging, shelf-life issues dominate safe life aspects.
SHELF LIFE OF PACKED FOOD AND PACKAGING FUNCTIONALITY
Table 2.1 Overview of Predominant Mechanisms that Influence Food Lifetime (Shelf Life or Safe Life) Together with Determining Factors and
the Influence of Packaging
Factors Inside the Package

Basic Mechanism (specific examples for (intrinsic product properties, Transfer through External Overall Influence
effects [and products]) headspace atmosphere) Package Involved Conditions of Packaging
Quality-related effects on product life → shelf life

Chemical mechanisms
Oxidative decay Specific product composition Oxygen transfer, Temperature, High
(autoxidation, rancidity [sunflower oil] Oxygen in product and light ingress illumination
photooxidation, rancidity, color changes headspace
[olive oil, meat products])
Other oxygen–food interactions Oxygen transfer Temperature High
(unwanted color changes [fresh meat])
Other photochemical processes Specific product composition Light ingress, Illumination High
(light struck taste [dairy products, beer, etc,.]) Oxygen in product and oxygen transfer
headspace
Physical mechanisms
Water-related textural changes Water activity and initial water Water transfer Temperature, High
(water uptake, loss of crispiness [bakery products], content of product humidity
water loss, drying [meat]) Water content of the headspace
Structural changes without water exchange Local temperature, water Heat transfer Temperature Low
with the outside activity, and water content of
(crystallization [ice cream, powders], product
agglomeration [powders])
Permeative/sorptive loss or access of Specific product composition Flavor/odor transfer Temperature, High
substances presence of odor
(loss of flavors [flavored products], substances
admission of off-odors (powdery products,
dairy products)
(Continued)
19
20
Table 2.1 (Continued) Overview of Predominant Mechanisms that Influence Food Lifetime (Shelf Life or Safe Life) Together with Determining
Factors and the Influence of Packaging
Factors Inside the Package

Basic Mechanism (specific examples for (intrinsic product properties, Transfer through External Overall Influence
effects [and products]) headspace atmosphere) Package Involved Conditions of Packaging
Quality-related effects on product life → shelf life (continued)

Biotic mechanisms

Growth of nonpathogenic (spoilage) Germ colonization/ Gas transfer Temperature Medium
microorganisms contamination
(smear, visible growth, and off-odor [fresh meat, Gas composition of headspace
fresh produce])
Decay of metabolic cells of the product Water activity and water content Gas transfer, Temperature, medium
(senescence, softening, and staining [fresh of product, water transfer humidity
produce]) composition of headspace
Declaration-related product life → shelf life

Chemical mechanisms
Decay of indicated constituents Specific product composition Oxygen transfer, Temperature, High
(oxidative loss of vitamins [fruit juices, milk]) Oxygen in product and light ingress illumination
headspace
Physical mechanisms
Global water loss Water activity and initial water Water transfer Temperature, High
(reduction of volume or weight [beverages, content of product humidity
dairy products, produce])
Safety-related effects on product life → safe life

Biotic mechanisms
Growth of pathogens, formation of toxins Initial germ contamination/ Gas transfer Temperature Medium/low
(health risks [meat and dairy products]) colonization
Composition of headspace
Note: Factors of high effect are italicized.

2.5 FACTORS RELEVANT FOR THE ASSESSMENT OF QUALITY

DECAY (QUALITY-RELATED SHELF LIFE)
As noted earlier, the shelf life of a product is limited in most cases by a loss of its
quality. In this case, a “best before” date will be given, which is reached as soon as one
or more quality attributes fall below a specified level, which is shown schematically in
Figure 2.1. Depending on the specific question, different sensory methods are applied
(DIN 10968 2003; Busch-Stockfisch 2008; Lawless and Heymann 2010). As is well
known, sensory attributes are widespread and cover olfactory, gustatory, visual, tac-
tile, and—in several cases—even acoustic aspects.
To obtain a single global or integrative parameter representing the typical attitude
of the average consumer and his overall acceptance, a hedonic assessment is often
applied. This, in its most common form, is based on a nine-point scale, ranging
from “like extremely” down to “dislike extremely.” This type of assessment can
be used as an initial benchmark in all of the three cases mentioned earlier—namely
the development of a new food product with its package, the introduction of an alter-
native package, and for quality control in the regular production of an existing
product. In the strictest sense, a relatively high number of untrained panelists
are required for a good statistical basis of the results, typically between 75 and 150
(Lawless and Heymann 2010)—a number that is rarely achieved in industrial practice.
As long as the results of this test already prove the required acceptance after the shelf
life, no further action is often needed.
Because, however, different decay mechanisms may occur in a product at the same
time and, as unexpected deviations, may be observed even in an existing product,
many different attributes are important that should be well separated for a good under-
standing of the whole package system. This calls for an analytic test (in addition to a
hedonic test), preferably a descriptive one, requiring a set of highly trained sensory
experts. More detailed approaches in sensory assessment use a set of descriptors
that are specific to the investigated product, and scores are assigned to each descriptor;
see Figure 2.3 (after Siefarth et al. 2014) as an example.
If we really want to link the technical parameters of the package to the observed
quality decay, we should be able to establish a stringent relationship between the
results of a sensory assessment and the following facts:
• The detailed nature of the deterioration mechanisms (e.g., the development of

specific off-odors by oxidative reactions)
• The substances responsible for the reactions (e.g., oxygen)
• The rate of transfer from the environment to the headspace of the package or
vice versa, determined by the permeation properties of the packaging material—
in this, its permeability for oxygen
Although some sensory attributes can be easily correlated with a measurable quan-
tity, such as in the case of visually perceptible color changes, the identification of the
relevant mechanisms generally is a difficult task, especially when chemical reactions
are involved.
Fishy
3
Sweet Metallic
2
Cooked milk-like 0 Oily
Fatty Green, grassy
Blood-like
Figure 2.3 A representation of eight different flavor attributes in an infant food formula. (After
Siefarth et al., Foods, 3, 1, 30–65, 2014.)
Industrial practices and even many scientific studies limit the scope of sensory
assessments to the correlation of a single-score hedonic quality indicator with a global
reaction parameter, for example, the oxygen consumption by the product or its water
uptake (see e.g., Katz and Labuza 1981). Although more refined attempts have been
made since the early 1970s, including computer-based modeling of the food-package
interaction (see e.g., Herlitze et al. 1973), more detailed knowledge about the mechan-
isms involved, especially in chemical decay processes, is still needed in the majority
of cases.
In the sector of physical processes of quality decay, it is easier to obtain measur-
able quantities. Here, in most cases, the product’s water content determines the phy-
sical properties related to quality and to consumer acceptance (Figura and Teixeira
2007). This is the reason why the influence of water on food quality is the most-
studied area and why the relationships among water exchange, product quality, and
water vapor permeability of packaging materials have been known for decades
(Heiss 1968; Labuza 1970, 1982, 1984).
2.6 FACTORS RELEVANT FOR DECLARATION-RELATED SHELF LIFE
An indication of the contents of industrially made food packages is mandatory

according to the regulations of most countries, which indicate the maximum tolerable
deviations; see for example, the EU’s CD 76/211/EEC. Although technically not seen
as a real offense, if the contents of a package fall below the legal limit due to water
losses through intact packaging walls, this could still create unnecessary complaints
and therefore should be avoided in the course of the packaging design.
Depending on the type of food and the relevant regulations, quantitative declara-
tions of food constituents may be given on the package on a voluntary or a mandatory
basis—for instance, for vitamins, but the actual value must not fall below the value
given in the declaration.
In any of these cases, a clear threshold can be provided and the allowed decrease in
total contents or amount of constituents is simply the difference between the actual
values at the moment of packing and the nominal values. If the rate of the decrease
is known, the shelf life can be calculated accordingly.
In this context, chemical mechanisms are mainly represented by the oxidative
degradation of vitamins. Ascorbic acid (vitamin C) and tocopherol (vitamin E) are
the most prominent examples. Simple water losses represent the predominant physical
mechanism that limits the declaration-related shelf life of high-moisture foods.
2.7 CHEMICAL MECHANISMS OF QUALITY DECAY
2.7.1 Oxidative Reactions
In the quality decay of packed food, oxygen is one of the most important drivers—
often in combination with visible or UV light. The quality-relevant effects of oxidative
reactions are the decay of important constituents (such as dyes/colorants or vitamins)
and/or the formation of new, mostly unwanted substances. The most prominent group
among the latter is off-flavors, predominantly generated by oxidation of lipids. Many
aldehydes or ketones of extremely high sensory activity are created via this route (see
e.g., Belitz et al. 2008), and the related amounts of oxygen involved may be as little as
some tenths of a milligram per kilogram of product.
Because most food products are complex mixtures of different substances, oxidative
reactions do not just comprise one single step but a whole cascade (Belitz et al. 2008).
This suggests that most reaction paths will be irreversible and that the total amount of
products from oxidative reactions directly depends on the amount of oxygen made
available. This is the basis for the concept of oxygen tolerance thresholds (Heiss and
Robinson 1975; Heiss 1980, 1990; Heiss and Eichner 1994), which is used to obtain
guidance values for packaging functionality.
2.7.2 Autoxidation
Most of the oxygen molecules present in food are in their ground state, the
triplet state, in which the molecules have two unpaired electrons. This triplet oxygen
reacts fastest with other radicals. Therefore, constituents of the food have to be
transformed into radicals for an oxidation via triplet oxygen to occur. This step is the
initiation of a chain reaction called autoxidation (see e.g., Labuza 1982; Frankel 1984;
Min and Boff 2002; Belitz et al. 2008). This initiation may be achieved by the action of
highly energetic light, especially UV light, or by the action of metal ions, with both being
able to create radicals.
This autocatalytic reaction needs an induction time for the formation of an initial
threshold concentration of hydroperoxide groups at specific constituents of the food,
mainly unsaturated fatty acids. The hydroperoxide groups decompose under formation
of other radicals, which then again may react with triplet oxygen. As soon as a threshold
concentration has been reached, a further oxidation reaction will proceed very fast.
For the long phase of low reactivity (i.e., before the induction time has been
reached), changes in product quality due to oxygen uptake can be virtually neglected.
Irrespective of the duration of the induction time, the critical amount of reacted oxy-
gen needed for the starting point of the faster reaction remains about the same. Even
though this threshold parameter cannot be directly correlated with the appearance of a
sensory-relevant substance in a critical concentration, it represents the initial concen-
tration needed for a fast decay reaction. If one takes this as the oxygen tolerance
threshold, there will be a good safety margin in the shelf-life period estimated via this
method. The packaging-related determining factors for shelf life will then be the
transmission of the packaging material to highly energetic (especially UV) light
and the oxygen permeation rate through the wall of the package. At sufficient protec-
tion from UV light, the induction time may be much longer than the time required for
the permeated amount of oxygen to exceed the nominal oxygen threshold. If the
induction time is longer than the required shelf life, the autoxidation process is no
longer relevant—as may be seen, for the example, in many fat-containing products
packed in totally opaque aluminum foil laminates. Food constituents such as ascorbic
acid or tocopherol are efficient in inhibiting autoxidation. Therefore, they may act as
“dual use additives” (i.e., as nutritive ingredients and as antioxidants at the same time)
(Belitz et al. 2008).
2.7.3 Photooxidation
Oxygen molecules may also be excited to other electronic states. When excited to
the singlet state at an energy level of 92 kJ/mol above the ground state, a molecule’s
valence electrons are paired. This singlet oxygen is metastable with a lifetime from 50
to 700 μs (Min and Boff 2002). The paired electrons may then react with other double
bonds (e.g., unsaturated fatty acids) and the presence of radicals is no longer needed.
In food products, the excitation of triplet oxygen to singlet oxygen mainly occurs via
the excitation of sensitizer molecules (see e.g., Buchner 1999). When the sensitizer, a
colorant molecule (such as chlorophyll), absorbs light, it is excited and may, in addi-
tion to other mechanisms, transfer this energy to an oxygen molecule, which then is
transformed into singlet oxygen. This mechanism is called photooxidation.
If a food containing sensitizers is illuminated, the oxidation of specific food
components will start immediately. The oxidation reaction may happen to the sen-
sitizing dye itself but also to unsaturated fatty acids. In relation to the absence of illu-
mination, photooxidation of unsaturated fatty acids is faster by a factor of more than
1000 (Heiss and Eichner 1994; Min and Boff 2002). The reaction will be driven at
the highest rate by light of the wavelength that corresponds to the absorption max-
imum of the sensitizers.
Under constant conditions of illumination and oxygen supply, the reaction will
show a constant rate over a relatively long period. The rate determining steps are
the supply of oxygen, whether it is initially present or permeating through the wall
of the package during shelf life, and the illumination. The packaging-related determin-
ing factors for shelf life are the initial amount of oxygen in the package as well as the
oxygen permeation rate and the light transmission (both of the latter through the wall
of the package). The relation between oxidation rate and illumination intensity is often
nonlinear and already has a relatively high rate at lower intensities. Thus, if one wants
to abstain from packaging under very low oxygen partial pressure, partial light protec-
tion is not sufficient in most application cases; then only an opaque package will help
to avoid this type of reaction.
2.7.4 Quantification of Oxygen Uptake
In order to identify the dominating factor for an oxidative decay process, the full
mass balance for the oxygen present inside the package has to be established depen-
dent on time. This means that the amounts of oxygen in the product and in the head-
space need to be known as well as the oxygen permeating through the package walls.
Because a very low amount of reacted oxygen is needed to create substantial quality
deficits, the analytical methodology used has to be able to discriminate, at a high pre-
cision, between reacted oxygen and oxygen that has been physically absorbed in
the food matrix—the precursor to any subsequent reaction. Unfortunately, not
many investigations have been performed that would fulfill all these requirements,
although the first successful examples date back to the 1960s (see e.g., Hintze et al.
1965).
If the initial amount of oxygen in the package has been kept low and if the
packaging material has high enough oxygen barrier properties, the oxygen that is
initially present in the package and the quantity of oxygen permeating through
the package walls will both undergo a complete reaction with the product. Thus,
the quantity of the reacted oxygen represents the determining factor for the end
of the shelf life.
It is still subject to discussion whether the critical amount of oxygen is best repre-
sented by the mass of oxygen already reacted (as just described) or by a threshold
value of the oxygen partial pressure inside the package (see e.g., Gavitt 1994; Belitz
et al. 2008; Piergiovanni and Limbo 2012). However, as the oxygen partial pressure
alone can only be used as the threshold value under constant conditions of illumina-
tion, it is of limited value in more detailed shelf-life investigations.
As an interim conclusion, there is still a lack of detailed knowledge on the oxida-
tive processes relevant for the quality decay of many food products. So far, the concept
of oxygen tolerance thresholds is still a simplification (Figure 2.4), and any packaging
system designed on the basis of these tolerance thresholds needs experimental verifi-
cation from a shelf-life test under realistic conditions.
Reacted amount of oxygen (a.u.) I IIa IIb
OTI
OTII
Time (a.u.)
SLI SLIIa SLIIb
Figure 2.4 Schematic representation of different oxidative reactions. I: photooxidation; IIa: autoxi-
dation with a shorter induction time, for example, due to UV light; IIb: longer induction
time in absence of illumination (OT = oxygen tolerance thresholds, SL = shelf life).
(Courtesy of Fraunhofer IVV, Freising, Germany.)
2.7.5 Pressure-Dependent Interaction of Oxygen with Food

Constituents: Myoglobin as an Example
One quality decay mechanism that definitely depends on the partial pressure of
oxygen is the color change in fresh meat. The molecule myoglobin is present in the
muscles of mammals, serving as intermediate storage for oxygen. In its nonoxidized
form, deoxymyoglobin, it has a reddish-brown color that changes into cherry red upon
the reversible oxygenation to oxymyoglobin. For fresh meat, this process is still rever-
sible post mortem. However, if exposed to a low, but nonzero, oxygen partial pressure
for a longer time period, oxymyoglobin as well as deoxymyoglobin will undergo a
quasi-irreversible oxidation to the unwanted gray metmyoglobin. This process may
only be reverted by specific enzymes, and it is assumed that such enzymes are perma-
nently active in the mammal organisms to recover myoglobin from the physiologi-
cally inactive metmyoglobin (Bekhit and Faustman 2005). The maximum rate of
formation for metmyoglobin has been reported to occur around an oxygen partial pres-
sure of 5 hPa. At that pressure, the rate is apparently much higher than the enzymatic
reduction. At very low oxygen partial pressure as well as above a partial pressure of
130 hPa, however, metmyoglobin formation is sufficiently hindered for the duration
of the normal shelf life of fresh meat (Forrest et al. 1975; Faustman and Cassens 1990).
The determining factor for this reaction is, therefore, the oxygen partial pressure pre-
sent in the package, which has to be kept either at very low values or above its atmospheric
value of about 210 hPa. The related shelf life–limiting mechanism is the reaction rate
toward metmyoglobin determining the optical appearance of fresh meat. In the case of a
package of initially low oxygen partial pressure (e.g., a vacuum package), the reaction
rate will be determined by the rate of oxygen permeation through the package walls. On
the other hand, in cases where an oxygen partial pressure above the atmospheric value
has been established in the package from the beginning, as in the case of high
oxygen-modified atmosphere packaging, the rate of oxygen depletion to values below
the atmospheric partial pressure is the decisive factor. Here, the oxygen consumption by
the meat product itself is the determining process, driven by some remaining post mortem
metabolism of the meat and the respiration of its microflora. The oxygen permeation
through the package will, in the first instance, be directed toward the outside and thus accel-
erate the quality degradation process. At a later stage, however, when the oxygen partial
pressure inside the package will have dropped below the atmospheric value, the oxygen
permeation will retard the quality decay. Because several partially counteracting processes
are involved in this case, a simple threshold value for oxygen transfer cannot be given here.
If cooked, smoked, cured, or otherwise treated, the myoglobin in meat products
will be changed irreversibly (e.g., into nitrosomyoglobin in case of curing). These
dyes may then be subject to photooxidation, as described earlier, and the related con-
siderations will apply.
2.7.6 Other Light-Induced Reactions
Another group of chemical reactions based on light and a sensitizer create the so-
called light-struck flavor, which is well-known for beer (Gunst and Verzele 1978; Kattein
et al. 1988; Cardoso et al. 2006; Bamforth 2011), wine, and milk (Allen and Parks 1975,
Töpel 2004). Generally, the absorption of light by riboflavin is seen as the initiating step,
which induces reactions among sulfur-containing amino acids. In the case of wine,
methionine and cysteine are discussed as precursors to thiols and dimethyl disulfide.
For milk, the transformation of methionine into methional is seen as the source of the
off-odor; for beer, it is the generation of 3-methyl-2-butene-1-thiol from isohumulones
and cysteine.
Although these reactions have been observed to occur without oxygen, the presence
of the latter may also have an impact on this reaction via a catalytic effect that leads to a
faster regeneration of the dye molecules after the energy transfer. In the case of milk
products, lipid oxidation and the formation of the light-struck flavor may even compete
(IVV 2014).
For these kinds of decay reactions, the packaging-related factors determining shelf
life are the transmission of the packaging material to light in the wavelength range of
the absorption of the sensitizer, to a greater extent, and the oxygen permeation rate
through the wall of the package, to a lesser extent. Different from photooxidative reac-
tions, a partially transparent packaging material will still supply good light protection
if properly selected according to the spectral transmission—as is well known for many
beverage containers.
2.8 PHYSICAL MECHANISMS OF QUALITY DECAY
2.8.1 Changes in Water Content
Changes in water content of packed products have a similar importance for the
limitations in shelf life as oxidative reactions, but they are much simpler to measure.
In contrast to oxygen-induced effects, which may start at amounts below 1 mg/kg of
product, water-induced effects typically begin at a 10 g/kg change in a product’s water

content and may be followed by gravimetric methods. We need to discriminate
between two main types of processes:
• Water uptake by dry products, causing their texture to change from crisp to
soggy, leading to agglomeration of powdery products or even creating condi-
tions that allow microorganisms to grow.
• Loss of water from moist products, also leading to different types of textural
changes, resulting a loss in the gross quantity of the food and, for fresh produce,
rapid senescence.
The physically determining factor for both processes is the water activity, aw, of
the packed product, which is defined as the ratio of the fugacity of the water above
the given food product and the fugacity of pure water under the given conditions of
temperature and pressure. With good accuracy, its value is given by the ratio of the
equilibrium water partial pressure created by the product in a closed environment to
the saturation water vapor pressure in the air for the same conditions (Scott 1957;
Labuza 1984). In equilibrium conditions, the water activity of a product will have a
direct relation to its water content, although it cannot be expected that both values
be equal. For low-moisture products, the water content is usually given as the ratio
of the mass of the water (H2O) in a given product to the mass of the dry product
(e.g., in grams of H2O/grams of dry solids; see Table 2.2). For high-moisture products,
the amount of water in relation to the mass of the total product is the predominantly
used measure (e.g., in grams of H2O/100 g of whole product; Table 2.3).
Table 2.2 Water Content Equivalent to the Adsorption of One Monolayer of Water
and Related Water Activity of Selected Dry and Low-Moisture Products
Water Content for Monolayer Corresponding Water

Food Product Group Coverage/g H2O/100 g of Dry Solids Activity, aw
Dried fruit 4–15 0.1–0.55

Dried legumes 4–7 0.15–0.55
Dried potato 5–7 0.1–0.35
Coffee 2–5 0.15–0.45
Flour 6–8 0.15–0.25
Dried starch, gelatin 7–11 0.1–0.25
Milk powder 2–7 0.1–0.4
Dried meat, fish 2–6 0.03–0.25
Snack foods 3–5 0.17–0.22
Source: Amalgamated from values of Katz, E. E., and Labuza, T. P, J. Food Sci., 46, 2,
403–409, 1981; Iglesias, H., Handbook of food isotherms: Water sorption
parameters for food and food components, Academic Press, New York, 1982;
Labuza, T. P., Moisture sorption: Practical aspects of isotherm measurement and
use. American Association of Cereal Chemists, St. Paul, MN, 1984; Bell, L. N.,
and Labuza, T. P. Moisture sorption: Practical aspects of isotherm measurement
and use, American Association of Cereal Chemists, St. Paul, MN, 2000.
Table 2.3 Equilibrium Moisture Content of

High-Moisture Products (aw > 0.9)
Equilibrium Moisture Content/g

Food Product H2O/100 g of Total Product
Fresh fruit or vegetables

Avocado 73
Banana 74
Pineapple 87
Grapefruit 89
Eggplant 92
Celery 93
Fresh meat/fish (muscle parts)
Chicken breast 74
Pork loin 75
Leg of beef 76
Trout 80
Codfish 82
Dairy or similar products
Butter 14–16
Margarine 18
Cheese, hard 37–42
Cheese, soft 48–65
Source: Iglesias, H.A., Equilibrium moisture contents of

food, In Encyclopedia of agricultural, food, and
biological engineering, ed. D.R. Heldman,
268–274, Marcel Dekker, New York, 2003;
Belitz, H.D., et al., Lehrbuch der Lebensmittel-
chemie, Springer, London, UK, 2008.
Usually, food products are separated into three different groups (Rockland 1969;
Karel 1976; Labuza 1984; Figura and Teixeira 2007; FSAI 2011), namely low-
moisture products, intermediate moisture products, and high-moisture products.
This classification can be made according to different criteria and, therefore, is
not consistent in the literature. The focus may be set as follows:
• On the physical nature of the water in the product

• From a packaging point of view, on the expected direction of water transport
through the packaging material
• On the sensitivity of the product to microbial growth
The following classifications and related ranges of water activity are found in the
literature:
• Low-moisture products: For this product group, (Rockland 1969; Figura and
Teixeira 2007) the limit of the water activity is set at aw = 0.25, thus covering,
for example, milk powder or other intensely dried powdery products. In this region
of water activity, the water content is equivalent to a coverage of the total surface
of the solid food of less than one monolayer of adsorbed water (Katz and Labuza
1981; Iglesias 1982; Labuza 1984; Bell and Labuza 2000). Up to a water activity
of 0.6, the limit used by Labuza (1984) for low-moisture products, the surface cov-
erage will not substantially exceed one monolayer in most cases; see Table 2.2.
From the packaging point of view, the direction of water transport is of great
importance. On the time average, it will be toward the inside of the package
for products with a water activity lower than 0.5 in practically all application
cases. For products within this group with levels of water activity close to
0.6, the amount of transported water will be negligible for temperate conditions
because the humidity difference between the interior and the surrounding atmo-
sphere will be low. Setting an upper limit at aw = 0.85 for low-moisture products
(see FSAI 2011) represents a focus on the microbial activity, which is low
below this value, leading to a low risk of microbial growth.
• Intermediate moisture products: Here, the relevant region of water activities has
been set to between 0.25 and 0.75 (Rockland 1969; Figura and Teixeira 2007)
or between 0.6 and 0.9 (Labuza 1984). Karel (1976) also gives examples for
water activities for this class of foods between 0.61 and 0.96. In this region,
the coverage of the product surface (as long as this can be defined) will often
exceed one monolayer of adsorbed water. In the higher range of aw (between
0.7 and 0.8), products can be found such as cured meat, cakes, biscuits, and pas-
tries with water contents above 15 to 45 g H2O/100 g as well as liquids or gels
such as honey, syrups, or jam. In liquids and gels, a lower water activity is
achieved by adding solutes such as salt or different sugars, which traditionally
act as a provision against easy microbial decay. At water activities between
0.6 and 0.9, the direction of water transport is strongly dependent on the
ambient climatic conditions. However, the amount of transported water generally
will be low whatever the direction of actual water transport. If defined from a
microbiological point of view (such as in FSAI 2011), intermediate moisture pro-
ducts have a water activity between 0.85 and 0.92 and are characterized by a
nonnegligible—but still moderate—risk of microbiological deterioration.
• High-moisture products: This group has been defined by water activities above
0.75 (Rockland 1969; Figura and Teixeira 2007), above 0.9 (Labuza 1984), or
above 0.92 (FSAI 2011). The physical nature of the water in the product is no
longer the adsorbed state but the liquid phase. For part of the products in this
group, water is incorporated in the product matrix—be it in a gel (such as for
cheese), in a tissue (such as for fruit, vegetables, and meat), or in an emulsion
(such as for butter and margarine). The other part of the group consists of liquid
foods or beverages. In all these cases, most of the water is in the liquid state, lead-
ing to a water activity above 0.9 and often even above 0.99 (Labuza 1984). For
goods packed in materials of nonzero water vapor permeability, water transport
will always occur toward the outside of the package. Above a water activity of
0.92, the conditions are favorable for growth of most microorganisms, and related
products show the highest sensitivity to microbial deterioration.
• Some foods cannot be classified in this way because they exhibit an internally
varying water activity, which means that they will never be in the equilibrium
state through their shelf life. Prominent examples are the different variants of
bread that consist of a humid crumb enclosed by a crisp crust. Typical water
contents of the crumb are 45 g/100 g of product with a water activity of 0.96
to 0.98, whereas the crust shows water content of 15 to 20 g/100 g of product
at a water activity slightly below 0.9 (Czuchajowska et al. 1989). This gives an
overall average water content of the total bread between 38 and 41 g/100 g
of product (Belitz et al. 2008). Thus, bread incorporates a transition between
intermediate- and high-moisture products. This imbalance needs to be maintained
over the shelf life of the bread. This explains why special bread types (especially
European ones) are among the foods that are most difficult to keep at a high level
of quality for a longer time span.
For the majority of climatic conditions for food storage and the resulting water
transport through the walls of a package, the limits given by Labuza (1984) best reflect
the packaging point of view and, therefore, are used in the following, with one exten-
sion after (Rockland 1969):
• Dry products for aw < 0.25, representing a water coverage of typically less than
one monolayer
• Low-moisture products for 0.25 < aw < 0.6, for a water coverage around one
monolayer, having at the same time the lowest risk for oxidative decay due
to fat oxidation or nonenzymatic browning (Heiss and Eichner 1971; Eichner
1975; Labuza 1975; Karel 1980; Labuza and Saltmarch 1981)
• Intermediate moisture products for 0.6 ≤ aw ≤ 0.9, with either several mono-
layers of water coverage or even a liquid phase, with dissolved solutes such
as salts or sugars
• High-moisture products for aw > 0.9, being either liquid or incorporating a
water phase
2.8.2 Water-Related Quality Changes: Increase in Water Content
If an initially dried product is exposed to air of higher relative humidity, a higher

value of its water content will be established, accompanied by higher water activity.
The sorption isotherm describes the relation between the water activity of a product
and its water content, measured at constant temperature. If the same curve is obtained
irrespective of the direction of the change in water activity, the sorption isotherm and
the desorption isotherm are identical. This implies that the whole process is reversible.
Figure 2.5 shows three examples of sorption isotherms, following Labuza (1984):
• Type I isotherms represent crystalline substances such as sugars or salts. At lower

values of water activity, the crystals remain intact, the available surface for
adsorbing water is relatively small, and the maximum free area for water adsorp-
tion is limited. At a certain well-defined point in the water activity, the water is
Water content / g / 100 g dry solids

20
Type III
10
Type II
Type I
0
0 0.2 0.4 0.6 0.8 1.0
Water activity, aw
Figure 2.5 Different types of sorption isotherms, schematic representation. (After Labuza,
Moisture Sorption: Practical Aspects of Isotherm Measurement and Use, American
Association of Cereal Chemists, St Paul, MN, 1984.)
able to dissolve the crystalline structure, leading to a rapid uptake of water. This
point, often called the point of deliquescence or the flow moisture point, is typical
for a specific crystalline substance. At room temperature, the related water activ-
ity is between 0.7 and 0.8 for common crystalline sugars and 0.75 for sodium
chloride (NaCl). Here, the crystalline part of the product changes into a liquid,
which often means a total loss of the consumer-related quality.
• Type II isotherms are typical for most dry or low-moisture products, such as flour,
cereals, ground coffee, or dried milk, but also for food ingredients such as starch
or proteins. These products generally have a higher specific surface area than
crystalline substances, leading to an overall higher uptake of water already at a
lower water activity. After a higher initial slope of the isotherm at low water activ-
ity, a smaller slope or even a plateau may be observed at higher aw. The onset of
this lower slope roughly represents the formation of a monolayer of adsorbed
water on the product’s surface. At higher water activity, multilayers of adsorbed
water will be formed, as described for instance by the Brunauer, Emmett,
and Teller (BET) theory (Brunauer et al. 1938). The transition from a submono-
layer toward multilayers also represents a reduction in enthalpy of sorption and,
at the same time, a reduction in binding energy in the food structure. Thus, in
the region above the completion of the first monolayer of adsorbed water mole-
cules, the binding forces between the single parts of the product decrease and
the product will gradually lose its original texture. This process may be reversible.
Because most dry products are porous, their actual surface area has a higher value
than that of their apparent geometrical surface area and, at still higher water activity,
allows for capillary condensation in different types of structures. Here, the slope of
the sorption isotherm curve again becomes steeper.
• Type III isotherms are typical for very specific substances showing a high bind-
ing energy to water already at low coverages. Examples are desiccants such as
zeolites, silica gel, and so-called anticaking agents.
Deviations from the reversible character of the water sorption process are indicated
by hysteresis. Here, a sorption isotherm measured upon adsorption (i.e., at rising
water activity) will show a lower water content at a given water activity than that
measured in a desorption experiment, where the starting point is at a high water
activity (see Figure 2.6). Irreversible effects are even more pronounced if a phase
transition occurs due to water absorption. Figure 2.7 shows a typical example for
an initially amorphous sample of, for example, powdery sucrose. Here, a typical sorp-
tion Type II isotherm begins to form if one starts at low humidity because the amorphous
modification of the sucrose is able to take up much more water than its crystalline coun-
terpart. If the experiment is done slowly enough, there will be a certain point where
enough water has been included in the amorphous sucrose to give a high mobility to
its structure. At this point, recrystallization will start, and most of the water previously
20
g/100 g dry solids
Water content/
10 Desorption
Adsorption
0
0 0.2 0.4 0.6 0.8 1.0
Water activity, aw
Figure 2.6 Hysteresis in an adsorption/desorption experiment.
10
g/100 g dry solids
Water content/
5
Phase I
Phase II
Phase III Phase IV
0
0 0.2 0.4 0.6 0.8 1.0
Water activity, aw
Figure 2.7 Change in water content of an initially amorphous substance upon water absorption.
Phase I: Water uptake of the amorphous substance. Phase II: Crystallization, accom-
panied by water release. Phase III: Low water content of the recrystallized substance.
Phase IV: Deliquescence. (Schematic consolidation of different measurements at
Fraunhofer IVV.)
absorbed in the amorphous phase will be released and redistributed inside the sample
and to the surrounding atmosphere, thus leading to a sudden rise in water activity.
This transition is irreversible under temperate conditions, and curves such as those
shown in Figure 2.7 no longer represent a sorption isotherm in the original sense because
the sample obviously changes its physical structure in the course of the measurement.
These considerations show that the concept of describing changes in foods via
sorption isotherms has its justification but also its limitations. In most cases, a critical
water activity can be identified for dry or low-moisture products in connection with an
increase in their water contents. This critical water activity corresponds to a critical
water content that usually is numerically lower. It may be associated with the follow-
ing quality-related phenomena:
• Reversible or irreversible losses of textural properties, leading either to a loss in

firmness or, on the contrary, to an embrittlement
• Alterations in the microstructure that lead to macroscopic changes, especially
those observed in agglomeration of powdery products
If these phenomena dominate the quality degradation process, the most important
packaging-related factor for shelf life is the water vapor permeation rate through the
wall of the package. For most materials, defects in the package may have an addi-
tional, but much smaller, effect on the water transport than the permeability of the
intact material. Only for virtually impermeable materials such as aluminum foil lami-
nates does the amount of defects determine the water transport.
For intermediate moisture products with water activity in the range of the ambient
relative humidity (e.g., at temperate conditions lower than 25°C and 75% relative
humidity), the direction of water transfer is difficult to predict. At temperate condi-
tions, microbial growth can only sometimes be observed due to water admission.
This is because the water activity threshold for some molds already starts at a water
activity of 0.65 but will be above 0.75 for most microorganisms. In tropical condi-
tions, however, even the water activity limits for toxin-forming microorganisms
may be exceeded; see e.g., Labuza (1984).
2.8.3 Water-Related Quality Changes: Decrease in Water Content of

High-Moisture Foods
High-moisture foods are characterized by a water activity above 0.9, which may
already be reached if a product’s water content is 14 g H2O/100 g, as in the case of
butter. As an approximation, the water activity of high-moisture foods can be taken
as constant for the duration of their shelf life. From a packaging point of view, the
water content of these foods will decrease nearly constantly over time. Known qual-
ity-related effects are the formation of a somewhat chewy outer layer of margarine or
butter, toughening of meat, or wilting of fresh produce. (It should be noted, however,
that the declaration-related effect of a simple weight loss will be the dominating
mechanism in many cases.) The determining factors in the package are the water
vapor permeability of the material used, additional perforations, and—to a much smal-
ler extent—possible deficits in package integrity.
A specific route of quality decay for frozen products is freezer burn. This phenom-
enon, characterized by whitening in the appearance and by toughening in the texture,
is generated by localized water losses from the surface of the frozen product—in most
cases, meat. It may be caused by macroscopic defects in the package where moisture
can directly escape. But, in the case of strong temperature gradients in an intact pack-
age, a local redistribution of water may lead to the same effect and is the subject of the
following section.
2.8.4 Localized Textural Changes without Overall Changes in

Water Content
Even without overall loss or admission of water vapor, textural changes may be
observed that are caused by a redistribution of water in the product in combination
with different crystallization phenomena.
As discussed earlier, water may be released because of an ingredient’s phase change
from amorphous into crystalline. In the case of a powdery food product with different
ingredients, the water released from one ingredient will be suddenly available for further
transformation of other constituents. In such a case, a powdery product containing, for
example, lactose and proteins will start to agglomerate, without the need for further
admission of water.
A similar effect is observed for the interaction of water with starch. Here, starch ret-
rogradation may start above a threshold value of water activity (Zeleznak and Hoseney
1986; Gudmundsson 1994). On a microscopic scale, this process is interpreted as the
recrystallization of amylopectin macromolecules (Labuza 1982; Belitz et al. 2008).
Because the threshold value of water activity is often already exceeded by the product
in its original state, its whole structure may change without external influence. Macro-
scopically, a greater firmness will be observed as is well known for bread staling.
Finally, water may be redistributed in frozen food, leading to an increase in the size
of water ice crystals. An example of the sensory effect is the typical “sandiness” of long-
stored ice cream. Although the water mobility is very low at the industrial freezing tem-
perature of below –18°C (Symons 2000), even including small temperature fluctuations,
sufficiently high water mobility is observed at higher temperatures, such as –5°C.
Because the effects shown in this section may happen without any exchange of
water vapor with the surrounding atmosphere, the main influencing factor is tempera-
ture. As a consequence, the specific effects of packaging on the shelf life of the related
products are minimal.
2.8.5 Loss of Flavors, Uptake of Off-Flavors, or Other Contaminants
Flavors can either be lost from a product via permeation through the wall of the
package to the outside or via absorption by the packaging material—the step preced-
ing permeation. The first effect can be observed for many products when the odor of
their flavor components is noticeable outside the package. The latter effect may even
occur in packaging laminates that, although showing no measurable total permeabil-

ity, are equipped with an inner polymeric sealing layer, such as in the case of card-
board/aluminum foil/polymer laminates. This is often called flavor scalping.
An identical process in the opposite direction is the uptake of off-flavors from the
surrounding environment by the packed product through the package. Because it is
much easier to identify the uptake of off-flavors than the partial loss of flavor consti-
tuents from a product, this uptake is observed much more often in daily practice. The
latter case can be observed especially in cases where a permanent source of off-flavors
is present outside but close to the product, such as for a cardboard box with an inner
polymeric pouch. Here, the cardboard may release the so-called cardboard flavor that
continuously permeates through the pouch into the product. Even worse, contami-
nants from the cardboard such as mineral oils may accumulate in the product by
the same mechanism.
The following characteristics relate to the shelf life of a product:
• The maximum admissible release of flavor from the product to the outside:
Even though usual shelf-life concepts do not take this process into account,
the quality of the surrounding air is sometimes relevant for the quality of a pro-
duct. Imagine highly flavored products such as scented cleaning agents or fra-
grances that may create odor problems when, after a certain time period, flavor
substances are being released into the store. In such cases, consumers’ choice of
other products may be negatively influenced.
• The maximum admissible loss of flavor from the product: As noted earlier, the
flavor is not necessarily transported to the outside but may stay within the pack-
age. The critical amount strongly depends on the individual composition of the
flavors of the product and the quality standards of the producer.
• The maximum admissible uptake of an off-flavor or another contaminant by the
product.
Although all these cases may be relevant in practice, they are not often treated sys-
tematically in packaging design. This is because the occurrence of off-flavors and con-
taminants in the store environment and the thresholds of detection of substances
outside the package are difficult to predict. Single observed cases are predominantly
treated as individual damage events.
2.8.6 Other Physical Limitations of Shelf Life
In many cases, modified atmosphere packaging (MAP) is used, predominantly to

reduce chemical or biotic processes. MAP, however, does not only affect the product
but, due to the difference in the composition between headspace and external atmo-
sphere, it also impacts the overall shape of the package. All polymers show different
values of permeability for different gases (e.g., Yasuda and Stannett 1974, Pauly
1999; Langowski 2008). When looking at the most abundant gases in modified atmo-
sphere packaging, the permeability for carbon dioxide (CO2) is always higher than
that for oxygen, which in turn is higher than that for nitrogen. This is valid for any
given polymer. Therefore, depending on its internal gas composition, the package may
expand or collapse with time. The former effect, often mistaken for microbial activity in
the product, even occurs in the case of totally inert goods. In a pure nitrogen atmosphere,
for instance, an expansion will be created just by the ingress of oxygen from the sur-
rounding atmosphere. In the other extreme, a collapsing effect can be seen on modified
atmosphere packages with a high initial content of CO2. This gas leaves the package
more rapidly than nitrogen, and oxygen is able to replace it by entering from the outside.
After some time in storage, such products look as if they were shrink-wrapped. Both
effects represent limiting factors for shelf life. And, in both cases, the gas permeability
of the packaging materials has to be well-adapted to the initial gas composition, to the
package geometry, and to the required shelf life in order to avoid unnecessary customer
complaints.
2.9 BIOTIC MECHANISMS
2.9.1 Microbiological Mechanisms
As shown in the first section of this chapter, a distinction usually is made between
nonpathogenic microorganisms (spoilage microorganisms) that implicate quality defi-
cits and those that create health risks. For some products, however, this classification is
ambiguous. In seafood, especially, spoilage microorganisms are able to create hista-
mines that, in turn, are pathogen-like for sensitive people. (This fact already shows
the difficulty in correctly selecting a “use by” or a “best before” date for sensitive pro-
ducts such as meat and fish.) In most cases, however, the effects of spoilage microorgan-
isms are clearly detectable by the consumer—for instance, putrescence or the apparent
presence of mold—before a health-relevant effect may occur.
For pathogenic microorganisms and pathogen-like products from spoilage micro-
organisms, specific guidelines are given by the authorities in many regions, especially
in the EU and the United States (see e.g., CR 2073/2005 or FDA 2011). Important
pathogenic microorganisms that are covered by guidelines and regulations are Listeria
monocytogenes, Salmonella, Enterobacter sakazakii, and Escherichia coli. The most
important toxins are staphylococcal endotoxins, the toxin Clostridium botulinum, and
histamine.
In addition, for spoilage microorganisms, guidance values are often given for the
total amount of viable microorganisms as a sum parameter—such as aerobic colony
count or total plate count. Such values have been established as criteria for process
hygiene in sensitive areas, meaning that their observance has to be monitored routinely
at critical points in the production chain and, to a lesser extent, for packed products up to
the end of their shelf life (see DGHM 2016 as an example). Guidance values for packed
food may be as low as 5 × 102 colony forming units (cfu) per gram of product, as in the
case of baby formulae, or typically as high as 106 cfu/g for different meat products and
up to 107 cfu/g for fresh produce (DGHM 2016).
In contrast to these figures, reported microbial contaminations detectable on
packaging materials are remarkably low (Buchner 1999). Populations found on
most films and laminates as well as on thermoformed cups were less than 1 cfu per
dm². Unfortunately, as data for this area are extremely scarce, these results still lack
representativeness. Apparently, however, the occurrence of microbial contamination
generated via packaging is much less probable than via direct food contamination.
2.9.2 Different Effects of Packaging on the Growth of Microorganisms
For the growth of microorganisms, the strongest direct effect of packaging is seen
in the avoidance of further contamination. This is especially important for products
having low guidance values for microbial contamination as described earlier. Such
products require excellent packaging integrity.
The separation of the interior of the package from the ambient atmosphere also
creates indirect effects. The most important indirect effect on microbial growth is
the control of the water activity inside the package. For dry and low-moisture products
having a water activity of aw = 0.6 at maximum, the growth of all kinds of microor-
ganisms is hindered effectively as long as this value is not exceeded. More specifi-
cally, most bacteria are hindered in their growth below a water activity of aw = 0.9,
and most yeasts and molds do not propagate below aw = 0.8. Some exceptions
exist: Halophilic bacteria with a lower limit of aw = 0.75 and osmophilic yeasts and
xerophilic molds that may already start to grow slightly above aw = 0.6 (Leistner
and Rödel 1976; Mossel 1982). As noted earlier, as far as dry and low-moisture pro-
ducts are concerned, these critical regions of water activity are usually not reached at
temperate conditions. On the other hand, the longer shelf life achievable for intermedi-
ate and high-moisture products due to packaging also requires increased attention to
microbiological processes. This is because the packaging keeps the water activity at its
initial level for a longer time compared to unpacked products.
If packed products show their own respiratory activity, such as fresh produce, the
packed product releases additional water. In such a case, it will be difficult to keep the
water activity below a critical value. On the other hand, saturation conditions may be
easily reached, followed by macroscopic condensation inside the package. This is a
condition that is obviously favorable for the growth of molds from spores. As will
be discussed later, avoiding condensation in an MAP for fresh produce is extremely
difficult.
Another indirect effect of the packaging on the growth of microorganisms is the
option to modify the gas composition of the headspace. Two specific types of packa-
ging will be presented in more detail later in this book: MAP, as discussed earlier, and
active packaging, which, in its form as an antimicrobial packaging, has yet to achieve
an industrial breakthrough.
In MAP, the most active agent against microbial growth is CO2, which is toxic at
high pressures and microbiostatic above a partial pressure of about 100 hPa, depend-
ing on the specific case (Buchner 1999). CO2 is, therefore, an important constituent of
many gas mixtures used to fill the head space of pouch and tray packages. Low con-
centrations of oxygen will have an additional effect on aerobic microorganisms, espe-
cially below an oxygen partial pressure of 2.5 hPa (Heiss and Eichner 1994).
If an excess of oxygen relative to the atmospheric composition is applied to enhance

the formation of oxymyoglobin, such as in fresh meat packaging, CO2 is again needed
to reduce the growth of aerobic microorganisms. Here, typically, a headspace content of
more than 20% by volume of CO2 is required to achieve a microbiostatic effect. Often
more than 50%, sometimes even 80%, by volume of CO2 are used in gas mixtures for
ready-to-bake products, which thus can be stored for months without chilling (IVV
2014). On fresh produce, the growth of molds such as botrytis is also known to be
inhibited by CO2 at concentrations already below 20% by volume (Hertog et al. 1999;
Sousa-Gallagher and Mahajan 2013).
For many other products, especially for meat and seafood, differing effects from
CO2-enriched atmospheres or vacuum packaging are reported in the literature
(Rodriguez-Aguilera and Oliveira 2009). Here, the effects of gas mixtures appear to
be less than the effects from cold or frozen storage (Phillips 1996). A common finding
from many investigations on MAP or vacuum packaging of meat or seafood is that a
shift in the gas composition of the headspace just leads to a shift in the populations of
the different species of spoilage microorganisms but, generally, not to a reduction in
their total number (Davies 1995; Jiménez et al. 1997). As an example, the population of
different species of Pseudomonas will be reduced by higher CO2 levels but at the cost
of increased growth of Lactobacilli as facultative anaerobes. The reason why MAP
and vacuum packaging of fresh meat products have gained increasing attention is the
difference between the effects of both types of bacteria on meat quality. Whereas
Pseudomonas is known to create strong off-odors, leading to consumer complaints,
Lactobacilli produce lactic acid, which has the negative effect of some sour odor but,
at the same time, has a positive impact by increasing the tenderness of meat. This exam-
ple shows again why global parameters such as total aerobic colony count cannot always
strongly correlate with the actual food quality.
For pathogenic microorganisms, the effects observed from different concentrations
of Molecular oxygen (O2) and CO2 are not consistent. Care has to be taken to apply low
O2 MAP or vacuum packaging for products such as meat with specific precautions,
especially due to the high risk represented by some anaerobic microorganisms such
as Clostridium botulinum. To limit the possible growth of anaerobic microorganisms,
packaging films of a certain minimum value of oxygen permeability are often used.
Although it can be said that increased concentrations of CO2 do not create an increased
risk for the growth of pathogenic microorganisms (Saucier et al. 2000), the presence of it
does not exclude this risk. Although E. coli and S. aureus are sensitive to CO2, clostridia
are more resistant. This means that there is no direct and controllable effect of different
types of packaging with respect to the safe life of most products. Therefore, the safe life
is predominantly determined by the quality of the meat processing chain prior to packa-
ging and of the temperature regime throughout the whole cold chain.
For spoilage microorganisms, the proper composition of the headspace atmo-
sphere has an influence on the shelf life of many packed products. As a consequence,
the packaging materials have to be well-selected with respect to their permeability for
the relevant gases if MAP or vacuum packaging is applied, and the selection has to be
verified by dedicated experiments. The dominating factor, however, again remains the
temperature control during storage.
2.9.3 Biotic Mechanisms, Relevant for Nonprocessed or Minimally

Processed Food
Nonprocessed or minimally processed food contains cells with a metabolic activ-

ity, either as post mortem activity (e.g., in fresh meat) or as still-living cells with reg-
ular activity (e.g., in fresh fruit or vegetables). These cells are subject to senescence,
which is a multifold process. The simplest mechanism is wilting (i.e., a simple loss of
water), followed by drying of the tissue. This process can be partly avoided by keeping
a high water activity inside the package. This is not difficult because the respiration of
cells leads to a transformation of oxygen into water vapor (and CO2). The rate of this
mechanism determines the lifetime of the product cells and should therefore be decel-
erated. This may be achieved by lower oxygen concentrations or by higher CO2 con-
centrations in the package (Zagory and Kader 1988; Peppelenbos and van’t Leven
1996; Peppelenbos et al. 1996). Such a change in gas composition always occurs in
a package of limited oxygen permeability due to the respiratory activity of the product.
This means that biotic processes are quasi-automatically reduced in the modified
atmosphere generated by the packed product.
When, on the other hand, very low oxygen concentrations on down to totally
anoxic conditions are reached in a package, the cell metabolism will change into fer-
mentation, followed by rapid quality decay. For many types of fruit, vegetables, and
similar products, optimum storage conditions have been experimentally determined in
CA storage. Suitable ranges for partial pressures of oxygen, CO2, and water vapor are
available in the literature (e.g., Saltveit 2001, 2003), often given together with the cor-
responding respiration rates for oxygen into CO2 and water vapor.
2.10 CLASSIFICATION OF FOOD TYPES AND THEIR

TYPICAL MECHANISMS OF DECAY
There are many different ways to classify food products. From a packaging point
of view, such a classification should reflect the mechanisms of decay, the interactions
with the environment, and the structure of the food because all these facts determine
whether the decay mechanisms may be influenced by packaging. Such a classification
attempt has been made in the following section, which is also compiled in Table 2.4.
In most cases, substance transport through the package is the key factor determining
product decay. Often, we may identify an upper limit for the transported amount of the
related substance (e.g., of oxygen or water vapor) that should not be exceeded within
shelf life. As has also been shown earlier, however, for specific products such as fresh
produce or fresh meat, a target concentration of gases or water vapor should be main-
tained in the package. Therefore, we should discriminate between two cases:
• Specific substance transport properties of the package can be specified as

important functionality parameters of the packaging material. The specified per-
meation rates should never be exceeded, but the substance transport rate may be
far below this maximum.
Table 2.4 Condensed Overview of Different Classes of Food Products, Their Decay Processes, and Their Structure, Together with Predominant
Characteristics for Storage and Packaging
Water Exchange
with Growth of
Environment Oxidative Sensitivity Microorganisms Regular Structure
Cell Specific Storage Conditions/
Autoxidation, Direct Uptake Metabolism Specific Packaging Methods
Water Water Spontaneous Photo- Light of Off and Liquid, and Needs/Substance Transport
Product Class Uptake Losses Oxidation oxidation Effects Flavors Spoilage Pathogens Respiration Compact Structured Porous through Package
Dried or low- X (x) (x) X (x) (x) X X Dry storage/high barrier for
moisture food, low moisture, often also gases, light,
fat content and flavors/LT
Dried or low- X X X X (x) (x) X X
moisture food,
high fat content
Compact food, high X X X X X (x) (x) X Ambient or chilled storage/some
fat content moisture and gas barrier, high
flavor barrier/LT
Beverages, X X X X X (x) (x) X Ambient or chilled storage/high
sterilized dairy barrier for gases, light, moisture,
products and flavors/LT
Ready-to-eat food X X X X Chilled storage/good moisture
barrier/LT
Ready-to-cook/ X X X X X X Often chilled storage/high barrier
convenience food for gases or light and moisture/LT
Fresh/minimally X X X X X X Chilled storage/either: MAP with
processed meat/ defined O2 partial pressure and
seafood good oxygen barrier, or:
atmospheric headspace, high
gas permeability/LT or DT
Fresh/minimally X X X X X X Chilled storage/MAP with defined
processed O2 and CO2 partial pressures,
produce high gas and moisture
permeability/DT
(Continued)
41
42
Table 2.4 (Continued) Condensed Overview of Different Classes of Food Products, Their Decay Processes, and Their Structure, Together with
Predominant Characteristics for Storage and Packaging
Water Exchange
with Growth of

Environment Oxidative Sensitivity Microorganisms Regular Structure
Cell Specific Storage Conditions/
Autoxidation, Direct Uptake Metabolism Specific Packaging Methods
Water Water Spontaneous Photo- Light of Off and Liquid, and Needs/Substance Transport
Product Class Uptake Losses Oxidation oxidation Effects Flavors Spoilage Pathogens Respiration Compact Structured Porous through Package
Frozen food X X X (x) X Frozen storage/medium moisture

barrier/LT
Fresh dairy X X X X X X X X Chilled storage/some moisture
products and light barrier/LT
Aged cheeses X X X X X Mostly chilled/often MAP or
vacuum packs, medium gas and
moisture barrier/LT
Retorted food X X X X X (x) (x) X Ambient storage/high barrier for
gases, light, moisture, and
flavors/LT
Ready-to-bake food X X X (x) X Ambient storage/high CO2 MAP,
high barrier for gases, moisture,
and flavors/LT
Fresh bakery X X X (x) X Ambient storage/high moisture
products permeability/DT
Note: Ambient storage: temperate climatic conditions; MAP: modified atmosphere packaging; X: important property or mechanism; X: lower importance; (x): observed only sometimes. Specific storage
conditions: LT, limited substance transport; DT, defined transport properties needed.
• A specific substance transport rate through the package can be identified that
has to be within a given range because a special gas composition is to be
kept in the headspace. In such a case, the functionality parameter is no longer
represented by a maximum specific substance transport property but by a target
range that it has to stay well within.
These two limiting cases are also shown in Table 2.4 and are denoted as “LT” for
limited transport properties and “DT” for defined range of transport properties. As a
common practice in packaging, we often use the word barrier if we mean limited
transport properties and permeability if a defined value of the latter is required,
although both properties are based on identical physical principles.
• Dried or low-moisture foods may strongly suffer from water uptake and, if they
are fat-containing, from oxidative reactions as well. Due to their porous struc-
ture, they offer a large specific area for absorption of off-flavors. As long as the
water activity remains in the range needed for maintaining the physical condi-
tions of the product, the danger of microbial growth is very low. These food pro-
ducts have to be stored under dry conditions, and their package has to offer
significant barriers against moisture and often against gases—especially oxy-
gen, light, and flavor substances.
• Compact foods provide an intrinsic barrier against oxygen transport, meaning
that the gas barrier requirements for their packaging are lower. Examples
include butter and chocolate but also edible oils. Depending on their water
activity (e.g., butter), moisture may be lost or taken up during storage, but
this mechanism is of lower importance for the decay of the quality. To avoid
sorption of off-flavors, a good flavor barrier is needed.
• Beverages and sterilized liquid dairy products will predominantly suffer from
water loss, a declaration-related mechanism. They may also undergo different
oxidative reactions, and light-struck flavors may be generated. An uptake of
off-flavors may occur, which would have a strongly negative effect. Carbonated
beverages will also lose CO2. The resulting packaging requirements are high
barriers against gases, moisture, light, and flavors.
• Ready-to-eat food is characterized by its high sensitivity to microbial growth,
and it has to fulfill dedicated requirements concerning the initial population
of microorganisms. From the packaging point of view, just a good moisture bar-
rier is required because the products will mostly bear a “use by” date with a rela-
tively short shelf life.
• Ready-to-cook/convenience foods may have a longer shelf life, which creates
more risks for oxidative reactions and therefore requires high oxygen barrier
properties in the packaging in addition to the moisture barrier that is a standard
requirement for moist products. Complementary to an oxygen barrier, a high
light barrier may be applied.
• Fresh or minimally processed meat or seafood may be marked either with a
“best before” or a “use by” date, depending on its microbial status at the
moment of packaging and the specificities of the logistic chain. Apart from
its microbial status, the product quality will be dominated by its visual appear-
ance, thus requiring proper control of the oxygen partial pressure inside the
package—either via vacuum packaging, packaging under a modified atmo-
sphere, or packaging under atmospheric oxygen pressure. Modified atmosphere
and vacuum packaging require sufficient gas barrier properties, whereas packa-
ging under atmospheric conditions requires packaging materials with signifi-
cant oxygen permeability. In this specific product group, the barrier (for
limited transport properties) or permeability (for defined transport properties)
requirements may change in accordance with the packaging method applied.
• Fresh or minimally processed fruit, lettuce, or vegetables contain living respir-
ing cells that have to be maintained alive as long as possible. This requires
reduced—but nonzero—levels of oxygen, elevated levels of CO2, and a defined
high water activity (if possible, somewhat below aw = 1). Moreover, they are
often contaminated by spoilage microorganisms such as mold, which can be
inhibited in its growth by the action of CO2. The requirements for packaging
materials are adapted high values of gas and moisture permeability. These
are extremely product specific and, to date, standard packaging materials cannot
completely maintain the internal conditions at the optimum.
• Frozen food generally shows low rates for most deterioration mechanisms due
to its low storage temperature. The most important quality-relevant process is
freezer burn, which requires that the packaging materials have a sufficiently
high moisture barrier to prevent this from occurring. Because all permeation
processes occur at lower rates, many polymeric materials are able to fulfill
this requirement unless damaged.
• Fresh dairy products such as milk or yogurt may be subject to oxidative reac-
tions, alone or in combination with light, as well as to direct light effects. Some
type of light barrier is needed as well as some moisture barrier to avoid water
losses. In spite of fresh dairy products’ high sensitivity to off-flavors, the
requirements for flavor barriers are not very pronounced due to the relatively
short shelf life.
• Aged cheeses, often packed in a high CO2-modified atmosphere to reduce micro-
bial growth, show some sensitivity to oxidation, which, however, is reduced by
the compact structure of the food. Medium barrier properties are sufficient in
most cases.
• Retorted food, which may be stored for a long time under ambient conditions,
requires very high barrier properties against gases, moisture, light, and flavors.
The extremely high barrier of traditional metal packaging sets a difficult bench-
mark for alternative packaging materials.
• Ready-to-bake food is usually packed in high CO2-modified atmosphere to
reduce microbial growth over a relatively long storage period without chilling.
This food has a high water content, and its structure is porous and soft. The
packaging requirements are significant barriers against gases, moisture, and
off-flavors.
• Fresh bakery products often do not have a shelf-life indication, although a cer-
tain shelf life is expected by the consumer—such as in the case of bread bought
daily at the bread shop. An ideal package is difficult to achieve because a per-
manent water transport has to be maintained across the crust to avoid premature
softening and, at the same time, premature drying of the crumbs should not
occur. Packaging materials with defined high water permeability, such as per-
forated film, are often used to pack these products.
2.11 METHODS TO CORRELATE PACKAGING FUNCTIONALITY

AND PRODUCT SHELF LIFE
If we take a synopsis of Table 2.1 and Table 2.4, it is obvious that the transport of
gaseous or vaporized substances through package walls is the key issue for the effect
of packaging on the shelf life of most products. Therefore, a small and simplified
excursus into the relevant parameters of substance transport into and through packa-
ging materials is given in the following section.
2.11.1 Basic Issues of Substance Permeation
In one dimension, the flux F of a substance through a plane sheet of a material,

defined by the amount of substance passing per unit area and unit time, is given
according to Fick’s first law (Barrer 1941; Piringer and Beu 2008; Cussler 2009) by
F = −D ∂c/∂x, (2.1)
where c is the concentration of the relevant substance in the material, x is the spatial
coordinate, and D is the diffusion coefficient of the substance in the material. The con-
centration c is dependent on the partial pressure p of this substance, in the ideal case
via Henry’s law with S = solubility coefficient:
c = Sp (2.2)
For the following considerations, constant values for solubility and the diffusion
coefficient and the validity of Henry’s law are assumed. The dependence of the con-
centration c from time t and spatial coordinate x is given by Fick’s second law:
∂c/∂t = D(∂2c/∂x2) (2.3)
If we want to know the total amount n of a substance that has permeated after time t
through a film sample of unit area from a gaseous region of a constant partial pressure
p1 on one side to another gaseous region of a lower partial pressure p2 on the other
side, an analytical solution can be obtained from Equations 2.1 through 2.3 (see espe-
cially Barrer 1941). The result is shown schematically in Figure 2.8. After an initial
phase where the substance starts to enter the film sample and where the overall con-
centration in the film sample rises, the slope of the curve of n versus t will also rise.
After some time needed for equilibration, there will be a linear slope of the curve,
representing a stationary flux F = ∂n/∂t. = const. This flux is also called the permea-
tion rate.
Reference
mass per unit area

Total permeated
time tr
Stationary state
with linear slope F
Lag time Θ Time (a.u.)
Figure 2.8 Curve of the permeated amount per unit film area, together with two linearizations of
the curve.
Under these stationary conditions, ∂c/∂x also is constant over a distance s, repre-
senting the thickness of the sample. Thus, the concentration is linear in space, going
from a higher value c2 to a lower value c1, leading to
F = D(c2 – c1)/s (2.4)
When looking at the partial pressure p of the relevant substance instead at its con-
centration c, Equation 2.4 can be transformed with the help of Equation 2.2 into
F = DS(p2 – p1)/s (2.5)
or into
F = P(p2 – p1)/s (2.6)
where P = DS is now the permeation coefficient and Q = P/s is the permeability.
If we extrapolate the linear slope in Figure 2.8 toward zero permeated amount, we
end at the so-called lag time Θ. Thus, as an extreme simplification, we may replace the
curve in Figure 2.8 by two connected straight lines—one going on the axis from the
point of origin toward Θ and the second starting at Θ and rising linearly. It is obvious
that this simplification underestimates the permeated amount at a given reference
time tr. If, as another simplification, the value of the lag time is set to zero, we will
have another straight line starting at the point of origin, which leads to an overestima-
tion of the permeated amount. This second simplification will be used often in the fol-
lowing in cases where the lag time is very small in light of the time scale of the relevant
processes.
2.11.2 Consideration of Substance Transport Rates in All

Compartments of the Package: Packed Products,
Package Head Space, and Packaging Materials
An additional complication, which is often neglected, is that the transport pro-

cesses through the package often cannot be evaluated alone but have to be looked
at together with their counterparts inside the package. In other words, the rate of
product deterioration will not be determined only by the rate of substance transport
through the package walls but must be considered in combination with the transport
rate in the product itself and in the package’s headspace.
The type and rate of substance transport in a product strongly depends on that pro-
duct’s structure. Here, we have to discriminate between compact foods without interior
gaseous spaces and porous foods. For the latter, the internal exchange of substances via
gas diffusion or thermal convection will happen much faster compared to the substance
transport through most packaging materials. Therefore, permeation through package
walls represents the determining factor. In compact foods, we have a more or less
homogeneous solid or liquid phase, or a combination of both, where substances
will be transported via diffusion. As will be discussed in more detail in the next sec-
tion, transport rates for substances in compact food products may be of the same
order of magnitude as in some packaging polymers. This means that the resulting
substance transport processes will happen at a lower rate and that the shelf life of
such products will be longer than deduced from simple considerations of the packa-
ging permeability alone.
To illustrate the relationship among substance transport rates in the different com-
partments of a filled package (product, headspace, and packaging material) in more
detail, consider the example of a compact or liquid high-moisture product in a polymer
package at temperate conditions (i.e., 23°C) and at an atmospheric pressure of 1013
mbar for the most important permeating substances, namely oxygen and water vapor,
and for steady-state conditions of the permeation process.
Thus, the maximum possible values of the substance flux for both substances in
the individual compartments (i.e., product, headspace, and package wall) are given
by the maximum possible concentration difference, the diffusion coefficients, and
the characteristic diffusion distance in the compartments.
For the product, we may assume a maximum value of oxygen concentration as
resulting from the solubility for oxygen (Hintze et al. 1965) and from the atmospheric
oxygen partial pressure. The maximum water concentration is given by the equilibrium
moisture content at a water activity of aw = 1; see Table 2.3. For simplicity, the mini-
mum concentrations for oxygen and water vapor can be taken as zero. Some diffusion
coefficients for oxygen in food are available in the literature (e.g., Schrader et al. 1980).
The diffusion coefficient for water in high-moisture food can be assumed to be the self-
diffusion coefficient of water (Cussler 2009). For fats, diffusion coefficient values on
the order of 10−6 cm²/s are reported in the literature (Higuchi and Aguiar 1959). Typical
product sizes range from centimeters to decimeters.
For the gaseous headspace, we can derive maximum concentration differences as
follows: For oxygen, the maximum concentration is represented by its atmospheric par-
tial pressure of 210 mbar, leading to a volume concentration of 1.32 mg/cm³ (23°C,
1013 mbar). For water vapor in air at 23°C, the saturation concentration is 20.62 g/m³,
giving a volume concentration of 0.02062 mg/cm³. The minimum concentrations for
oxygen and water vapor may again be taken to be zero. Typical sizes for the headspace
also range from centimeters to decimeters.
For the packaging material, we will use the available values for the oxygen and
water vapor transmission rates, which are proportional to the permeation coefficient.
For this specific example, the following typical packaging polymers have been
selected: polyvinylidene chloride (PVDC), as a material with very low permeability
both for oxygen and water vapor; polyethylene terephthalate (PET), as a material of
low oxygen permeability; low-density polyethylene (PE-LD), as a material of
relatively low permeability for water vapor but high permeability for oxygen; poly-
styrene (PS), as a material of very high oxygen permeability; and regenerated cellulose
(CE), also known as cellophane as a material of extremely high permeability for water
vapor. The range of diffusion coefficients and the permeability values have been taken
from (Pauly 1999). Typical figures for the thickness of polymeric packaging materials
range from 30 to 300 μm.
The results of this comparison are shown in Table 2.5. The following conclusions
may be drawn:
• For water vapor, transport rates in the product or the gaseous headspace are gen-
erally much higher than in the packaging material, except for extremely high
permeable polymers such as cellulose. This means that the water transport
through the packaging material is the limiting step, and the transport through
the two other compartments can be neglected for most practical cases.
• For oxygen, the transport rate in the gaseous headspace is higher by a factor of
more than 1000 compared to the transport in the product or in the packaging
material. Oxygen transport rates in compact products, however, may be in
the same range as in packaging materials of higher oxygen permeability.
• Therefore, if the transport processes in the packed products are not considered,
as will be the case for purposes of simplification in the examples in the follow-
ing sections, this leads to an overestimation of the oxygen-induced damages in
the product because the product’s additional barrier effect against oxygen has
been neglected.
2.11.3 Packaging Functionality and Product Shelf Life with Regard to

Flavors, Off-Flavors, and Contaminants
The principle shown in Figure 2.8 has been extended to the specific case in Figure 2.9.
Here, the amount of a certain substance adsorbed by a polymeric packaging material
on its inner side (upper curve) and the release of it from its outer side (lower curve) are
shown schematically and time dependently. For simplification, it is assumed that
the packaging material is homogeneous, that the concentration of the substance inside
the package and the coefficients of diffusion and solubility remain constant, and that the
concentration of the substance outside the package remains negligible—all for the whole
duration of the shelf life. At any time, the difference Δ between the upper and the lower
curves gives the amount of substance that is located in the polymeric wall. In the equi-
librium state that is reached after the lag time Θ, the amount adsorbed in the wall remains
constant. Its value will be exactly half of the amount that would be adsorbed by a poly-
meric wall covered by an impermeable layer on the outer side, as in the case of a lami-
nate with an aluminum foil.
Table 2.5 Characteristic Figures for Oxygen and Water Vapor Transport in Compact High-Moisture Food, Gaseous Packaging
Headspace, and in Selected Common Polymeric Packaging Materials
Food Product Gaseous Headspace Polymeric Packaging

Typical size range cm to dm cm to dm 30 to 300 μm
−6 −5 −9
Range for diffusion coefficients, Water vapor 2 × 10 2 × 10 0.26 Some 10
in cm²/s (fats) (water) to
Oxygen 1.4 × 10−6 1.8 × 10−5 0.20 Some 10−7
(butter) (water)
Maximum concentration Water vapor 135 890 0.021 3 × 10−3 (PVDC) to 40 (CE)
difference over typical size (butter) (grapefruit)
range, in mg/cm³
Oxygen 0.82 9 × 10−3 0.28 1.5 (PE-LD) to 5.3 (PS)
(butter) (water)
Resultant range for maximum Water vapor 3 × 10−5 to 2 × 10−3 6 × 10−4 to 6 × 10−3 PVDC: 1.5 × 10−9 to 1.5 × 10−8
substance flux, in mg/(cm² s) PE-LD: 3.9 × 10−7 to 3.9 × 10−6
CE: 1.1 × 10−4 to 1.1 × 10−3
Oxygen 2 × 10−8 to 2 × 10−6 6 × 10−3 to 6 × 10−2 PVDC: 2 × 10−10 to 2 × 10−9
PET: 2.4 × 10−9 to 2.4 × 10−8
PE-LD, PS: 2 × 10−7 to 2 × 10−6
Note: To facilitate the comparison, consistent units have been used for concentrations and substance fluxes/permeation rates that differ from
those generally used for packaging materials.
CE: regenerate cellulose film; PE-LD: low-density polyethylene; PET: polyethylene terephthalate; PS: polystyrene; PVDC: polyvinylidene
chloride.
49
Absorption
Total amount of transferred b: Acceptable loss of flavor on the
inside
Δ
substance (a.u.)
Release to
a: Detection threshold the outside
from outside
Lag time Θ Shelf life a Shelf life b 2.76 Θ Time (a.u.)
Figure 2.9 Amount of a specific flavor substance absorbed on the inside of a package (upper
curve) and released to the outside (lower curve), with hypothetic threshold values
(see text for details). (Courtesy of Fraunhofer IVV, Freising, Germany.)
There are two different characteristic figures that could theoretically be related to
the shelf life of the product:
• The maximum admissible release of flavor to the outside, related to its detection
threshold (a).
• The maximum admissible loss of flavor from the product, related to its qual-
ity (b). This depends on the individual composition of the flavors of the product
and the quality standards of the producer.
For both effects, different shelf-life periods could be estimated, provided that the
sorption and permeation data for the relevant flavor substances in the packaging mate-
rials and the related threshold figures are known. Some sorption and permeation data
can be found, for example, for alkanes and ketones in biaxially oriented PET (Dhoot
et al. 2004); but for the majority of substance-polymer combinations, quantitative data
are largely missing in the literature. Although flavor losses due to flavor absorption
have often been analytically proven to occur (Stöllman et al. 2000), changes in sensory
perception could not even be detected in the extensive investigations of van Willige
(2002; van Willige et al. 2002a, 2002b), who used worst-case conditions via flavor
absorption in PE-LD.
As a consequence, it is still difficult to establish a coherent relation between per-
meation data for flavors and contaminants and shelf life, predominantly due to the lack
of available data. Therefore, threshold figures for flavor losses have to be identified via
sensory assessments in every specific case, and the values will depend entirely on the
individual composition of the product.
Similar considerations can be applied for the ingress of external substances. In such
a case, the direction of substance flow will be inverted, and the lower curve shown in
Figure 2.9 will show the amount of substance absorbed by the product. The detection
threshold now can be replaced by an acceptance threshold, if known. Such estimations
have been presented by Diehl and Welle (2015) in the case of mineral oil components
migrating from cardboard through plastic pouches into packed products.

Oxidative Processes
It was shown earlier that, in many cases of oxidative decay of products, an oxygen
threshold value can—in a good approximation—give the relation between the amount
of oxygen reacted with the product and a quality threshold that determines the shelf
life. Values for this oxygen tolerance are given in Table 2.6 for selected products.
(For other products, where the concept of oxygen tolerance cannot be applied—either
because the mechanism of the oxidative decay depends on additional parameters or
because a specific oxygen partial pressure has to be maintained—the following con-
siderations cannot be applied and dedicated, product-specific investigations have to be
performed.)
Table 2.6 Guidance Values for the Oxygen Tolerance of Selected Products, Given in
mg O2/kg of Product
O2 Tolerance
[Heiss 1975], O2 Tolerance O2 Tolerance,
Product [Heiss 1990] [Piergiovanni] Consolidateda
High moisture products, aw > 0,9

Beer 1–4 1–5 0.5–1b
Wine 3 1–5 1–5c
Milk 8 n.a. 1d– 8b (UHT milk)
UHT cream n.a. n.a. 0.8–1.2b
Fruit juices, soft drinks 20–85 10–40 10–40
Retorted food < 15 n.a. 15
(vegetables, baby
food, …)
Hard cheese 420 n.a.f 100d–400b
Fats n.a. 50–200 20–200e
Dry or low moisture products, aw < 0,6
Nuts, snacks, chips < 15 n.a. 15–75
Coffee 110 (roasted) 15–50 (instant coffee) 20
Other dried foods <15 5–15 5–15
Oils 30–40 (soybean) 50–200 20–200e
a
Based both on literature sources and internal measurements at Fraunhofer IVV.
b
Stored dark.
c
Depending on sulfite addition.
d
Stored under illumination.
e
Depending on fat/oil type and illumination.
f
Not available
Together with the oxygen tolerance, the following properties of the packed pro-
duct, packaging materials, and packaging media are relevant for shelf life:
• The initial amount of oxygen present in the product and the headspace at the
time of packing
• The oxygen permeability of the packaging material
• Possible additional porosities in the final package (e.g., at the sealing seams)
For the processes of photooxidation and autoxidation, the oxygen threshold figure
is only valid for a given light transmittance of the package, which is to be measured in
the specific wavelength range relevant for the product under study.
If the oxygen consumption of the packed product is faster than the oxygen supply
from the outside, the shelf life of a product in a package without additional defects made
from a material of known oxygen permeation properties can then be estimated as sche-
matically shown in Figure 2.10: The red curve represents the cumulated amount of oxy-
gen that has permeated into the package after a given time. If we take the oxygen
tolerance threshold of the product under study (or, in the case of new product develop-
ment, the threshold valid for a similar product) and subtract the initial amount of oxygen
in the food, the intercept of this difference with the curve of the cumulated amount of
permeated oxygen will give an estimate for the product’s shelf life.
In most cases, the lag time for oxygen will be very short in comparison to the shelf life,
so it can be neglected. The curve representing the cumulated amount of admitted oxygen
can then be represented by a straight line starting at the point of origin with a slope given
by the oxygen permeability of the packaging material, QO2, the surface area of the pack-
age, A, and the difference in oxygen partial pressure between the inside and outside of the
package, Δp. The oxygen permeability, Qr O2 as required for the shelf life ts then becomes
Qr O2 = Δm/(AtsΔp) (2.7)
It is obvious that this simple scheme will always underestimate the shelf life if
the oxygen consumption by the product is slower than the oxygen ingress in the
Oxygen tolerance of product

Total admitted mass
Minus initial content

of oxygen (a.u.)
Allowed O2 admission Δm
Lag time Θ Shelf life ts Time (a.u.)
Figure 2.10 Estimation of the shelf life of an oxygen-sensitive product from its oxygen tolerance
and the oxygen permeation properties of the packaging medium for a product show-
ing rapid oxidative reactions (a.u.= arbitrary units). See text for further details.
package or if, as shown previously, the oxygen transport in the product is subject to a
similar rate as in the packaging material. As a worst-case approximation, however, it
may well be used as a first attempt for the selection of appropriate packaging mate-
rials to be used for an initial shelf-life study before starting an optimization proce-
dure.

Water Uptake/Losses
As shown previously, in the absence of irreversible reactions, water-related dete-

rioration processes may be described via the initial water content of a product and a
quality-related threshold value of its water content, with their difference giving the
maximum water uptake Δm. In addition, the water activity values corresponding to
both values of water content are needed, aw,in and aw,c, as well as the ambient water
activity aw,out, describing the storage conditions. From these figures, we may either
estimate the shelf life for a given water vapor permeation rate of the packaging mate-
rial or, vice versa, estimate the required maximum of the water vapor permeation rate
for a given shelf-life period.
For high-moisture products, water losses are the relevant mechanism. Here, we
may assume a constant water activity inside the package, aw,in equal to 1 with suffi-
cient accuracy, and an ambient water activity aw,out of 0.5, representing average sto-
rage conditions. In such a case, we will have a constant difference in water activity,
Δaw, equal to 0.5, resulting in a constant loss of moisture over time.
For dry or low-moisture products showing a regular sorption isotherm, the follow-
ing procedure can be applied. Here, the difference of the water activity between inside
and outside is no longer constant, meaning that there will be a continuously decreasing
difference between the water activity in the environment, aw,out, and the water activity
at the inner side of the package, aw,in. For such a situation, a calculus was first pub-
lished by Becker (1974) and later by Labuza (1984), using the fact that the region
of the sorption isotherm between the initial water content and water activity and the
critical water content and activity can be linearized (see Figure 2.11).
This calculus may be further simplified if the maximum tolerable water activity in
the package, aw,c, is far below the ambient water activity, aw,out. For a worst-case
estimate, the usual maximum humidity for temperate climate, 75% relative humidity
(aw = 0.75), may be used as the ambient water activity value. Then, we may replace the
integration of the time-dependent difference in water activity from the outside to the
inside, as demonstrated by Becker (1974) and Labuza (1984), by using a constant dif-
ference Δaw between the outside water activity, aw,out, and the arithmetic mean of the
water activity inside the package over the duration of the shelf life, (aw,c + aw,i)/2. This
difference is given by
Δaw = aw,out − (aw,c + aw,i)/2 (2.8)
The following parameters are needed (in addition to Δaw) to estimate a gui-
dance value for the water vapor transmission rate of the package that is required
to keep the product dry enough for the given shelf life: The required shelf-life
(aw,c+ aw,i)/2
Water content, e.g. in g/100g dry solids

10 Δaw
6 aw,c
aw,out
4
Δm/m
2 aw,i
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 aw
Figure 2.11 A hypothetical sorption isotherm of a low-moisture product linearized between initial
water activity aw,i and critical water activity aw,c. See text for further details.
period, ts, the admissible change in water content of the product, Δm, the surface
area of the package, A, and the water activity aw,p that are valid under the con-
ditions that were used to measure the water vapor permeation rate of the packa-
ging material.
Then, the guidance value for the required water vapor transmission rate of the
packaging material, TRr,H2O, is given, approximately, by
TRr,H2O = (Δmaw,p)/(AtsΔaw) (2.9)
It can be shown that this strong simplification leads to an error of less than 8% in
comparison to the calculus of Becker (1974) and Labuza (1984), if the critical water
activity of a dry or low-moisture product is below 0.5 at an outside water activity of
0.75 or above. Moreover, it represents a worse case because it always leads to a slight
underestimation of either the required water vapor transmission rate or of the resulting
shelf life. For comparison, the result according to Becker and Labuza is given as fol-
lows, which yields

Δm aw,p aw,out − aw,i
TRr,H2O = ln (2.10)
ts A ðaw,c − aw,i Þ aw,out − aw,c
Quantitative examples for allowed changes in water content and of admissible

uptake or loss of water are given in Table 2.7.
2.11.6 Guidance Values for Oxygen Permeability and Water Vapor

Permeation Rate of Packaging Materials
In the following, a summarizing representation is offered for guidance values of

the oxygen permeability and the water vapor permeation rate of packaging materials
intended for use for selected products. The values represent maximum figures with
Table 2.7 Initial Water Content, Deterioration Mechanisms due to Water Losses and Resulting Admissible Uptake or Loss of Water for
Selected Products
Initial Water
Contenta/g H2O/kg Admissible Uptake (+) or Loss (−) of
Product of Product Mechanism of Deterioration Watera/g H2O per kg of Product
High moisture products, aw > 0.9

Beer >945 Water loss: exceeding of maximum deviation of contentsb Ranges for losses in relation to
Wine >885 (declaration related, most probably reached before quality nominal contentsb:
effects can be observed) −45 for 100–200 ml or g
UHT milk >870
−30 for 500 ml or g
UHT cream >650–850
−15 for >1000 ml or g
Fruit juices, soft drinks 850–900
Retorted food 750–900
(vegetables, baby
food, …)
Hard cheese 380–450
Fats 140–180
Dry or low moisture products, aw < 0,6

Nuts, snacks, chips 6–60 Water uptake: texture losses +20–+50
Coffee (instant or 20–25 Water uptake: exceeding of allowed water contentc +25–+30
ground)
Other dried foods 20 –150 Water uptake: texture losses, agglomeration +20–+50
Oils 0.3–0.6 Not relevant, very low water uptake at ambient conditions
a
Based on both literature sources and internal measurements at Fraunhofer IVV.
b
Council Directive (1976) 76/211/EEC.
c
Directive 1999/4/EC and KaffeeV (2006).
55
their typical spread—not target ranges as would be applicable in case of, for example,
fresh produce. They have been calculated with the help of Equation 2.7 (for the
required oxygen permeability) and Equations 2.9 and 2.10 (for the required water
vapor transmission rate) based on the simplifications as described in the two preceding
sections and on the following additional facts and assumptions:
• Only permeation through the intact walls of the packages is considered.

• Storage is assumed at temperate conditions of 23°C, 75% relative humidity for
dry or low-moisture products and of 23°C, 50% relative humidity for high-
moisture products.
• A fast oxidative reaction is assumed, leading to zero oxygen partial pressure
over the whole storage time and thus to an oxygen partial pressure difference
across the packaging material of 0.21 bar.
• The admissible uptake or loss of water has been taken from the same sources as
in Table 2.7.
• Values for the ratio of the contents to the surface area and for typical indicated
shelf-life periods have been taken from shop surveys for the related products
(IVV 2014).
Consolidated results are shown in Table 2.8 and in Figure 2.12.
2.11.7 Packaging Functionality and Product Shelf Life for

Respiring Products
In contrast to the cases discussed before, respiring or highly reactive products

such as fresh meat or fresh produce do not simply require maximum permeation
rates for their packages (e.g., for oxygen, CO2, and water vapor). To keep the living
cells or the reactive colorants in optimum conditions, and to minimize microbial
growth at the same time, gas composition and humidity in the package have to
stay within defined ranges. Moreover, the decay processes are dependent on tem-
perature to a large extent.
The respiratory release of water creates an additional, fundamental problem: If
one wants to keep the internal oxygen concentration at a value well below atmo-
spheric conditions and, at the same time, to maintain the water activity at a value a
bit below aw = 1.0 to avoid condensation, this will be impossible for nonactive
packaging because the water vapor permeation rate of virtually all packaging
materials is much lower than their oxygen permeation rate. (It should be noted
here that the permeation rate at the relevant conditions is addressed not the per-
meability.)
The number of these effects would require a multifactorial approach. This has to
take into account the respiration rates of the product, the permeation rates of the
package and its geometry, the temperature, and the response of the product and
its microflora to all these parameters, in dependence on time. The most advanced
information in this context has been collected over the last two decades for packed
Table 2.8 Selected Products and Related Permeability Values for Their Packaging Materials as Derived from Oxygen Tolerances, Admissible
Changes in Water Contents, Typical Packaging Geometries, and Typical Figures for Indicated Shelf Life, with a Focus on the German
Food Market
Required H2O
Transmission
O2 Tolerance, Admissible Uptake (+) Contents-to- Average Difference Required O2 Permeability Rate TRr H2O/g/
Consolidateda/ or Loss (–) of Watera/g Surface Ratio/ Typical Indicated in aw (Inside vs. Qr O2/cm³(STP)/(m² d bar) (m² d) @ 23°C,
Product mg/kg H2O per kg of Product kg m−2 Shelf Life Outside) @ 23°C 85 → 0 % r.h.
High moisture products, aw > 0.9

Beerb 0.5–1 −30 9.8–10.9 (0.5 l) 8.3 6–12 months 0.5 0.045–0.200.038–0.15 1.4–3.01.2
(0.33 l) with sufficient
accuracy
Wineb 1–5c −20 (0.75 l) −15 11 (0.75 l) 20.7 not required 0.10–0.50c0.19–0.95c 1.0 1.4
(3 l bag-in-box) (3 l bag-in-box) (calculated for
12 months)
Fruit juices, soft 10–40 −15 10–14.6 1 to 18 months 0.61–61.4 0.47–12.2
drinks
UHT milk 1d–8b −15 14.6 10 to 20 weeks 0.35d–5.6b 2.7–5.3
b
UHT cream 0.8–1.2 −15 14.6 10 to 20 weeks 0.28–0.83b 2.7–5.3
Hard cheese 100b–400c −45 5.3 2 months 86–345e 50e
(cool storage)
Retorted food 15 −45–−20 9.1 (pouch) 10 3–12–36 months, 0.59–5.0 0.40–7.6
(vegetables, (cup) lower for plastics,
baby food, …) 13 (jar, can) higher for metal
or glass
Fats 20–200 −45–−30 9.3 butter 3 months 6.8–80 5.2–9.2
11 margarine
(Continued)
57
58
Table 2.8 (Continued) Selected Products and Related Permeability Values for Their Packaging Materials as Derived from Oxygen Tolerances,
Admissible Changes in Water Contents, Typical Packaging Geometries, and Typical Figures for Indicated Shelf Life,
with a Focus on the German Food Market

Required H2O
Transmission
O2 Tolerance, Admissible Uptake (+) Contents-to- Average Difference Required O2 Permeability Rate TRr H2O/g/
Consolidateda/ or Loss (–) of Watera/g Surface Ratio/ Typical Indicated in aw (Inside vs. Qr O2/cm³(STP)/(m² d bar) (m² d) @ 23°C,
Product mg/kg H2O per kg of Product kg m−2 Shelf Life Outside) @ 23°C 85 → 0 % r.h.
Dry or low moisture products, aw < 0.6

Nuts, snacks, 15–75 20–50 1.2–3.5 3 to 12 months 0.55–0.6 0.16–9.6 0.093–3.0
chips
Coffee (instant or 20 25–30 7.1 12 to 18 months 0.45 0.87–1.3 0.61–1.1
ground)
Other dried/ 5–15 20–50 3–6 12 to 24 months 0.4–0.5 0.068–0.82 0.14–1.7
powdery foods
Oils 20–200f n. r. 14 > 12 months n. r. 2.6–26f n. r.→ 30g
Note: n.r., not relevant.

a
Based on literature sources, shop surveys, and internal measurements.
b
Stored dark.
c
Depending on sulfite addition.
d
Stored under illumination.
e
Estimated for storage conditions of 6°C and 50% r.h., permeation values changed accordingly.
f
Depending on oil type and illumination.
g
Value for PET taken as basic requirement.
Water vapor permeability / mol/(m2s Pa)

–9
10 10–8 10–7 10–6
1000
@ 50...75 % r.h. / cm3(STP) / (m2 d bar)
Coffee Hard
10–12
Fats cheese
@ 50...75 % r.h. / mol / (m2 s Pa)

100
Fruit juices
Oxygen permeability
Oxygen permeability
10–13
Nuts, snacks
10
Oils
Retorted
food 10–14
1
UHT milk
UHT cream 10–15
0.1
Other dried food
Beer
Wine 10–16
0.01
0.01 0.1 1 10 100
Water vapor transmission rate @ 85 → 0 % r.h. / g/(m2 d)
Figure 2.12 Graphical representation of Table 2.8. Guidance values of required oxygen and
water vapor permeability and of water vapor transmission rate for a reference tem-
perature of 23°C, for selected products.
fruit and vegetables. Quantitative models have been set up that are able to describe
the time behavior of the gas composition of the headspace and to correlate this with
specific mechanisms of decay such as the growth of mold (Hertog and Tijskens
1998; Hertog et al. 1999; Fonseca 2002a, 2002b; Caleb et al. 2012; Souza-Galla-
gher and Mahajan 2013). Because the required permeation rates of the packages
are often very high, perforation is taken as an additional way to modify the transport
properties of the packaging in addition to the selection of a material (González-
Buesa et al. 2009). As an example, required permeation rates for oxygen may be
some 1000 cm³(STP)/(m²day) up to some 100,000 cm³(STP)/(m²day) in the case
of fresh produce.
For meat products, such complex approaches are still not in use. In most cases,
microbial growth is taken as the main decay mechanism, with temperature being
the predominant influencing factor (Dalgaard 1995; Raab et al. 2008; Bruckner
et al. 2013). A multifactorial approach that also takes into account the headspace
atmosphere and the evolution of color and oxidative status as quality parameters
has been shown by Limbo et al. (2010).
In all these cases, however, an iterative approach has to be applied when looking
for the optimum properties of a packaging for a given instance. Due to the inherent
complexity of a product/packaging system, simple rules cannot be given here, and
any optimization asks for a careful consideration of the very specific properties of
the related product.
2.12 CONCLUSIONS AND OUTLOOK
We observed that the exchange of substances between the outer atmosphere and
the inner side of the package and the ingress of light are decisive factors for the quality
decay processes of most packed food products. Therefore, the permeation and light
transmission properties of packaging materials are the most important functional
determinants for the shelf life. Although the principal relationships among product
properties, storage conditions, and functional parameters of the packaging materials
are well known, there is still a lack of detailed quantitative information, especially
concerning the decay mechanisms of many foods.
If an appropriate package for an existing or new product has to be found, general
guidelines have been given in this chapter that allow for an initial selection of the
related packaging material on the basis of its available functional properties. After
this initial selection, however, practical tests have to be performed under realistic con-
ditions, and these procedures cannot be circumvented.
Several attempts have been published for computer-based modeling of the quality
decay of products in relation to packaging, some dating back to the 1980s and even the
1970s (Herlitze et al. 1973; Labuza 1982). The practical usage of such models for real
shelf-life predictions still seems to be very limited. In most cases, only one or two
mechanisms of decay were considered (Gavitt 1994; Dalgaard 1995; Raab et al.
2008; Piergiovanni and Limbo 2012; Bruckner et al. 2013).
In addition, ways to accelerate shelf-life tests—often by using elevated storage
temperatures—have their limitations. Although most decay processes may be modeled
in a certain temperature range by Arrhenius-type equations, their energies of activation
are largely different for different food ingredients (Labuza 1982; Labuza 1984). Their
combined behavior is extremely difficult to predict, and the following still seems to
be valid (Ellis and Man 2000, p.31): “… It is a general rule that the more rapid the degra-
dation induced, and thus the further from normal storage conditions, the less reliable the
shelf-life estimate is likely to be.”
As a consequence, the specific variations and uncertainties in the individual charac-
teristics of products are large, and modeling still cannot replace a thorough assessment
of their decay processes. Therefore, many more facts are needed for many different
types of food before quantitative knowledge-based predictions of shelf life may be
widely applied in practical applications.
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CHAPTER 3
Testing of Physical, Optical, Electrical,

Thermal, and Rheological Properties for
Plastic Packaging Materials
Young T. Kim, Hezhong Wang, and Byungjin Min
CONTENTS
3.1 Introduction.....................................................................................................68
3.2 Physical Properties of Plastic Packaging Systems..........................................69
3.2.1 General Features: Molecular Weight, Color, and
Optical Properties................................................................................69
3.2.2 Testing Methods for Physical Properties ............................................70
3.2.2.1 Molecular Weight Determination ....................................... 70
3.2.2.2 Color Measurements ........................................................... 72
3.2.2.3 Opacity Measurements........................................................ 72
3.3 Electrical Properties of Plastic Packaging Systems ........................................73
3.4 Thermal Properties of Plastic Packaging Systems..........................................73
3.4.1 General Features of Thermal Properties .............................................73
3.4.2 Testing Methods of Thermal Properties .............................................75
3.4.2.1 Change of Energy Absorption or Release .......................... 75
3.4.2.2 Change of Dimension ......................................................... 76
3.4.2.3 Change of Weight ............................................................... 78
3.4.2.4 Modulus Measurements ...................................................... 79
3.4.2.5 Heat Distortion Temperature (HDT)................................... 79
3.5 Morphological Property ..................................................................................80
3.5.1 General Features of Synthetic Polymers.............................................80
3.5.1.1 Crystallinity......................................................................... 81
3.5.1.2 Orientation .......................................................................... 84
3.5.2 Testing Methods for Morphological Properties..................................85
3.5.2.1 X-Ray Diffraction ............................................................... 85
3.5.2.2 Calculation of Crystallinity................................................. 87
3.5.2.3 Density Measurements........................................................ 88
67
3.5.2.4 Calorimetry ......................................................................... 90

3.5.2.5 Microscopy ......................................................................... 91
3.5.2.6 Infrared Spectroscopy and Raman Spectroscopy ............... 91
3.5.2.7 Electron Microscopy........................................................... 91
3.5.2.8 Transmission Electron Microscopy .................................... 92
3.5.2.9 Scanning Electron Microscopy ........................................... 92
3.5.2.10 Atomic Force Microscopy .................................................. 92
3.6 Rheological Property ......................................................................................93
3.6.1 Rheology in Plastic Packaging Polymers ...........................................93
3.6.2 Rheology Properties and Measurements.............................................94
3.6.2.1 Stresses and Strains............................................................. 95
3.6.2.2 Viscosity ............................................................................. 96
3.6.2.3 Melt Index........................................................................... 97
3.6.2.4 Cone and Plate Rheometer.................................................. 97
3.6.2.5 Capilliary Rheometry.......................................................... 99
3.7 Conclusion ......................................................................................................99
References ..............................................................................................................100
3.1 INTRODUCTION
For several decades, plastic packaging films or containers have been produced by
a variety of processes including extrusion, injection, or thermoforming, using various
synthetic polymers or biobased polymers by various food product systems. The prop-
erties of commercial plastic polymer packaging products are also highly dependent on
the processing conditions used to produce the final product. Food packaging is the lar-
gest portion of plastic packaging applications among various business sectors. Unfor-
tunately, when foods are packed into a plastic packaging system and delivered for sale
in the marketplace, the quality of both the food and packaging product gradually starts
to reduce during transportation, distribution, storage, and display before consumption
by consumers. By using appropriate packaging materials supported by advanced food
packaging techniques, the quality of food products will be extended and consumer
satisfaction and safety will be achieved. Plastic packaging materials for food products
are extremely complicated and specialized for individual food products because
numerous types of food products are available in the market. These products include
fresh or cooked, refrigerated or frozen, plant-based or animal-based, liquid or solid,
and so on. Furthermore, foods are served or consumed in various ways, such as
dry, wet, oily, cold, and hot. Thus, food packaging plays a crucial role in maintaining
quality and safety of foods during the entire life cycle of both the food and packaging
products. To develop and optimize a plastic food packaging system for the best fit for
particular food items, many properties and characteristics of packaging materials
should be examined in multiple aspects such as physical, thermal, morphological,
rheological, electrical, and so on. A better understanding of properties and character-
istics of packaging materials will provide fundamental knowledge to narrow down the
appropriate material selection to ensure the basic functions of packaging: protection,
TESTING OF PLASTIC PACKAGING MATERIALS 69
quality assurance, safety enhancements, communication, good exterior design, and

functionality (Robertson 2012). Very recently, advanced packaging technologies
designed for reinforcing the technical function of the packaging system have been
actively introduced and developed. These new trends in the food packaging area
include the following technologies: active packaging, modified atmosphere packaging
(MAP), biodegradable packaging, smart packaging, intelligent packaging, microwa-
vable packaging, edible packaging, nano-based packaging, radio frequency identifica-
tion (RFID) packaging, biosensor embedded packaging, and so on. However, these
novel technologies are still challenged by the cost of materials, efficiency, processa-
bility, compatibility with existing processes, and feasibility for mass production. To
overcome the hurdles and maximize the use of novel packaging technologies, it is
important to evaluate various properties with appropriate testing methods and to pro-
vide a relevant quality assurance for individual food products.
In this chapter, therefore, the most significant physical, thermal, morphological,
rheological, and electrical properties are described, and relevant basic evaluation
methods are introduced.
3.2 PHYSICAL PROPERTIES OF PLASTIC PACKAGING SYSTEMS
3.2.1 General Features: Molecular Weight, Color, and

Optical Properties
To understand physical properties and characteristics of plastic polymers, basic prop-

erties such as color, transparency, molecular weight (MW), molecular structure, molar
mass, polymer distribution, and so on must be considered. Thermoplastic polymers
that are widely used in the food packaging area possess the following typical features:
• Relatively long chain molecules, often without branching

• Solubility in some solvent (including water, for biopolymeric system)
• Crystalline and/or amorphous—mostly semicrystalline structure
• Having a certain level of flexibility or rigidity
• Certain level of viscosity; can flow under pressure and temperature
• Highly flammable compared to other packaging materials
In general, the molecular weight of polymers needs to be at least higher than

25,000 g/mol for physical properties to be useful for packaging materials. As
polymer MW increases, so does the tensile strength of packaging products. In some
cases, MW distribution in the same type of polymers could be different due to the
manufacturer, type, and level of monomers and comonomers, different catalysts,
and polymerization processes according to the purpose and function of plastic
polymers (Table 3.1).
An optical property with a different color or level of transparency in plastic packa-
ging products will influence both the marketing aspect due to customer preference
and the quality of food products because some foods are very sensitive to visible light.
Table 3.1 General Characteristics of Polyethylenes Sorted by Density
Density Distortion Tensile Strength Hardness,

PE Type (g/cm3) Temperaturea (°C) (N/mm2) Rockwell R
LDPE 0.910–0.925 30–40 4–16 10

MDPE 0.926–0.940 40–50 8–25 15
HDPE 0.940–0.959 40–55 21–38 65
UHMWPE 0.96 and aboveb Over 50b 27–38b 67b
Source: Keating, M., et al., Thermochim. Acta, 284, 47–56, 1996; Czaja, K. and Bialek, M.,
J. Am. Chem. Soc., 45, 22, 2002.
Note: HDPE, highdensity polyethylene; LDPE, low-density polyethylene; MDPE, medium-
density polyethylene; UHMWPE, ultrahigh molecular weight polyethylene.
a
Determined at 1.82 N/mm2.
b
Obtained from the following link: http://www.sdplastics.com/uhmwphys.html
It is important to measure how clear or cloudy plastic packaging is to determine how it

can be used. Surface irregularities also affect the characteristics of transparent and
opaque plastic. There are macroscopic and microscopic irregularities. Some plastic
polymers used in food packaging have high levels of transparency that provide a func-
tion similar to a glass packaging system. This unique property can be modified by
chemical or physical treatments on either polymers or products and then applied to
diverse types of food products.
Gloss can be a considerable value as one of the optical properties and mostly
describes the surface area. A different level of gloss could change the feeling of
and the consumer’s outlook about the package. On the other hand, packaging that
blocks light or gas permeation is necessary to increase the shelf life of certain
foods. Recently, more colored packages have been introduced into the market to
attract more consumers, who also may be induced by a better first impression of the
food products. In the plastic polymer market, the majority of products are colored
by pigments (approximately 98%) (Elias 1997). Color is the property detected by
one of the five typical human sensations related to recognizing and understanding
various materials existing in our lives.
3.2.2 Testing Methods for Physical Properties
3.2.2.1 Molecular Weight Determination
Due to the strong correlation between physical properties and MW of plastic poly-
mers, evaluating the MW of plastic materials is very crucial for the application of
packaging. Typically, to ensure the strength of packaging products, it is important
to be certain that the quality of the entire packaging system is highly dependent on
MW and its distribution. Basically, there are two practical testing methods to deter-
mine the average MW and MW distribution for plastic materials. The two tests are
gel permeation chromatography (GPC) and size-exclusion chromatography (SEC)
(Figure 3.1). The mechanism of SEC or GPC is based on steric exclusion of the
Normalized signal
0 0.04 0.08 0.12 0.16 0.20 0.24 0.28 0.32 0.36 0.40
Minutes
Figure 3.1 Chromatograms observed for polystyrene standards (From Uliyanchenko et al.,
J. Chrom. A, 1218, 1509–1518, 2011.). Note that polystyrene MWs (from right
to left): 92 (toluene); 1990; 9920; 52,400; 523,000 Da. Acquity UPLC (Ultra Performance
Liquid Chromatography) BEH (Ethylene Bridged Hybrid) C18 column, 50 × 2.1 mm I.D.
Mobile phase: THF (tetrahydrofuran). Flow rate: 0.5 mL/min. Pressure 25 MPa.
analytic molecules from the pores of the column packing material (Striegel et al.
2009). These methods are often combined with advanced technologies such as light
scattering, refractive index, and ultraviolet (UV) spectroscopy techniques, providing
sufficient information about above-average MWs and even polydispersity.
Based on the GPC, the following ASTM (2002) standard methods are often used
for MW evaluation specific polymers:
• ASTM D2503, Standard Test Method for Relative Molecular Mass (Molecular
Weight) of Hydrocarbons by Thermoelectric Measurement of Vapor Pressure
• ASTM D4001, Standard Test Method for Determination of Weight-Average
Molecular Weight of Polymers By Light Scattering
• ASTM D5296, Standard Test Method for Molecular Weight Averages and
Molecular Weight Distribution of Polystyrene by High Performance Size-
Exclusion Chromatography
• ASTM D6474, Standard Test Method for Determining Molecular Weight Dis-
tribution and Molecular Weight Averages of Polyolefins by High Temperature
Gel Permeation Chromatography
• ASTM D6579, Standard Practice for Molecular Weight Averages and Molecu-
lar Weight Distribution of Hydrocarbon, Rosin and Terpene Resins by Size-
Exclusion Chromatography
• ASTM F2214-02(2008), Standard Test Method for In Situ Determination of

Network Parameters of Crosslinked Ultra High Molecular Weight Polyethy-
lene (UHMWPE)
3.2.2.2 Color Measurements
In modern consumer product businesses, color is one of the most fundamental fac-
tors for interaction with customers because it affects their initial impression, perception,
and recognition, which are parts of brand identity and quality. For example, most global
brand products, logos, or trademarks are closely tied to certain specific colors. There-
fore, accurate and consistent color measurements are essential in terms of quality control
for the packaging system, including printing and labeling. To determine the color of
packaging products, spectrometers, spectrophotometers, spectrodensitometers, color
data software, and other spectroscopic tools are often used by packaging scientists.
Basically, the color of packaging films can be measured by colorimeters. For
instance, total color difference (ΔE*), as well as other color values (L*, a*, b*), is
collected by detecting the differences of light reflectance of films or objects. The
equation for different color values is as follows:
ΔE* = [(ΔL*)2 + (Δa*)2 + (Δb*)2]1/2
where L* = lightness, a* = redness, and b* = yellowness.
3.2.2.3 Opacity Measurements
Opacity refers to how well pigmented packaging components block light. Opacity
is beneficial for packaging materials that are sensitive to visible and UV light. Some
fundamental optical properties of plastics that are tested are gloss, haze, refractive
index, yellowness index, UV and visible light absorption and transmission, and
color analysis using a spectrophotometer. Gloss is the measure of light reflected by
the surface of the material. It is measured at angles of 20°, 40°, and 85°. Haze is the
scattering of light that passes through the material causing a glare. Changes in color
from clear to white or yellow is the yellowness index. Because it is so common, a stan-
dard ASTM test was established to test the change in yellowness of transparent plastic.
The following ASTM (2002) standard methods are used for optical property evaluation:
• ASTM D542, Standard Test Method for Index of Refraction of Transparent

Organic Plastics
• ASTM D1746, Standard Test Method for Transparency of Plastic Sheeting
• ASTM D1003, Standard Test Method for Haze and Luminous Transmittance of
Transparent Plastics
• ASTM D2457, Standard Test Method for Specular Gloss of Plastic Films and
Solid Plastics
• ASTM D6290, Standard Test Method for Color Determination of Plastic Pellets
• ASTM E179, Standard Guide for Selection of Geometric Conditions for Mea-
surement of Reflection and Transmission Properties of Materials
• ASTM E313, Standard Practice for Calculating Yellowness and Whiteness

Indices from Instrumentally Measured Color Coordinates
• ASTM E2539, Standard Test Method for Multiangle Color Measurement of
Interference Pigments
3.3 ELECTRICAL PROPERTIES OF PLASTIC PACKAGING SYSTEMS
Most plastic packaging polymers are dielectrics. Due to this property, plastics have
been used in certain types of food packaging application such as microwaveable plastic
containers for food products. Furthermore, these plastics have served as high-quality
electrical insulators with easy compatibility and processability during production. Basi-
cally, the electrical insulation property of plastic polymers stops the flow of the current
and sustains high levels of electrical fields without breakdown (Young and Lowell,
2011). Ironically, this distinct insulation property may generate some issues in industrial
packaging applications such as a buildup of static electricity on a component that can
attract more dust and then give electric discharge shocks. Even though such problems
are not common in food packaging systems, food packaging engineers must have an
understanding of the general electrical characteristics of plastic polymers that might
be an issue in future technology. The electrical conductivity of plastic polymers can
be easily enhanced or controlled by the addition of enhancers such as vapor-grown car-
bon fibers (VGCFs) or by the addition of antistatic agents (which are very common in
the industrial plastic packaging area). Also, a plastic polymer can be chemically mod-
ified by the addition of a conductive second phase (then it has intermediate levels of con-
ductivity to make a conductive composite) or by the incorporation of certain functional
groups in the main chain of polymers. As a result, these materials can be used in a wide
range of applications in the industrial packaging area. Furthermore, conducting poly-
mers are, in general, lightweight, more flexible, noncorrosive, and low-cost materials
compared to simple metallic films. The following ASTM (2002) standards are used
to determine the electrical properties of plastic polymers:
• ASTM D2305, Standard Test Methods for Polymeric Films Used for Electrical
Insulation
• ASTM D2902, Standard Specification for Fluoropolymer Resin Heat-Shrinkable
Tubing for Electrical Insulation
• ASTM D5213, Standard Specification for Polymeric Resin Film for Electrical
Insulation and Dielectric Applications
3.4 THERMAL PROPERTIES OF PLASTIC PACKAGING SYSTEMS
3.4.1 General Features of Thermal Properties
The behavior of most plastic packaging polymers and products, especially thermo-
plastics, is dependent on temperature during production, storage, application processes,
and distribution. Major thermal properties that are critical in the plastic packaging area
include not only basic thermal properties such as melting point, glass transition,
crystallization temperature, and decomposition temperature but also practical thermal

properties such as heat expansion rate and heat deformation (deflection/deformation)
temperature (HDT). These properties are commonly measured by sophisticated instru-
ments called thermal analyzers: differential scanning calorimetry (DSC), thermogravi-
metric analyzer (TGA), thermomechanical analyzer (TMA), and dynamic mechanical
analyzers. In this chapter, fundamental thermal properties and practical thermal proper-
ties will be briefly discussed, and various testing methods that are often used in the real
packaging world will be introduced.
The melting process of plastic polymers, abbreviated as Tm, is the reverse of crys-
tallization, but it is more complicated than the melting of low molar mass crystals
(Young and Lovell 2011). Technically, a phase transition at a range of temperature
from a crystalline or semicrystalline structure to a solid amorphous structure is referred
to as the melting temperature of plastic polymers. Due to a broad MW distribution, and
chemical and structural properties, the phase transition is not placed at a single tem-
perature, but it takes place over a broad range of temperatures. In plastic packaging
polymers, only semicrystalline or crystalline (which is not feasible in the real world)
thermoplastics can have a melting range. Thermosetting plastic packaging materials
will have decomposition temperatures rather than melting. Below melting temperature,
another phase transition in thermoplastic polymers is a very common feature.
Typically, a phase transition from glass to a rubber-like state, called glass transi-
tion, is the reversible transition in the amorphous region within semicrystalline and
amorphous plastic polymers (Figure 3.2). This characteristic is very crucial for defin-
ing the application of each plastic polymer in the packaging system. For example, the
polyolefin group, which has a relatively low glass transition temperature (Tg), is used
for frozen product packaging systems due to its significant flexibility. In general,
I II III
ln θ0 Liquid
ln θ1
ln (θ)
ln θTP
Turning point
ln θ2
Solid
ln tTP
ln t1 ln t2 ln (t)
Figure 3.2 Schematic illustration of the typical cooling curve (in double logarithmic scale) of crys-
talline polymers during injection molding. Stage I: liquid-state cooling; Stage II: phase-
change process; Stage III: solid-state cooling; θ is the dimensionless temperature.
(From Yang et al., Appl. Polymer, 128, 1922–1929, 2012.) Note that θ is the dimension-
less temperature defined by θ = (T − Tw)/(T0 − Tw), with θ0, θ1 − θ2, and θTP denoting
the initial temperature, phase change temperature range (mushy zone), and turning-
point temperature, respectively.
Td: 105°C Tm, PET

5
PET control
Normalized heat flow, endo up

Tg , PET
Tcc, PET
4
0.5 W/g
Tm, P(VDF-TFE)
3
P(VDF-TFE) control
Td: 105°C
2
50/50 PET/P(VDF-TFE)
50 100 150 200 250

Temperature (°C)
Figure 3.3 Crystallization temperature of 200 μm PET thick extruded sheet (first top thermo-
gram) was measured by DSC during first heating (heating rate 10°C min−1). Arrows
indicate the effect of physical treatment (biaxially stretching) on the temperatures.
(From Carr, J. M., et al., Polymer, 54, 1679–1690, 2013. With permission.)
polyesters have high Tg and show higher brittleness, and they are often used in rigid
packaging due to their toughness and durability. The glass transition temperature may
be modified by altering the degree of branching or cross-linking in the polymer or by
additives such as fillers or plasticizers.
Crystallization phase transition is often observed at a certain range of temperature
in semi-plastic polymers during the heating or cooling process. Among plastic packa-
ging materials, polyethylene terephthalate (PET) often shows this thermal character-
istic (Figure 3.3). At this temperature range, crystal nuclei grow and form a large and
well-organized number of spherulites in the shape of rods, discs, or spheres. This pro-
cess is significantly affected by diverse factors such as the chemical structure of the
polymer, types of physical treatment, additives, temperature change rate, and previous
heat treatment history. This transition is also an important characteristic in plastic
packaging applications.
3.4.2 Testing Methods of Thermal Properties
3.4.2.1 Change of Energy Absorption or Release
To determine various basic thermal properties of plastic packaging materials, a

calorimetry method using DSC is widely used in the packaging world. The following
parameters are often measured by DSC:
• Melting temperature (Tm)

• Heat of fusion
• Latent heat of melting
• Reaction energy and temperature

• Glass transition temperature (Tg)
• Crystalline phase transition temperature and energy
• Precipitation energy and temperature
• Denaturation temperatures of biopolymeric packaging materials
• Oxidation induction times
• Specific heat or heat capacity
Based on these observations, general thermal stability, the reaction kinetics of materi-
als, exothermal energy of polymer cure (as in epoxy adhesives), and the degree and
rate of cure could be determined. Furthermore, this method could be used as one of
multiple techniques to identify an unknown material or by itself to confirm that
what is being tested is the expected material. The related ASTM standards are:
• ASTM E793, Standard Test Method for Enthalpies of Fusion and Crystalliza-
tion by Differential Scanning Colorimetry
• ASTM E794, Standard Test Method for Melting and Crystallization Tempera-
tures by Thermal Analysis
• ASTM E928, Standard Test Method for Purity by Differential Scanning
Calorimetry
• ASTM E1356, Standard Test Method for Assignment of the Glass Transition
Temperatures by Differential Scanning Calorimetry
In general, DSC evaluation is based on comparison of the amount of energy

absorbed or released by a plastic sample and a reference sample during the heating or
cooling process in a small chamber equipped with a highly sensitive chromel wafer
and chromel-alumel thermocouple (Figure 3.3). A plastic sample (0.5–100 mg) is
placed in a suitable sample pan, which is usually made out of aluminum (Al), copper
(Cu), gold (Au), platinum (Pt), alumina, or graphite to avoid any reaction between
sample and pan, and sits upon a constant disc on a platform in the DSC cell with a
chromel wafer immediately underneath, while a reference pan is kept empty in the
same DSC cell during processing. Heat flow is measured by comparing the differences
in temperature across the sample and the reference chromel wafers, and this provides
quantitative and qualitative data on endothermic (heat absorption) and exothermic
(heat evolution) processes. For example, DSC is a very useful tool to make qualitative
statements about whether or not polymer blend systems are miscible or immiscible,
provided the inherent homopolymer transition temperatures of the blend components
are sufficiently well separated. Temperatures can range from −120°C to 725°C with
the help of the cooling system, though an inert atmosphere is required above 600°C.
The temperature is measured with a repeatability of ±0.1°C.
3.4.2.2 Change of Dimension
A thermomechanical analyzer (TMA) has often been used to measure diverse

thermal properties (Figure 3.4). It is equipped with interchangeable probes at varied
Tg
α (μm/m °C)
α (μm/m °C)
Dimension change
Dimension change
Tgα
Tgα α=0
Tg
Temperature Temperature
(a) (b)
400
Macroprobe, 0.5 g load PE
PBT
300
α (μm/m °C)
PP
200
PA 46
(dry)
100
0
–50 0 50 100 150 200
Temperature (˚C)
(c)
Figure 3.4 Examples of TMA measurement: (a) Expansion and (b) penetration behavior in the
grass transition region. Herein, Tgα stands for glass transition from α. (c) Coefficient of
linear thermal expansion of general packaging plastics measured by TMA at macrop-
robe, specimen cross section approximately 6 × 6 mm, load 0.5 g, heating rate 3°C/min.
loads to make a number of measurements. TMA probe configuration depends on the

type of testing. Typically, four types of probes (expansion, penetration, compression,
and flexure) are used for evaluation of the packaging system. In general, the most com-
monly used TMA probe is the expansion probe. Using either expansion or penetration
probes upon the sample, the coefficient of linear thermal expansion (also known as the
coefficient of thermal expansion or CTE, α) can be easily determined, and it provides a
quantitative assessment for multilayer packaging production, which is oftentimes
critical to ensure that the materials will have similar CTE values to avoid failures
such as undesirable thermal stresses, leaks, or component malfunctions. Moreover,
the inflection point of the step (α-curve) and the maximum of the expansion curve
can be characterized by the temperature (Tgα) at which α assumes the value 0, as
shown in Figure 3.4a and b.
A cylindrical or oblong specimen measuring 2–6 mm in diameter or length
and usually 2–10 mm in height is subjected to slight loading (0.1–5 g) via a vertically
adjustable quartz glass probe. The probe is integrated into an inductive position
sensor. The system is heated at a slow rate. If the specimen expands or contracts,
it moves the probe. A thermocouple close to the specimen measures the temperature.
This is considered a sensitive method for the transition, which is hardly determined
by the energy absorption/release method in DSC. Various types of packaging
polymer samples such as films, powders, plugs, or fibers could be applied into
TMA. Using this equipment, the following thermal properties will be easily
measured:
• Glass transition temperature

• Modulus: tensile modulus, compression modulus
• CTE (α)
• Melting temperature
• Crystalline phase transition temperature
• Creep under load, by measuring the change of a dimension of a material that
indicates thermal stability of plastic packaging materials
The related ASTM standards are:
• ASTM E228, Standard Test Method for Linear Thermal Expansion of Solid
Materials With a Push-Rod Dilatometer
• ASTM E831, Standard Test Method for Linear Thermal Expansion of Solid
Materials by Thermomechanical Analysis
• ASTM E1545, Standard Test Method for Assignment of the Glass Transition
Temperature by Thermomechanical Analysis
3.4.2.3 Change of Weight
Using a very sensitive balance, the amount of weight change of a plastic

polymer can be determined by a TGA, according to either a function of increasing
temperature or a time in isothermal condition. Plastic samples can be in the
form of either powder or small pieces of products. Sample loading amounts
range from 1 to 150 mg. This test can be placed in an atmosphere of nitrogen,
helium, air, or other gas, or in a vacuum. Often, this equipment is combined
with a mass spectrometer or Fourier transform infrared (FTIR) spectroscopy,
and it provides the identification of vapor generated during the process. Therefore,
this equipment can be used to identify the unknown sample in combination with
other equipment. Using this equipment, the following thermal properties will be
easily measured:
• Decomposition and oxidation temperature (overall thermal stability, especially

for plastic resin)
• Weight of volatile components or adsorbed liquids such as water, fuel, or oils
that are incorporated into plastic products
• Weight of fillers in plastic products such as carbon black, calcium carbonate,
aluminum trihydrate, silica, talc, and mica used as fire retardants, UV blockers,
or colorants
• Weight of reinforcing materials like fiberglass or carbon fiber
The related ASTM standards are:

• ASTM E1131, Standard Test Method for Compositional Analysis by Thermo-
gravimetry
• ASTM D2584, Standard Test Method for Ignition Loss of Cured Reinforced Resins
3.4.2.4 Modulus Measurements
A variety of plastic packaging materials are, in general, heterogeneous and tem-

perature dependent. Their interfacial characteristics are widely determined with
dynamic mechanical analyzers (DMAs) and thermal analyzers. Using DMA measure-
ments that are compiled under a wide range of temperatures, it is easy to understand
the viscoelastic behavior of molten polymer systems such as the glass transition region
and the level of interactions within the polymer matrix inside (Ray et al. 2002).
Dynamic modulus E∗, storage modulus E′, loss modulus E″, and mechanical damping
tan δ are obtained from DMA measurements, and total evaluation of plastic packaging
products will be achieved in combination with other thermal analyses (Figure 3.5a).
Herein, dynamic modulus is defined as the modulus of a viscoelastic material that
is a true complex number because it contains both a real and an imaginary component
of the modulus. In the real packaging world, the storage modulus E′ is associated with
the “stiffness” of a material. It is strongly related to the Young’s modulus, E. The
dynamic loss modulus is often associated with “internal friction.” This molecular
level behavior is very sensitive to different kinds of factors such as additives, molecu-
lar motions, relaxation processes, transitions, morphology, and other structural hetero-
geneities. Figure 3.5 shows the effect of plasticizer on the glass transition temperature
of a polyvinyl chloride (PVC) polymer. In general, plasticizers are low MW ingredi-
ents that are sued to soften rigid polymers. They help to lower the glass transition tem-
perature and broaden the tan delta peak. Also, glass transition temperature can be
easily determined by DMA according to ASTM E1640, Standard Test Method for
Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis.
3.4.2.5 Heat Distortion Temperature (HDT)
Thermal stability in plastic packaging products is often expressed with HDT. Thermal
stability of plastic products can be improved with morphological modifications such
as controlling the amount of the crystalline or semicrystalline region, addition of reinfor-
cing materials such as fiberglass, or the use of other advanced stabilizers. The maximum
thermal stability can be measured by observing the temperature at which the polymer dis-
torts under controlled stress. This temperature is commonly found between Tg and Tm
for the semicrystalline plastic polymers and below Tg for the amorphous plastic polymers.
This property can often be measured by TMA. Applicable ASTM standards are:
• ASTM E2092, Standard Test Method for Distortion Temperature in Three-
Point Bending by Thermomechanical Analysis
• ASTM D648, Standard Test Method for Deflection Temperature of Plastics
Under Flexural Load in the Edgewise Position
0° < δ < 90°

E
E˝
Stress δ
E´
Strain E = Stress/strain
E´ = Ecos δ
E˝ = Esin δ
Viscoelastic tan δ = E˝/E´
(a)
4000 2.8
PVC high plasticizer content
PVC med. plasticizer content
PVC low plasticizer content 2.4
Storage
2000 modulus 2.0
Storage modulus (MPa)
1.6
Tan delta
0
99.45 °C 1.2
Tan delta 5.90 °C

0.8
–2000
DMA conditions: 51.13 °C
Clamp: single cantilever 0.4
Frequency: 1Hz
–4000 0
–150 –100 –50 0 50 100 150
Temperature (˚C)
(b)
Figure 3.5 (a) Diagram and (b) measurement of modulus of PVC, incorporating different levels of
plasticizer content. (Courtesy of TA Instruments, http://www.tainstruments.com.)
3.5 MORPHOLOGICAL PROPERTY
3.5.1 General Features of Synthetic Polymers
Unlike natural polymers, synthetic plastic polymers are often referred to as “plas-
tics,” which are derived from petroleum oil or artificial polymers. The well-known
synthetic polymers include nylon, polyethylene (PE), polyester, Teflon, and epoxy.
They are commonly found in a variety of consumer products such as food packaging,
paper, films, tubing, pipes, super glue, and so on. Based on their practical application,
synthetic polymers can be classified into four main categories: thermoplastics,

thermosets, elastomers, and synthetic fibers. They are commonly found in a wide
range of consumer packaging products, including special applications such as
certain medical packaging articles or electronic device casings. Packaging plastic
polymer morphology is the overall form of polymer structure, including crystallinity,
branching, MW, cross-linking, and so on (Iler et al. 2006). Most plastic polymers
are mixtures in the ordinary chemical sense of the term. Their MWs are typically
distributed over a broad range as the sequence, orientation, and connectivity of the
individual monomers (Lower 2009). A wide variety of different types of plastic
polymers are available with variations in the main chain as well as the side chains.
The backbones of common synthetic polymers such as polythene and polystyrene,
polyacrylates are made up of carbon-carbon bonds, as opposed to chain polymers
(such as polyamides, polyesters, polyurethanes polysulfides, and polycarbonates),
which have other elements (e.g., oxygen, sulfur, nitrogen) inserted along their back-
bones. Through polymerization, chemists are able to engineer polymers to yield a
desired set of properties, including strength, stiffness, density, heat resistance, and
electrical conductivity.
The properties of plastic polymers are determined by their chemical structure,
degree of polymerization (DP), chain molecule orientation, crystallinity, density,
viscosity, and cross-linking among individual molecules. Crystallinity is one of
the important properties of all polymers. Crystallization of polymers is a process
associated with partial alignment of their molecular chains. It has been observed
that relatively short chains organize themselves into crystalline structures more read-
ily than longer chains of molecules. These chains fold together and form ordered
regions called lamellae, which are composed of large spheroidal structures named
spherulites (Gowariker et al. 1986; Sawyer et al. 2008; Syed 2010), as shown in
Figure 3.6. For most crystalline polymers, it is generally accepted that spherulites
are developed from a single crystal through unidirectional growth (Li et al.
1999). The dimensions of spherulites range from micrometers to millimeters,
depending on the structure of the polymer chain and the crystallization conditions,
such as cooling rate, crystallization temperature, and the content of the nucleating
agent (Li et al. 2001). If polymer chains are very long, it is impossible for the chains
to fit into a perfect arrangement equivalent to that observed in low MW materials.
Low MW polymers (short chain) are generally weaker in strength, although they are
crystalline; only weak Van der Waals forces hold the lattice together. In the plastic
packaging area, the crystallization process can be observed under either strain or
heat treatment. For example, molten PET can be cooled down either to a quasi-
fully amorphous or to a semicrystalline state depending on the cooling rate. Once
it has been quenched into its amorphous state, PET can further crystallize under
strain in its rubber-like state (Gorlier et al. 2001).
3.5.1.1 Crystallinity
Crystalline materials have their molecules arranged in repeating patterns. The

crystallization takes place between glass transition and the melting state; it is always
Amorphous
Lamella region
1μm
(a) (b)
200μm
(c)
Figure 3.6 (a) Schematics for suggested fold models of polymer crystals (from Sawyer, L.C., et al.,
Polymer Microscopy, Springer London Limited, London, 2008) and (b) lamella texture
of a developing spherulite of linear low-density PE grown at 124°C (from Bassett, D. C.,
Polymer characterization, In: Comprehensive polymer science, Pergamon, Oxford,
UK, 841, 1989). (c) Spherulites of iso-polypropylene viewed between crossed polari-
zers while crystallizing from the melt at 130°C (from Bassett, D. C., Phil. Trans. Roy.
Soc. A-Math. Phys. Eng. Sci., 348, 1686, 29–43, 1994).
exothermic and a stabilization process of polymeric molecules. Amorphous materials,

by contrast, have their molecules arranged randomly and in long chains that twist and
curve around one another, making large regions of highly structured morphology unli-
kely. An amorphous solid is formed when the chains have little orientation throughout
the bulk polymer. Solid plastic polymers are composed of crystalline and/or amor-
phous regions (disordered arrangements of randomly coiled and entangled chains).
Thermoplastics, for example, usually are semicrystalline, a combination of crystalline
and amorphous regions. The properties of thermoplastics are strongly influenced by
their morphology. The fraction of the ordered molecules in polymer is characterized
by the degree of crystallinity (i.e., the volume fraction of crystalline regions in a poly-
mer). Typically, the value of the degree of crystallinity is in the 10% to 80% range,
depending on the crystallization conditions (Gowariker et al. 1986; Carraher 2012).
The degree of crystallinity affects the optical, thermal, and mechanical properties of a
polymer. Although crystallinity is a powerful tool for improving strength and stiffness,
such strengthening is always directional—that is, the properties are not the same in all
directions (Allcock and Lampe 1981) (Figure 3.7). A crystalline polymer will be much
stronger in the direction of molecular alignment and much weaker at right angles to
that alignment. Amorphous polymers are, in general, clear and transparent. On the
other hand, visible light can pass through them, and semicrystalline polymers can
be recognized easily because they are normally opaque and hazy. Light is not trans-
mitted through the polymers; rather, it is reflected or scattered by the crystalline planes
(Carraher 2012). The different properties of amorphous polymers and semicrystalline
polymers are shown on Table 3.2.
Crystalline region
Amorphous region
Figure 3.7 Mixed amorphous and crystalline macromolecular polymer structure. (From
Gowariker, V. R., et al., Polymer science, Wiley Eastern Limited, Mahim, India,
1986. With permission.)
Table 3.2 Properties of Amorphous and Semicrystalline Polymers
Amorphous Polymers Semicrystalline Polymers
Random structure Ordered structure

• Highly organized molecular alignment
Less intermolecular cohesiveness High intermolecular cohesiveness
No melting temperature observed Clear melting temperature
• Broad softening band by heat flowable • All secondary bonds are broken by heat
Higher transparency Higher opacity
Relatively lower strength Relatively higher strength
• Higher strength, stiffness, and density
than comparable amorphous polymer
Higher toughness Higher rigidity
• Amorphous region gives toughness to • Crystalline region gives rigidity to the
the materials materials.
Relatively lower gas barrier properties Relatively higher gas barrier properties
The crystallinity of a polymer is significantly affected by the DP and chemical struc-

ture, size, and type of monomer that is a repeating unit of polymer. Polymers with high
DP have great strength because the molecules become tangled between layers, and
more secondary bonds are associated. In general, when the monomers are larger and
irregular, a more amorphous region is easily formed. Likewise, smaller monomers
and monomers that have a very regular structure (e.g., rod-like) will form more crystal-
line solids, which are highly ordered three-dimensional arrays of the molecules.
Crystallinity can be enhanced by pulling the bulk material either when it is synthe-
sized or during its processing (Carraher 2012). This is common for both films and
fibers. When a film is formed, the small crystallites tend to be randomly oriented rela-
tive to each other. Drawing (stretching) the film pulls the individual chains into a
roughly parallel organization as is shown in Figure 3.8 (Allcock and Lampe 1981).
3.5.1.2 Orientation
Films can either be uniaxially oriented (oriented in only one direction) or biaxially
oriented (oriented in two directions).
Stretching direction
Tension
Tension
Figure 3.8 Schematic diagram of stretching the individual polymer chains into a roughly parallel
organization. (From Ehrenstein, G. W., Polymeric materials: Structure, properties,
applications, Hanser Gardner Publications, Cincinnati, OH, 2001; Syed, K. A., Polymer
crystallinity, Polymer engineering and science, 2010, retrieved from http://
www.scribd.com/doc/64493489/3-Polymer-Crystallinity-Polymer-engineering.)
Moreover, orientation affects a significant reduction in the permeability of a poly-

meric structure only when the orientation is “locked in” (Lasoski and Cobbs 1959).
Fibers normally are drawn so that they are oriented in one direction (Carraher
2012). For instance, unstretched nylon fibers are brittle. When the fibers are stretched,
the oriented fibers are strong and tough. PE can be unentangled by forming a gel with
a low MW solvent. When the gel is drawn, the resulting fibers are highly oriented
(Flam 1991). Ultra-oriented PE formed in this way is used in bulletproof vests.
3.5.2 Testing Methods for Morphological Properties
Morphology of a plastic polymer is a microscale property that is largely dictated

by the amorphous or crystalline portions of the polymer chains and their influence on
each other. Testing methods have been studied including microscopic assessment,
density measurement, DSC, X-ray diffraction, IR spectroscopy, and nuclear magnetic
resonance. The measured value depends on the method used, which is therefore
quoted together with the degree of crystallinity (Ehrenstein 2001). In addition to
the aforementioned integral methods, the distribution of crystalline and amorphous
regions can be visualized with microscopic techniques, such as polarized light micro-
scopy and transmission electron microscopy (TEM).
Microscopy techniques are especially useful in determining these microscale
properties because the domains created by the polymer morphology are large enough
to be viewed using modern microscopy instruments. Some of the most common
microscopy techniques used are X-ray diffraction, TEM, scanning TEM (STEM),
scanning electron microscopy (SEM), and atomic force microscopy (AFM). Polymer
morphology on a mesoscale (nanometers to micrometers) is particularly important for
the mechanical properties of many materials. TEM, in combination with staining tech-
niques, but also SEM and scanning probe microscopy are important tools to optimize
the morphology of materials such as polybutadiene-polystyrene polymers and many
polymer blends. Most methods of evaluation of the degree of crystallinity assume a
mixture of perfect crystalline and totally disordered areas. The transition areas are
expected to amount to several percent.
3.5.2.1 X-Ray Diffraction
As indicated earlier, crystallinity is crucial to polymer properties. The discovery of

X-rays in 1895 enabled scientists to probe crystalline structures at the atomic level
(Wikipedia 2013). Dickinson and Raymond first used the X-ray method to detect
an organic compound structure in 1923 (Dickinson and Raymond 1923). Since
then, X-ray methods have been extensively studied and utilized in chemistry, poly-
mers, and materials science (Crowfoot 1935; Kendrew et al. 1958; Lundstrom
2004; Scapin 2006; Blackwell 2012). Use of monochromatic X-radiation showed
that many polymers gave what we now call Bragg reflections, characteristic of repeat-
ing planes in three-dimensional lattice (Bragg 1912, 1922). The interatomic spacing in
polymers can be determined with wide-angle X-ray diffraction or small-angle X-ray
diffraction. Typically, wide-angle X-ray diffraction measures scattering angles from
approximately 2o to 90o and determines interatomic spacing to a precision of one-

thousandth of an angstrom (1 × 10−13m) (Peacock and Calhoun 2006a). Small-
angle X-ray diffraction analyzes the periodic spacing of stacked lamellae, and the scat-
tering angles’ measured range is from less than 0.1o to 2o, but it requires sophisticated
equipment and is used for polymers that are high-intensity and crystalized.
The determination of the degree of crystallinity implies use of a two-phase model
(i.e., the sample is composed of crystals, is amorphous, and has no regions of semi-
crystalline organization). When a beam of X-rays passes through a polymer sample,
some of the regular arranged atoms reflect the X-ray beam constructively and produce
an enhanced intense pattern (Ashraf et al. 2008; Bhandari 2012). Figures 3.9 and 3.10
show simple schematic patterns of X-ray diffraction. Amorphous samples give sharp
–
( 103) Fiber axis
–
( 112)
–
(111)
–
( 110)
(100)
–
(011) (010)
–
( 111)
Figure 3.9 Schematic X-ray diffraction pattern for a fiber texture of PET. (From Gupte, K. M., et al.,
J. Polym. Sci. B. Poly. Phys., 21, 1927–1953,1983. With permission.)
Intensity (a.u)
001
002
5 15 25 35 45 55
2θ (degree)
Amorphous Semicrystalline PLA after casting
Figure 3.10 Standard X-ray diffraction patterns of amorphous polymer, semicrystalline polymer,
and actual semicrystalline polylactic acid (PLA) polymer.
Measured
spectrum
Intensity
Amorphous Crystalline
halo Peaks
5 10 15 20 25 30 35 40 45 50 55 60
Angle (2θ)
Figure 3.11 Wide-angle X-ray diffraction spectrum from high-density PE.
arcs because the intensity of the emerging rays is greater; whereas, for crystalline
samples, the incident rays are scattered. The arc length of the diffraction pattern
depends on orientation. If the sample is highly crystalline, the arc length will be
smaller (Gupta and Kothari 1997). X-ray patterns can be quantified by plotting
the scattering intensity as a function of the diffraction angle (which, by convention,
is reported as the 2θ angle; i.e., twice the actual scattering angle), as shown in
Figure 3.11. The measured spectrum can be deconvoluted into its component crys-
talline peaks and an amorphous halo. The angular position of the peaks reveals the
interatomic spacing in the unit cell according to well-established crystallographic
principles. The degree of crystallinity can be calculated from the relative areas of
the crystalline peaks and the amorphous halo. The widths of the crystalline peaks
can be analyzed to obtain a measure of the perfection of the atomic array with crys-
tallites. The broader the peaks, the less well-ordered and smaller are the crystallites
within a sample.
3.5.2.2 Calculation of Crystallinity
The crystallinity is calculated by separating intensities due to amorphous and

crystalline phases on diffraction phases. A computer-aided curve-resolving techni-
que is used to separate crystalline and amorphous phases of diffracted graph
(Gupta and Kothari 1997). The diffraction profile is divided into two parts: Peaks
are related to diffraction of crystallines; broad alone is related to scattering of the
amorphous phase. The crystalline polymer usually has a higher density than the
amorphous phase because the regular packing in the crystal structure is a more effi-
cient use of space. The density of the crystalline phase can be determined easily if we
have the unit cell and know how many monomers it contains. Higher values of
degree of crystallinity are only achieved in materials having small molecules,
which are usually brittle, or in samples stored for a long time at temperatures just
below the melting point. The latter procedure is costly and is applied only in special
cases. It is important to note that moisture, which is often present in the sample, does
affect this type of measurement.
After separation, the total area of the diffracted pattern is divided into crystalline
(Ac), amorphous components (Aa). Percentage of crystallinity xc % is measured as the
ratio of crystalline area to total area (Moly et al. 2005).

Ac
xc % = 100 ð%Þ (3.1)
Ac + Aa
where:
Ac = area of crystalline phase
Aa = area of amorphous phase
xc = percentage of crystallinity
Often the crystalline polymer reflections are broad, and it is more difficult to sepa-
rate them from the amorphous component for crystallinity below 15% to 20%. There-
fore, X-ray diffraction generally is not as powerful for this class of materials because
they are either amorphous or poorly crystallized. Small angle X-ray scatteringIR spec-
troscopy can also be used to measure crystallinity (Gupta and Kothari 1997). Among
common plastics that are mostly used in packaging, isotactic polypropylene, high den-
sity PE, and crystallized PET show up to 80% crystallinity, while copolymers or engi-
neered highly branched plastics are lower than that of the same type of homopolymer
based on structural regularity. Polyethylene terephthalate glycol (PETG) and atactic
PS are 100% amorphous.
3.5.2.3 Density Measurements
Crystalline areas generally are more densely packed than amorphous areas. This
results in a higher density—up to 15% depending on the material. The density of a
polymer depends upon the relative densities and masses of its components. It can
be obtained by using Equation 3.2 (Peacock and Calhoun 2006).
ðm1 + m2 Þ
ρ = m1 m2 (3.2)
+
ρ1 ρ2
where:
ρ = polymer sample density
m1 = mass of Component 1
m2 = mass of Component 2
ρ1 = density of Component 1
ρ2 = density of Component 2
In the case of a semicrystalline polymer, the two components are the crystalline
and amorphous regions. If we know the densities of the crystalline and the amor-
phous regions, we can estimate a sample’s degree of crystallinity from Equation 3.3
(Peacock and Calhoun 2006).
1 1
−
ρ ρa
Degree of crystallinity ð%Þ = 100 (3.3)
1 1
−
ρc ρa
where:
ρ = sample density
ρc = density of crystalline component
ρa = density of amorphous component
Two methods can be used to measure a polymer’s density: density gradient
column analysis and densimetry. A density gradient column consists of a glass
tube, one or two inches in diameter, filled with a pair of liquids that possesses
a smooth density gradient—a low density gradient at the top and a high density
gradient at the bottom. The gradient density is calibrated with hollow glass
beads, the density of which are known, that float at various heights within the
column. The calibration curve is obtained by plotting the height of each bead
against its known density. When a small polymer sample is dropped into the col-
umn, it sinks until it reaches a point of neutral buoyancy. The sample’s height is
measured, and its density is read from the calibration curve (Peacock and Cal-
houn 2006).
Densimetry applies Archimedes’ principle to measure a sample’s density. The
sample is weighed twice—once when suspended in air and again while suspended
in a liquid of known density. The density of the sample is calculated from Equation
3.4 (Peacock and Calhoun 2006).
ðρ1 wa − ρ2 w1 Þ
ρ= (3.4)
ðwa − w1 Þ
where:
ρ = sample density
ρa = density of air
ρl = density of liquid
wa = weight of sample in air
wl = weight of sample in liquid
For example, polyamide 6 (nylon) has a crystalline density ρc = 1.24 g/cm3 and an
amorphous density ρa = 1.08 g/cm3). However, moisture, which is often present in the
sample, affects this type of measurement (Ehrenstein 2001).
The related ASTM standard is ASTM D792-08, Standard Test Methods for
Density and Specific Gravity (Relative Density) of Plastics by Displacement.
3.5.2.4 Calorimetry
As discussed earlier in the thermal property section, another useful technique is

DSC, which measures heat flow into or out of a material as a function of time or tem-
perature. This instrument determines the energy (calories) necessary to increase the
temperature at a steady rate (i.e., the specific heat). Plastic polymer crystallinity can
be determined with DSC by quantifying the heat associated with melting (fusion) of
the polymer and comparing that with the heat released upon melting of the standard
sample of the same material with the known crystallization degree. If the theoretical
heat of fusion of the pure polymer is known, the degree of crystallinity can be cal-
culated from its measured heat of fusion using Equation 3.5 (Figure 3.12) (Peacock
and Calhoun 2006). This heat is reported as percent crystallinity by normalizing the
observed heat of fusion to that of a 100% crystalline sample of the same polymer.
Because authentic samples of 100% crystalline polymer are rare, literature values
are often used for this value (Wunderlich 1990; Sichina 2000; Ehrenstein et al.
2004).
Measured heat of fusion

Degree of crystallinity % = 100 (3.5)
Theoretical heat of fusion
Glass transition
Crystallization
10
mω Exothermic
Gla
Melting
endothermic
20 40 60 80 100 120 140 160 180 200 220 240 260 280 °C
Figure 3.12 Schematic representation of a differential scanning calorimetry thermogram. (From

Peacock, A. J. and Calhoun, A. R., Polymer Chemistry: Properties and Applications,
Hanser Gardner Publications, Cincinnati, OH, 2006.)
3.5.2.5 Microscopy
Polymer microscopy provides nanoscale up to microscale images of polymer sam-

ples, which includes optical microscopy, IR microscopic spectroscopy, and electron
microscopy (EM) such as TEM, SEM, and AFM. However, polymer analysis fre-
quently uses microscopy techniques, especially at high magnification, to obtain
images of a small portion of the sample, which does not necessarily represent the
material as a whole. Before drawing any conclusion, many images from different
parts of a sample must be examined and compared. It is also a good practice to
apply more than one technique to analyze any given sample.
3.5.2.6 Infrared Spectroscopy and Raman Spectroscopy
IR and Raman spectroscopy can be used if one can identify absorption bands that
are exclusively characteristic of the crystalline or amorphous phases. The crystalline
phase contains chains with a regular repeating conformation, essential for a three-
dimensional crystalline lattice, and bands due to coupling of the vibrations on identical
neighboring monomers, which may occur but are not possible for the amorphous
phase. However, the random chains contain local conformations that do not occur
in the crystal, and these may give rise to their own vibrational modes. An estimate
of the degree of crystallinity can be determined from the intensities of the assigned
peaks in the spectrum, provided that the intensity of these bands in the 100% pure
phases is known.
IR spectroscopy is based on absorption spectroscopy and deals with the IR region
of the electromagnetic spectrum, which is light with a longer wavelength and lower
frequency than visible light. IR spectroscopy exploits the fact that molecules absorb
specific frequencies that are characteristic of their structure. These absorptions are
resonant frequencies (i.e., the frequency of the absorbed radiation matches the transi-
tion energy of the bond or group that vibrates). By comparing the spectrum with a
library of reference samples, the chemical structure of the area of interest can be iden-
tified. IR absorption or reflection spectra from crystalline polymers, on the other hand,
contain additional peaks that are absent in amorphous materials with the same com-
position. These signals may originate from deformation vibrations of the regular
arrangement of molecular chains. From the analysis of these bands, the degree of crys-
tallinity can be estimated.
3.5.2.7 Electron Microscopy
An electron microscope uses an electron beam to illuminate a specimen and pro-

duce a direct “view” with a high local resolution of the material studied. The techni-
ques of EM have been used to study the structure of surfaces, the internal structure of
polymers and their chemical compositions, and to improve morphological control
(Michler 2008). These techniques include transmission and SEM. Polymer scientists
use EM to examine polymer samples at magnifications ranging from approximately
15× up to 250,000× (Peacock and Calhoun 2006). With the shift in interest to smaller
and smaller structural details, high-resolution EM and AFM are now making it possi-
ble to view molecular arrangement and to further reveal polymer micro- or nanome-
chanical properties and mechanisms, enhancing understanding of the structure–
property correlations in polymers (Michler 2008).
3.5.2.8 Transmission Electron Microscopy
TEM uses a high-voltage electron beam to create an image by transmitting the

beam through the specimen that is in part transparent to electrons and in part scatters
them. When it emerges from the specimen, the electron beam carries information
about the structure of the specimen that is magnified by the objective lens system
of the microscope. TEM relies on differences in electron density within the sample
to provide contrast. Regions of high electron density scatter the incident beam more
than low electron density regions and thus appear darker in the electron micrograph.
Material analysis commonly stains the sample with a solution of a heavy metal oxide
such as ruthenium tetroxide (Peacock and Calhoun 2006). TEM generally is used to
examine the relationships between amorphous and crystalline regions in semicrystal-
line samples or in a multiphase blend.
3.5.2.9 Scanning Electron Microscopy
SEM was introduced in the 1960s, and since then it has been used to investigate
fracture surfaces, phase separation in polymer blends, and crystallization of spheru-
lites (Michler 2008). SEM produces images by probing the specimen with a focused
electron beam that is scanned across a rectangular area. When the electron beam inter-
acts with the specimen, it loses energy by a variety of mechanisms. The lost energy is
converted into alternative forms such as heat, emission of low-energy secondary elec-
trons and high-energy backscattered electrons, and light emission or X-ray emission,
which provide signals carrying information about the properties of the specimen’s sur-
face, such as its topography and composition. Polymer scientists make extensive use
of SEM when analyzing fracture surfaces and other textured samples, such as those of
breathable films and polymer fabrics. The advantage of SEM is its great depth of field,
which permits us to visualize a surface in detail.
3.5.2.10 Atomic Force Microscopy
AFM is a very high-resolution type of scanning probe microscopy and one of the
foremost tools for imaging, measuring, and manipulating matter at the nanoscale.
AFM examines the surfaces of a molded polymer item’s fracture surface or etched sur-
face. The information is gathered by "feeling" the surface with a mechanical probe and
is created as a series of pixels by tapping the surface of a sample with an ultra-sharp
probe that is scanned in lines across the sample to build up the image. In more
advanced versions, currents can be passed through the tip to probe the electrical con-
ductivity or transport of the underlying surface, but this is much more challenging and
few research groups report consistent data (Lang et al. 2004).
Electron microscopes are expensive to build and maintain because the microscopes
designed to achieve high resolutions must be housed in stable buildings (sometimes
underground) with special services such as magnetic field cancelling systems. Because
the molecules making up air scatter electrons, the samples usually have to be viewed
in a vacuum. One exception is the environmental scanning electron microscope,
which allows hydrated samples to be viewed in a low-pressure (up to 20 Torr or
2.7 kPa) and/or wet environment. SEM usually images conductive specimens; there-
fore, nonconductive materials require a conductive coating (gold/palladium alloy,
carbon, osmium, and so on). The low-voltage mode of modern microscopes makes
it possible to observe nonconductive specimens without a coating. Nonconductive
materials also can be imaged by a variable pressure (or environmental) scanning
electron microscope.
3.6 RHEOLOGICAL PROPERTY
3.6.1 Rheology in Plastic Packaging Polymers
Traditionally, rheology is defined as the study of flow and deformation of materials

and how that flow is affected by stresses, strains, and time, or how its behavior changes
when a mechanical force is applied (i.e., its reaction to deformation and flow). The
behavior of a plastic polymer is the relationship between external action (force applied
to a body) and internal reaction (change of a body shape). The flow properties depend
not only on the magnitude and directionality of the external forces but also on the
molecular composition and structure of the material that experiences the force, for
example, the orientation and elongation of polymer molecules (Peacock and Calhoun
2006).
Many commonly used materials and formulations exhibit complex rheological
properties whose viscosity and viscoelasticity can vary depending upon the external
conditions applied—such as stress, strain, timescale, and temperature (Malvern
2013). Rheological properties impact all stages of materials used across multiple
industries—from formulation development and stability to processing and product
performance. By utilizing rheological measurements with new materials, process con-
ditions can easily be determined, and the final product’s properties and performance
can be predicted. For example, in the making of plastic articles, the manufacturer often
starts with pellets of plastic and ends up with the finished article; the material at the
starting point and the final article are both in a “solid” state. During this process,
the shape was changed into an intermediate state through either the viscous flow
region or the rubbery region. In these regions, the material can be deformed using rela-
tively small force (Figure 3.13).
The graph in Figure 3.13 shows that temperature is an extremely important factor
in the design of polymers. An increase in temperature to above its glass transition
temperature (Tg) can convert a polymer from a rigid brittle material to a viscoelastic
material that exhibits both elastic and viscous qualities (Askeland et al. 2010). After
shaping and forming, the polymer is quenched to a temperature below Tg, where it will
11
Glassy
10
Log (modulus)
Rubbery
8
7 Melt
6
5
Tg
Temperature
Figure 3.13 Changes in a polymer's stiffness or modulus with respect to temperature.
keep its new shape. That is, as temperature increases, the properties of a material will
change. Sometimes the changes are small, sometimes they are large. For polymers, if
we look at the mechanical properties as a function of temperature, we see a behavior
similar to that shown on this graph.
3.6.2 Rheology Properties and Measurements
Typical rheological properties are viscosity, modulus, compliance, yield stress,

and relaxation times (Winter 2008). In practice, rheology is principally concerned
with extending continuum mechanics to characterize a flow of materials that exhibits
a combination of elastic, viscous, and plastic behavior by properly combining elasti-
city and Newtonian fluid mechanics. The experimental characterization of a material’s
rheological behavior is known as rheometry. The viscoelastic properties of polymers
are determined by the effects of temperature, pressure, and time. Much of theoretical
rheology is concerned with associating external forces and torques with internal stres-
ses and internal strain gradients and velocities (Schowalter 1978; Bird et al. 1989).
Materials with the characteristics of a fluid will flow when subjected to a stress
that is defined as the force per area. There are different types of stress (e.g., shear,
torsional), and materials can respond differently to different stresses. The measure-
ment of rheological properties is applicable to all materials—from fluids such as
dilute solutions of polymers and surfactants to concentrated protein formulations to
semisolids such as pastes and creams to molten or solid polymers. Examples of
rheological measurements include normal stresses and strains, shear stresses, and
viscosity to determine the viscosity profiling for non-Newtonian shear-dependent
behavior to simulate processing or use conditions, or viscoelastic fingerprinting for
material classification to determine extent if behavior is “solid-like” or “liquid-
like,” and so on.
3.6.2.1 Stresses and Strains
As indicated previously, rheological studies of polymeric materials explore the

flow of a material as an external force acts upon it. Mathematically, a force is the
work (which is a form of energy) required to move an object over some distance.
In a polymer system, the term “forces” becomes a bit complicated. Polymer scientists
use “stress” instead of “force.” A stress is the force perpendicularly applied to a system
over a cross-sectional area (Figure 3.14) (Peacock and Calhoun 2006). Consequently,
the imposed stress induces a strain within the specimen experiencing the applied force.
Strain is defined as deformation of a material in the direction of the applied stress as
related to its length in that direction (Equation 3.6). It is important to note that the per-
pendicular directionality of force applied to an area is an example of the effect of a
normal stress on a material (Peacock and Calhoun 2006). In addition to the normal
stress, a stress applied parallel or tangential to a face of a material and inducing a
deformation is defined as a shear stress (Figure 3.15).
Change in length Δl
Strain = = (3.6)
Original length L
Force
Tensile deformation Length = L + ΔL
Length = L
Force Strain = ΔL
Figure 3.14 Rectangular samples undergoing tensile strain.

Shear
stress, δ
Shear
deformation
Figure 3.15 Shear strain induced by shear stress.
τ= F
A
. dγ
γ=
dt F
γ
Figure 3.16 An amount of a liquid moving at shear rate γ_ under an applied shear stress τ.
3.6.2.2 Viscosity
Rheology, particularly the study of the viscous flow of polymers, is very important
in processing and proves useful as a quality control tool. Viscosity is an important
characteristic for all materials, especially polymers. For liquids, viscosity will influ-
ence flow characteristics, heat transfer, and mass transfer. For polymers, viscosity is
used in processing as a measure of velocity profile, magnitude of pressure drops, or
amount of heat generation. As defined by Peacock and Calhoun (2006), a material’s
viscosity (η) is the ratio of the applied stress (δ) to the strain rate (γ) (Equation 3.7).
δ
η= (3.7)
γ
For many materials, the applied stress and its induced strain are in a linear
relationship. In other words, the rate of strain is proportional to the applied stress.
The more resistant a material is to an applied stress, the higher is its viscosity.
However, this linear relationship is only defined for a Newtonian fluid. Most
molten polymers respond to stresses in a nonlinear fashion—the greater the applied
stress, the more effective the stress is at inducing a strain rate. Typically, the viscosity
drops at high shear rates—a phenomenon known as shear thinning.
The shear strain in Figure 3.16 is
du
γ= (3.8)
dy
where u is displacement in the x direction. The strain rate is therefore
d du dvx
γ_ = = (3.9)
dt γdy dy
where vx is velocity in the x direction. The relations between viscosity (η), shear stress (τ),
and shear rate (_γ) are
τ τ
τ = ηγ_ or γ_ = or η= (3.10)
η γ_
Related ASTM (2002) standards are:
• ASTM D1238, Standard Test Method for Melt Flow Rates of Thermoplastics
by Extrusion Plastometer
• ASTM D1243, Test Method for Dilute Solution Viscosity of Vinyl Chloride
Polymers
• ASTM D2857, Standard Practice for Dilute Solution Viscosity of Polymers
• ASTM D4603, Standard Test Method for Determining Inherent Viscosity of
Poly(Ethylene Terephthalate) (PET) by Glass Capillary Viscometer
3.6.2.3 Melt Index
Melt flow indexing (MFI) is a measure of the ease of flow of the melt of a thermo-
plastic polymer to determine the material viscosity. This property is very crucial for
finding packaging applications because it is highly related to processability using a
variety of processing techniques. MFI measures how many grams of polymer pass
through a standardized capillary under a standard load over 10 min (Figure 3.17).
The method is described in the similar standards, ASTM D1238 and ISO 1133.
The value obtained through the melt flow index test is a single data point. The melt
flow index only tests the material at one shear stress and temperature. In general, a
higher melt flow index indicates a lower material viscosity. The MFI information
from different materials and material grades may be used for a rough comparison
of flow characteristics for different materials. However, to obtain more accurate and
relevant viscosity data, it is better to perform rheology tests using a capillary rhe-
ometer or a parallel plate rheometer.
3.6.2.4 Cone and Plate Rheometer
Another important method of measuring the rheological properties of polymer

solutions and melt is by using the cone-and-plate rheometer (Figure 3.18). From
this method, we can obtain the steady shear or dynamic viscosity of the polymer
(Heuser and Krause 1979; Anonymous 2002; Sunthar 2010; Wassgren 2010).
Weight
Piston
Thermometer
Polymer melt
Die
Extrudate
Figure 3.17 Melt flow index apparatus.
Rc
β
Figure 3.18 Idealized illustration of a cone-and-plate rheometer.

In this method, the cone angle, β, is typically very small. At low angles, the shear rate,
γ , is given as:
Ω
γ = (3.11)
β
where Ω is the angular velocity of the cone. Dynamic viscosity can be obtained by
applying an oscillatory shear on the cone. The shear stress, τ, is determined as
3M
τ= (3.12)
2πR3c
where M is the measured torque on the cone having radius Rc. The viscosity is then
obtained from steady-shear measurements as:
τ
η= (3.13)
γ′
3.6.2.5 Capilliary Rheometry
Capillary rheometers have been used to measure the shear viscosity and elasticity
of viscous materials at high shear rates, typically from 10 to 10,000 s−1. Such shear
rates can be reached easily in capillary flow and also in polymer processing. The mea-
surement principle is that liquid is forced through a tube of constant cross section and
precisely known dimensions under conditions of laminar flow—that is, the motion of
the particles of fluid orderly with all particles moving in straight lines parallel to the
pipe walls (Sleigh 2001)—to measure the steady-shear viscosity. According to the
Hagen–Poiseuille law, the pressure drop (Δp) in a fluid flowing through a long capil-
lary (radius R, length L) at a volume flow rate (Q) depends on the shear viscosity for
Newtonian fluids (Equation 3.14) (Winter 2008). For non-Newtonian fluids, the pres-
sure drop versus flow rate must be analyzed using the Weissenberg–Rabinowitsch–
Mooney equation (Equation 3.15) (Salas-Bringas et al. 2010).
Δp πR4
η= (3.14)
L 8Q
Z
2 3
3Q d ðπRQ3 Þ
γ = τw = + σw 4 5 (3.15)
πR3 dτw
3.7 CONCLUSION
For food packaging engineers or scientists who are developing new packaging
products with polymers in industry or who need to find the solutions for industrial
problems during the entire product life cycle, complete understanding of packaging
polymer properties, which relies on the basic principles of chemistry, physics, rheology,
morphology, and even mechanics of polymers, is truly essential. Moreover, the suc-
cessful assessment of the different types of properties of packaging polymers depends
on the types, conditions, and purposes of testing methods and testing materials.
Food packaging engineers must understand the overall relationship between the testing
method and the property that is retained in the plastic packaging polymer. Through
these steps, the functionality of packaging polymers will be successfully conveyed
to the individual component of the entire food packaging system. In the future, the eva-
luation of packaging polymer properties will become easier and more convenient for
users, bringing with it higher accuracy for better assurance in food products as new
and advanced technology is continuously invented and introduced.
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CHAPTER 4
Testing of Mechanical Properties for

Plastic Packaging Materials
Laszlo Horvath, Byungjin Min, and Young T. Kim
CONTENTS
4.1 Introduction...................................................................................................104
4.2 Regulation in Plastic Packaging Testing Methods .......................................104
4.2.1 ASTM International ..........................................................................105
4.2.2 International Organization for Standardization (ISO).......................105
4.2.3 International Safe Transit Association (ISTA) .................................106
4.2.4 Hazardous Goods Packaging Regulations ........................................106
4.3 Plastic Packaging Material Testing Methods................................................106
4.3.1 Plastic Packaging Materials and Products ........................................106
4.3.1.1 Tensile Properties.............................................................. 106
4.3.1.2 Impact Strength................................................................. 109
4.3.1.3 Tear Strength..................................................................... 110
4.3.1.4 Coefficient of Friction (COF) ........................................... 110
4.3.1.5 Adhesion Test of Multilayer Plastic Films ....................... 111
4.4 Testing Methods for Plastic Packaging Systems During
Logistical Packaging.....................................................................................113
4.4.1 Shock Testing ...................................................................................113
4.4.2 Vibration Testing ..............................................................................115
4.4.3 Compression Testing ........................................................................116
4.4.4 Environmental Testing......................................................................117
4.4.4.1 Sample Conditioning ........................................................ 117
4.4.4.2 Pallet Testing .................................................................... 118
4.4.4.3 Unit Load Testing ............................................................. 120
4.5 Conclusion ....................................................................................................121
References ..............................................................................................................121
103
4.1 INTRODUCTION
Historically, plastic is one of the major packaging materials and the largest market
for general plastic resins. The use of plastic materials in the packaging field extends
from the primary to the tertiary packaging area, including distribution and transporta-
tion. The magnitude of global distribution is expanding exponentially every year.
Companies are outsourcing their production to less-developed countries where labor
is cheaper, or manufacturing operations are moved close to the raw materials’ sources
to improve the efficiency of manufacturing. It is expected that the global distribution of
goods increased to 235.7 million TEU in 2015 (herein, TEU stands for 20-ft equivalent
unit, 6.1 m) from 116.6 million TEU in 2005 (UNESCAP 2007). Transportation of
food products is an especially important part of the global economy. Complex distribu-
tion networks are used to effectively transport various food products from the farm to
the final customer. During this process, food products are transported in bulk or semi-
containers, unitized loads, or individual display-ready packages. Meanwhile, the trans-
portation of package-product systems could occur using a variety of methods including
full truckload (FTL), less than truckload (LTL), maritime transport, rail, air transport, or
parcel delivery. Each of these transportation modes produces hazards that are unique to
the particular mode of handling. One of the main functions of packaging is protection
against these hazards. Hazards include shock, vibration, compression, and atmospheric
conditions—among others—that can damage products or reduce their quality. To
ensure that a package has the required protective function for each type of distribution,
materials and performance testing is used. There are multiple standard testing proce-
dures available to assess the distribution performance of packaging materials in a
laboratory setting. Standards developed by the American Society for Testing Materials
(ASTM) International have been widely used in the United States, while standards
developed by the International Standards Organization (ISO) are more accepted inter-
nationally. The International Safe Transit Association (ISTA) has also been developing
more focused standards for preshipment testing that are updated more frequently and
provide information for more specialized distribution channels. However, the testing
results always need to be compared to the damages observed in the physical distribution,
and field trials need to be conducted before final implementation.
In an effective packaging system, each of the levels of packaging should be designed
to endure different levels and types of hazards. In this chapter, standards and design
methodologies will be presented that will help identify the required level of protection
and provide evaluation methodologies to simulate those hazards in the laboratory.
4.2 REGULATION IN PLASTIC PACKAGING TESTING METHODS
In general, various nonprofit, governmental, or international testing standards for

packaging materials and systems have been developed since the importance of packa-
ging was recognized. Once plastic packaging materials are converted into packaging arti-
cles, preshipment laboratory testing is an essential part of an effective packaging design.
Preshipment testing methods evaluate whether the performance of the packaging system
TESTING OF MECHANICAL PROPERTIES FOR PLASTIC PACKAGING MATERIALS 105
is adequate to endure the hazards of the physical distribution. There are various preship-
ment procedures available from multiple agencies. The following section will list the
main ones.
4.2.1 ASTM International
ASTM International, formerly known as the American Society of Testing Materi-

als (ASTM), was established in 1898. It has more than 30,000 members representing
150 countries. Standards developed by ASTM are voluntary consensus standards that
are published annually in its standard books. ASTM International has 144 technical
standard writing committees among which ASTM Committee D10 on Packaging
has been developing the standards and procedures related to packaging. The commit-
tee meets twice a year to update existing standards and to consider new ones. The
majority of the packaging-related standards are published in Volume 15.10 in the
Annual Book of ASTM Standards, although Volumes 08.01 and 08.02 also contain
some information related to plastic packaging materials and containers.
There are two main standards that provide information on the sequence of tests
required to simulate a specific distribution system and that also provide test severity
levels for products with different levels of fragility. The two standards in this group
are ASTM D4169, Standard Practice for Performance Testing of Shipping Containers
and Systems, and ASTM D7386, Standard Practice for Performance Testing of
Packages for Single Parcel Delivery Systems. Although ASTM D4169 is a more general
procedure for a wide range and type of packaging materials, ASTM D7386 provides
general simulation tests specific for the small parcel distribution environment.
Compared to other preshipment standards, ASTM standards provide a great cus-
tomization opportunity to simulate specific distribution systems. Another advantage
of ASTM D4169 compared to other testing standards is that it recognizes that some
products, such as high-value electronics, might require different levels of assurance
than those required by low-value commodity products, such as bags of rice. Therefore,
ASTM D4169 lists three different assurance levels. Assurance Level I is used for high-
value products, Assurance Level II should be used in every general case; and Assurance
Level III should be used for low-cost commodities.
4.2.2 International Organization for Standardization (ISO)
The ISO was founded in 1947, and today it is the world’s largest organization that
develops voluntary standards. Within ISO, technical committees (TCs) encompassing
experts all around the world are working on updating existing standards and are envi-
sioning new standards. Among all technical committees, TC-122 is responsible for the
standardization in regards to terminology and definitions, packaging dimensions, per-
formance requirements, and tests. TC-52 and TC-63 are more specialized committees
that specifically focus on light-gauge metal containers and glass containers, while
TC-51, TC-104, and TC-110 work on the standardization of pallets, freight containers,
and industrial trucks, respectively.
4.2.3 International Safe Transit Association (ISTA)
The history of ISTA began in 1948. Since then, ISTA has grown to more than 500
members, including shippers, carriers, manufacturers, and laboratories. ISTA develops
preshipment tests that are clustered into five series. ISTA 1-Series contains nonsimula-
tion integrity tests that evaluate the ruggedness of the products and packages but do not
provide an accurate simulation of the hazards in physical distribution. ISTA Procedures
1A and 1B are the first standards developed by the organization, and they are also the
oldest preshipment testing procedures in continuous use. ISTA 3-Series contains gen-
eral simulation tests that are based on the detailed investigation of the hazards in phy-
sical distribution. The procedures are based on ASTM D4169 and ASTM D7386,
but they provide much more specialized and defined testing requirements for specific
packaged-product systems. ISTA 5-Series is not currently used, but it is designed for
forced simulations based on user-measured hazards. ISTA 2-Series and 4-Series are
combinations of the aforementioned series with elements of each. In general, ISTA pro-
cedures are more tailored to specific situations and package configurations, and some
of the series requires less-expensive equipment and less-specialized operator skills.
4.2.4 Hazardous Goods Packaging Regulations
Although the preshipment testing of packaging solutions using ASTM, ISO, or

ISTA standards is voluntary and the testing severity levels are based on statistically
likely occurrences, the testing of dangerous or hazardous goods is mandatory, and
the testing levels are based on the concept of “catastrophic incident.” The most widely
accepted regulations are published by the United Nations (UN) in Transport of
Dangerous Goods: Recommendations of the Committee of Experts on the Transport
of Dangerous Goods. In the United States, the performance requirements for contain-
ers of hazardous goods are defined by the Title 49 of the Code of Federal Regulations
(CFR), while in Canada it is regulated by the Canadian General Standards Board
(CGSB). The regulations for hazardous goods packaging in the United States and
in Canada are not entirely compliant with the UN regulations.
In addition, the Intergovernmental Maritime Consultative Organization (IMCO)
and the International Air Transport Association (IATA) have been developing perfor-
mance standards covering the transportation of hazardous goods in respect to maritime
and air transportation.
4.3 PLASTIC PACKAGING MATERIAL TESTING METHODS

4.3.1 Plastic Packaging Materials and Products
4.3.1.1 Tensile Properties
Tensile properties are among the most important mechanical properties of plastics.
Some widely used test methods of packaging materials for various food products can
be generally described by parameters including tensile strength (MPa), elongation at
Elongation at break
oint
ak p
Bre
Ultimate stress
nt
d poi
Yield stress Yiel
Stress (σ) MPa
Young’s modulus = stress/strain
Plastic region
Elastic
region
Strain (є)
Figure 4.1 A pattern of the stress–strain curve for thermoplastics.
break (%), yield strength (MPa), and elasticity. These values can be obtained with
direct readings or by calculating the values using the equation from the graph pro-
duced under the conditioned test practice called “stress–strain.” This curve is presented
in Figure 4.1. Tensile properties of test specimens can be influenced by thickness,
sample preparations, and test conditions. Each test specimen can be divided into
Types I, II, III, and IV by rigidity and thickness. According to ASTM D638, Standard
Test Method for Tensile Properties of Plastics, Type I is defined by rigid or semirigid
plastic materials having a thickness of 7 mm (0.28 in.) or less. Type IV plastics should be
nonrigid or semirigid with a thickness of 4 mm (0.16 in.) or less. This method requires at
least five specimens, and the speed of the testing is very dependent on the specimen type,
which is presented in Table 4.1. The most important values in tensile properties can be
calculated and are described as follows:
• Tensile strength: Calculate by dividing the maximum load in newtons by the

average original cross-sectional area in the gauge length segment of the specimen
in square meters (ASTM D638).
• Percent elongation at break: Calculate the percent elongation at break by read-
ing the extension at the point of specimen rupture; divide the extension by the
original gauge length and multiply by 100 (ASTM D638):
L/L0 × 100 = Elongation (%);
where
L = the length of polymer specimen after the stretching is performed.
L0 = the length of polymer specimen before the stretching is performed.
Table 4.1 Designations for Speed of Testing (ASTM D638)
Nominal Strain Rate Start

Speed of Testing, of Test, mm/mm · min
Classification Specimen Type mm/min (in./min) (in./in. · min)
Rigid or Semi-rigid I, II, III rods and tubes 5 (0.2) ± 25% 0.1
50 (2) ± 10% 1
500 (20) ± 10% 10
IV 5 (0.2) ± 25% 0.15
50 (2) ± 10% 1.5
500 (20) ± 10% 15
V 1 (0.05) ± 25% 0.1
10 (0.5) ± 25% 1
100 (5) ± 25% 10
Non-rigid III 50 (2) ± 10% 1
500 (20) ± 10% 10
IV 50 (2) ± 10% 1.5
500 (20) ± 10% 15
• Modulus of elasticity (Young’s Modulus): calculated by extending the initial

linear portion of the load extension curve and dividing the difference in stress
corresponding to any segment of the section on this straight line by the corre-
sponding difference in the strain (ASTM D638):
The initial slope of stress (σ) versus strain (Є);

Where
stress = force/area (unit: Pa or MPa)
strain = deformation of original size (mm/mm)
• Yield point: Calculate the stress at which the elastic material undergoes increas-
ing force and ceases to behave elastically.
• Break point: Calculate the stress at the point where the elastic specimen is
ruptured.
The following standards provide guidance to test the tensile properties of plastic
materials:
• ASTM D618, Standard Practice for Conditioning Plastics for Testing

• ASTM D638, Standard Test Method for Tensile Properties of Plastics
• ASTM D6287, Standard Practice for Cutting Film and Sheeting Test Specimens
• ASTM D6988, Standard Guide for Determination of Thickness of Plastic
Film Test Specimens
• ASTM D882, Standard Test Method for Tensile Properties of Thin Plastic
Sheeting
• ISO 291, Plastics—Standard Atmospheres for Conditioning and Testing

• ISO 472, Plastics—Vocabulary
• ISO 527-1, Determination of Tensile Properties
Once we have collected the data from these unspecified plastics for tensile strength
testing, the data provide significant information needed to understand the characteri-
zation of each plastic before the application process in general. In addition to tensile
properties, there are other existing properties that could be considered as important
values when we further specify the plastics in order to determine whether or not packa-
ging materials are appropriate for target food products.
Tests for bioplastic, biobased, or biopolymeric materials that are derived or
synthetized out of biocomponents—biomass, bio-based monomers, or polymers by
microorganisms (Siracusa et al. 2008) that have, in general, highly sensitive charac-
teristics against environmental and physical conditions—are slightly modified from
currently used test methods for common synthetic polymers in food packaging mate-
rials. Testing methods are highly dependent on the material itself, and various adjust-
ments should be considered for individual bioplastics. These adjustments might
include ways of sample preparation, testing parameters, and environmental conditions
such as temperature, pH, relative humidity, and so forth.
4.3.1.2 Impact Strength
This property is generally considered as “toughness.” The impact strength is the

measurement of force that is required to resist the penetrating power of a rounded
probe by a conditioned test practice. Test specimens can be prepared with condition-
ing at 23 ± 2°C and 50 ± 10% RH for more than 40 h before the test. Impact strength
could be obtained by calculating the given area of the stress versus strain curve before
the specimen is broken or stretched.
The following standards provide guidance in testing the impact resistance of
plastic films:
• ASTM D618, Practice for Conditioning Plastics for Testing

• ASTM D883, Standard Terminology Relating to Plastics
• ASTM D1709, Standard Test Methods for Impact Resistance of Plastic Film by
the Free-Falling Dart Method
• ASTM D1922, Standard Test Method for Propagation Tear Resistance of
Plastic Film and Thin Sheeting by Pendulum Method
• ASTM D4272, Standard Test Method for Total Energy Impact of Plastic Films
by Dart Drop
• ASTM D6988, Standard Guide for Determination of Thickness of Plastic Film
Test Specimens
• ASTM E177, Standard Practice for Use of the Terms Precision and Bias in
ASTM Test Methods
• ASTM E691, Standard Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
• ISO 180, Plastics—Determination of Izod Impact Strength

• ISO 7765, Plastics Film and Sheeting—Determination of Impact Resistance by
the Free Falling Dart Method—Part 1: Staircase Methods
4.3.1.3 Tear Strength
This property is considered as the “tear

resistance,” which is the force required to Force
start tearing flexible plastic films. One side,
with a movable grip, holds the plastic sample
and stretches it at a constant rate of speed Sample
using a constant rate of grip separation test
from a fixed grip (Figure 4.2). This method
is not be applicable with those plastic samples Force
that have an extension of more than 101.6 mm.
The following standards provide guidance
for testing the tear resistance of plastic films: Figure 4.2 Diagram of tear strength test.
• ASTM D618, Practice for Conditioning Plastics for Testing

• ASTM D1004, Test Method for Tear Resistance of Plastic Film and
Sheeting
• ASTM D4000, Standard Classification System for Specifying Plastic
Materials
• ASTM D5947, Standard Test Methods for Physical Dimensions of Solid
Plastics Specimens
• ASTM D6988, Standard Guide for Determination of Thickness of Plastic Film
Test Specimens
• ISO 6383-2, Plastics—Film and Sheeting—Determination of Tear Resistance—
Part 2 Elmendorf Method
4.3.1.4 Coefficient of Friction (COF)
This property is considered as the “friction” and is determined by the surface adhesiv-
ity (surface tension and crystallinity), additives (slip, pigment, and antiblock agents), and
surface finish (Hernandez et al. 2000). It is not a material property but the property of a
tribological system, which refers to the “interacting surfaces in relative motion” in the
field of science and technology.
The coefficients are calibrated from initial and sliding friction of plastic films or
sheeting. COF measurement is based on observation of the relative motion between
two bodies in contact and the coefficient that can be expressed as a ratio of force
related to friction from different surfaces. It is expressed as
Ff = μ · N,
where
Ff = frinctional force (N),
μ = static or kinetic frictional coefficient,
N = normal force (N)
Kinetic frictional coefficients are associated with relative motion between objects.
Static frictional coefficients are associated with the force required to start moving an
object without relative motion. Static coefficients are, in general, higher than kinetic coef-
ficients. The COF can be affected by intrinsic characteristics of plastic samples as well as
environmental factors such as machine speed, blooming (referring to the migration of the
additive from the bulk of the film to the surface), temperature, humidity, and electrostatic
buildup. In the real world, friction is often associated with worn surfaces (inducing loss of
materials), frictional heat, or problems of squeak (undesirable noise).
In the testing practice, it is very important to consider the interface between the
testing sample and the contact surface. For example, the COF for polymer film passing
over surfaces harder than the film itself is a function of the shear strength of the mate-
rial. The following standards provide guidance to test the ratio of friction of plastics:
• ASTM D618, Standard Practice for Conditioning Plastics for Testing

• ASTM D883, Standard Terminology Relating to Plastics
• ASTM D1894, Standard Test Method for Static and Kinetic Coefficients of
Friction of Plastic Film and Sheeting
• ASTM D3574, Standard Test Methods for Flexible Cellular Materials—Slab,
Bonded, and Molded Urethane Foams
• ASTM D4000, Standard Classification System for Specifying Plastic Materials
• ASTM E177, Standard Practice for Use of the Terms Precision and Bias in
ASTM Test Methods
• ASTM G143, Standard Test Method for Measurement of Web/Roller Friction
Characteristics
• ISO 8295–1995, Plastics-Film and Sheeting: Determination of the Coefficients
of Friction
4.3.1.5 Adhesion Test of Multilayer Plastic Films
Adhesion refers to the bond (chemical or physical) between two adjacent materi-
als, and it is related to the force required to affect their complete separation. In plastic
packaging systems, coating or multilayer structures often have been applied to provide
desirable functionality. In the flexible packaging area, delamination is the mode of
failure where the materials begin to separate. There is a weakening of bonds from
either the adhesives or other contacting layers. The separation can happen inside
the material; therefore, they may not show any signs of wear. There are several
factors—such as pressure, temperature, humidity, shock and vibration, and irradiation—
that increase the delamination process. For example, a rapid increase or decrease in
pressure and temperature will break the layers from the substrate much faster. Adhe-
sives are particularly susceptible to humidity (Oreski and Wallner 2005). Adhesion
testing can be performed in two different ways: qualitatively and quantitatively.
Qualitative tests include the Scotch tape test, bending, abrasion, heating, scribing,
grinding, and impacting tests, while quantitative tests include tensile, shear, peel,
ultrasonic, centrifuge, and flyer plate tests.
Diverse adhesive test methods for plastic are found in ASTM standards:
• ASTM D904-99(2008), Standard Practice for Exposure of Adhesive Specimens

to Artificial Light
• ASTM D1828-01(2007), Practice for Atmospheric Exposure of Adhesive-
Bonded Joints and Structures
• ASTM D2093-03(2011), Standard Practice for Preparation of Surfaces of
Plastics Prior to Adhesive Bonding
• ASTM D3163-01(2008), Standard Test Method for Determining Strength of
Adhesively Bonded Rigid Plastic Lap-Shear Joints in Shear by Tension Loading
• ASTM D3164-03(2011), Standard Test Method for Strength Properties of
Adhesively Bonded Plastic Lap-Shear Sandwich Joints in Shear by Tension
Loading. This test method is intended to complement the test methods
ASTM D1002, Standard Test Method for Apparent Shear Strength of Single-
Lap-Joint Adhesively Bonded Metal Specimens by Tension Loading (Metal-
to-Metal), and ASTM D3163 and to extend its application to single-lap-shear
adhesive joints employing plastic adherends. The test method is useful for
generating comparative shear strength data for joints made from a number of
plastics. It can also provide a means by which several plastics’ surface treat-
ments can be compared.
• ASTM D3807-98(2012), Standard Test Method for Strength Properties of
Adhesives in Cleavage Peel by Tension Loading (Engineering Plastics-
to-Engineering Plastics)
• ASTM D3808-01(2007), Standard Test Method for Qualitative Determination
of Adhesion of Adhesives to Substrates by Spot Adhesion
• ASTM D3929-03(2010), Standard Test Method for Evaluating Stress Cracking
of Plastics by Adhesives Using the Bent-Beam Method. This test is used to show
the compatibility of adhesives with different plastic materials based on whether
the adhesive causes cracking. It can be used on injection molded tensile speci-
mens and can be in the form of a sheet or a strip.
• ASTM D4501-01(2009), Test Method for Shear Strength of Adhesive
Bonds Between Rigid Substrates by the Block-Shear Method. This test is used to
determine the shear strength of an adhesive with various substrate materials. It is
particularly applicable for testing bonds among ceramic, glass, magnet moldings,
and plastic parts with one flat face where machining would be difficult.
• ASTM D5041-98(2012), Standard Test Method for Fracture Strength in Cleavage
of Adhesives in Bonded Joints
• ASTM D5573-99(2012), Adjunct to D5573 Practice for Classifying Failure
Modes in Fiber Reinforced Plastic (FRP) Joints
• ASTM D5868-01(2008), Standard Test Method for Lap Shear Adhesion for
Fiber Reinforced Plastic (FRP) Bonding
• ASTM D6105-04(2012), Standard Practice for Application of Electrical
Discharge Surface Treatment (Activation) of Plastics for Adhesive Bonding
4.4 TESTING METHODS FOR PLASTIC PACKAGING SYSTEMS

DURING LOGISTICAL PACKAGING
4.4.1 Shock Testing
Product-package systems such as foods in plastic containers encounter multiple

forms of shock during physical distribution. This testing is often conducted to either
get information on the fragility of the product or to evaluate the protective function of
the packaging system. The majority of the shocks occur during material handling such
as rail cart switching, forklift handling, containerization, and manual handling. Every
product has a fragility that can be measured with the product fragility test according to
ASTM D3332, Standard Test Methods for Mechanical-Shock Fragility of Products,
Using Shock Machines. The result of the product fragility test is the damage boundary
curve, which provides information to the package designer about the regions where
the product more likely will be damaged. An example damage boundary curve is pre-
sented in Figure 4.3. In a case where both the acceleration and velocity change values
encountered in physical distribution exceed the critical acceleration and critical velo-
city values of the product, various forms of cushioning materials need be utilized to
prevent damage from occurring. The following standards provide guidance for testing
the effectiveness of cushioning materials:
• ASTM D4168, Standard Test Methods for Transmitted Shock Characteristics

of Foam-in-Place Cushioning Materials
• ASTM D1596, Standard Test Method for Dynamic Shock Cushioning Charac-
teristics of Packaging Material
Critical velocity change

Acceleration (g)
Damage region
No damage region Critical acceleration
Velocity change (m/sec.)
Figure 4.3 Damage boundary curve.

Once the protective packaging system is developed, the effectiveness of the system
to withstand shocks occurring in physical distribution can be evaluated using the fol-
lowing standards:
• ASTM D5265, Standard Test Method for Bridge Impact Testing

• ASTM D5276, Standard Test Method for Drop Test of Loaded Containers by
Free Fall
• ASTM D5487, Standard Test Method for Simulated Drop of Loaded Contain-
ers by Shock Machines
• ISO 2248, Packaging—Complete, Filled Transport Packages—Vertical Impact
Test by Dropping
The differences among the aforementioned standards are the means of performance
evaluation. ASTM D5276 and ISO 2248 utilize free-fall drop testers, while ASTM
D5487 utilizes mechanical shock testers. Free-fall drop testers use gravity to produce
repeatable drops at a selected orientation. Mechanical shock testers are much more
sophisticated, using a programing device to produce different shock durations and
shock shapes.
ASTM D5265 evaluates the ability of long and narrow shipping containers to
withstand impacts close to their center point. The standard utilizes free-fall drop tes-
ters and simulated mechanical testing equipment to produce the required impact. The
exact drop heights, drop orientations, and acceleration values are published in ASTM
D4169 and also in various ISTA standards.
Unitized packages experience a significant amount of horizontal shock during rail
and over the road shipments. These horizontal shocks can damage products and can
cause unit load instability. Horizontal shocks can be simulated using incline impact tes-
ters where the unit load or package is placed on a movable carriage that rides down a
10° incline and collides with a fixed backstop at the end of the path (Figure 4.4). The
Figure 4.4 Incline impact tester of shipping containers. (Courtesy of Lansmont Corp, http://
www.lansmont.com/PDF/Impact/Lansmont_Inclined_Impact.pdf.)
shock impact can be controlled using impact velocity and impact programmers. A more
expensive but more accurate solution is provided by horizontal impact testers where
the carriage is accelerated along a horizontal track into a programmable backstop.
The following standards provide exact specifications for horizontal shock testing.
• ASTM D880, Standard Test Method for Incline Impact Testing for Shipping
Containers and Systems
• ASTM D4003, Standard Test Methods for Programmable Horizontal Impact
Testing for Shipping Containers and Systems
• ASTM D5277, Standard Test Method for Performing Programmed Horizontal
Impacts Using an Inclined Impact Tester
• ISO 2244, Packaging—Complete, Filled Transport Packages and Unit Loads—
Horizontal Impact Tests
Another common form of horizontal shock in palletized distribution occurs

during forklift handling. With some modifications, incline impact testers can be
used to evaluate the resistance of pallets against fork tine impact to the posts and
end boards. More information on the incline impact testing of pallet components
can be found in ASTM D1185, Standard Test Methods for Pallets and Related Struc-
tures Employed in Materials Handling and Shipping, or in ISO 8611, Pallets for
Materials Handling—Flat Pallets.
4.4.2 Vibration Testing
Vibrations naturally occur during different modes of transportation (air, maritime,

over the road, and so on), and they are highly dependent on the speed, suspension,
type of vehicle, and road characteristics or weather conditions in cases of maritime
shipping. During transport, multiple modes of vibrations are acting simultaneously—
such as vibrations of the trailer’s suspension system, vibration of the truck’s engine, or
even vibration of the truck chassis. The combinations of these vibrations are described
by the random vibration spectra that incorporate the resonance frequencies of each of
the component vibrations with their respective intensities. In general, maritime transport
produces the lowest frequency vibrations, followed by over the road transport, rail trans-
port, and air transport.
Vibration tests can be grouped into two categories: repetitive-shock vibration tests
and variable-frequency vibration tests. Repetitive-shock vibration tests are conducted
at 25.4 mm amplitude, 1.1 G vibration, at 4.5 Hz frequency. These tests are ideal
for evaluating the scuff resistance of packaging solutions but, due to their fixed
frequency and fixed amplitude, they are very limited in their ability to simulate
real world complex vibrations. Variable-frequency vibration tables have the ability
to control amplitude, frequency, and acceleration. During random vibration testing,
multiple frequencies are vibrated simultaneously with their applicable intensity; there-
fore, this testing is much better at simulating the complex nature of physical distribution.
Random vibration profiles are produced by ASTM and ISTA working groups, and they
are published in ASTM D4169 or in the applicable ISTA standards.
The following standards provide guidance for vibration testing of shipping containers:
• ASTM D999, Standard Test Methods for Vibration Testing of Shipping

Containers
• ASTM D3580, Standard Test Methods for Vibration (Vertical Linear Motion)
Test of Products
• ASTM D4728, Standard Test Method for Random Vibration Testing of Shipping
Containers
• ASTM D5112, Standard Test Method for Vibration (Horizontal Linear
Motion) Test of Products
Vibration Tests at Fixed Low Frequency
Sinusoidal Vibration Tests using a Variable Frequency
• ISO 13355, Packaging—Complete, Filled Transport Packages and Unit
Loads—Vertical Random Vibration Test
4.4.3 Compression Testing
During physical distribution, packages are often stacked on top of each other,
which applies a great amount of compressive forces on the package itself and some-
times on the product carried by the package. Therefore, information on the compressive
resistance of packaging containers is essential. To assess the load carrying capacity of
packaging containers, compression tests are conducted. During the compression test,
load is applied to the container by a fixed or a swivel platen (Figure 4.5).
Figure 4.5 Fixed-platen compression test. (Courtesy of Center for Packaging and Unit Load
Design at Virginia Tech, Blacksburg, VA.)
The following standards provide guidelines for the compression testing of ship-
ping containers, components, and unit loads:
• ASTM D642, Standard Test Method for Determining Compressive Resistance

of Shipping Containers, Components, and Unit Loads
• Technical Association of the Pulp and Paper Industry (TAPPI)/American
National Standards Institute (ANSI) T804, Compression Test of Fiberboard
Shipping Containers
• ISO 12048, Packaging—Complete, Filled Transport Packages—Compression
and Stacking Tests using a Compression Tester
The common practice in industry is to evaluate single empty shipping containers;

however, care must be taken during the interpretation of the results because it has been
shown by multiple researchers that differences exist between the compression perfor-
mance of stacked and unstacked, unitized and nonunitized packages, and filled and
unfilled packages.
4.4.4 Environmental Testing
4.4.4.1 Sample Conditioning
Plastic packaging materials encounter a wide range of environmental conditions

during physical distribution. Some packages will be used in refrigerated storage
where the temperature could be −18°C or lower, while some packages will be
sent to tropical countries where the temperature could be as much as +40°C and
the relative humidity is more than 80%. Therefore, evaluating the ability of packa-
ging materials to withstand those conditions and to evaluate the performance of
packaging materials in different environmental conditions is essential. The environ-
mental conditions used to evaluate the performance of packaging materials always
need to be determined on a case by case basis using the actual conditions in the
particular distribution chain. Table 4.2 presents some of the most commonly used
testing conditions according to ISO 2233, Packaging—Packaging—Complete,
Table 4.2 Special Atmospheric Conditions Defined by ISO 2233 and ASTM D4332
Environment (ISO 2233 Condition) Temperature, °C (°F) Relative Humidity, %
Cryogenic (A) −55 ± 3 (−67 ± 6) …

Frozen food storage (C) −18 ± 2 (0 ± 4) …
Refrigerated storage (D) 5 ± 2 (41 ± 4) 85 ± 5
Temperate high humidity (F) 20 ± 2 (68 ± 4) 90 ± 5
Tropical (L) 40 ± 2 (104 ± 4) 90 ± 5
Desert 60 ± 2 (140 ± 4) 15 ± 2
Source: ASTM D4332.

Filled Transport Packages and Unit Loads—Conditioning for Testing, and ASTM
D4332, Standard Practice for Conditioning Containers, Packages, or Packaging
Components for Testing. The following two standards provide guidelines on the
conditioning procedures:
• ASTM D4332, Standard Practice for Conditioning Containers, Packages, or

Packaging Components for Testing
• ISO 2233, Packaging—Packaging—Complete, Filled Transport Packages and
Unit Loads—Conditioning for Testing
4.4.4.2 Pallet Testing
Pallets are an important part of the distribution system because they make hand-
ling of the unit loads easier and faster, and they provide protection for the contents
of the unit loads. In the United States, the majority of pallets are made out of wood,
but demand for plastic pallets is continuously increasing due to the higher sanita-
tion requirements from the food industry. Pallets also interact with the packages.
Therefore, evaluation of the load carrying capacity and durability of unit loads is
crucial.
The main pallet characteristics that need to be investigated are strength, stiffness,
durability, and functionality. The following standards provide guidelines for the
comprehensive evaluation of pallets:
• ASTM D1185, Standard Test Methods for Pallets and Related Structures
Employed in Materials Handling and Shipping
• ISO 8611 Part 1–3, Pallets for Material Handling—Flat Pallets
Strength and stiffness of pallets provide information about their load carrying
capacity in a specific support condition. Recent research conducted by Jiyoun Yoo,
in 2011, showed that the stiffness of the pallet can significantly influence the distribu-
tion of compression stresses experienced by the products (Yoo 2011). In light of this
information, the stiffness of the pallet does not just influence the load carrying capa-
city but also influences the way in which the components of the unit load interact with
each other. The main support conditions that are investigated for pallet bending are
rack support, floor support, conveyor support, and fork tine support. Pallet bending
tests using fork tine and conveyor supports provide information about the dynamic
load carrying capacity of the pallet. Pallet bending using floor support provides infor-
mation about the static load carrying capacity of the pallet, while pallet bending using
rack support provides information about the load carrying capacity of the pallet in
warehouse racking. One of the main differences between ASTM D1185 and ISO
8611 is the type of loading conditions. While ASTM D1185 uses an airbag to simulate
a continuously distributed flexible load on the pallet, due to lower repeatability of the
airbag test across multiple laboratories, ISO 8611 uses loading methods whereby a
series of loading beams are used to apply load on the pallet in a more repeatable fashion.
Example test setups are presented in Figure 4.6. Other than the loading condition,
(a) (b)
Figure 4.6 Loading conditions of fiber-reinforced plastic pallet bending test using (a) ISO 8611
and (b) ASTM D1185. (Courtesy of the Center for Packaging and Unit Load Design at
Virginia Tech, Blacksburg, VA.)
there are other important aspects that are different between the ISO and ASTM tests for
pallet strength and stiffness. For example, ISO 8611 uses a safety factor of 2, while
ASTM D1185 has a safety factor close to 2.5. There is also a minor difference between
the deflection limits required by the two standards.
In addition to the strength and the stiffness, the durability of the pallet has great
importance because it will influence how long the pallet will be in circulation.
Information on the durability of the pallet design can be obtained using incline impact
tests and free-fall drop tests. Incline impact test methods may include a set of fork
tines that are secured to a rigid backstop. When the pallet rides down the incline, the
fork tines impact either the block of the pallet or the end boards of the pallet depending
on the test purpose. In general, the test setup is similar in both ISO 8611 and ASTM
D1185, but there are also important differences. The experimental design for the incline
impact testing of the lead deck boards is presented in Figure 4.7.
In general, free-fall drop testing is conducted to evaluate the durability of pallet cor-
ners and edges during free-fall dropping of the pallet, including plastic pallets. ISO 8611
Figure 4.7 Experimental design for incline impact test of lead deck boards in fiber-reinforced plastic
pallet. (Courtesy of the Center for Packaging and Unit Load Design at Virginia Tech,
Blacksburg, VA.)
only recognizes corner drop tests, while ASTM D1185 recognizes corner and edge drop
tests. The main difference between durability tests recommended by ASTM D1185 and
ISO 8611 is that ASTM D1185 provides a single or multiple uses rating for the pallet
design, while ISO 8611 uses the durability tests for comparative purposes only.
4.4.4.3 Unit Load Testing
Globally, the majority of products are transported in a unit load form. In general,
unit loads are composed of a medium such as a pallet or slip-sheet, stacked secondary
package and sometimes are secured with stretch wrap or strapping. Unit loads are
manipulated by various forms of material handling equipment throughout their phy-
sical distribution; the interaction between unit loads and material handling equipment
can significantly influence the efficiency of the physical distribution. Therefore, it is
always a good idea to validate packaging solutions in a unit load form before the
end of the final design phase to make sure that all of the possible interactions are
accounted for. One of the most important interactions is between the packages and
pallets. The load securement method, stacking pattern, and the type of packages
have a significant effect on the load carrying capacity of the pallet. Based on these
findings, ISO included a maximum working load test into their testing procedure.
The maximum working load test uses the actual unit load to apply load to the pallet
(Figure 4.8), while testing methodology accounts for the load bridging among the
packages. The maximum working load testing methodology is presented in the
following standard:
• ISO 8611, Pallets for Material Handling—Flat Pallets—Part 3—Maximum

Working Loads
Figure 4.8 Experimental setup for maximum working load test based on ISO 8611—Part 3.
(Courtesy of the Center for Packaging and Unit Load Design at Virginia Tech,
Blacksburg, Virginia.)
4.5 CONCLUSION
Plastic packaging materials are widely used to protect, contain, display, and sell
multiple types of food products. To ensure quality and customer safety, it is essential
to test the properties of the packaging materials at different levels. The fundamental
mechanical properties of packaging materials such as tensile strength, impact resis-
tance, tear strength, adhesion, and coefficient of friction provide essential information
on the performance of primary packaging systems, while preshipment testing proce-
dures such as shock, vibration, and compression tests ensure that the protective func-
tion of the package is adequate to resist the hazards of physical distribution.
Nonetheless, the different levels of packaging systems do not exist in a silo. There
is significant interaction among the primary packages, secondary packages, and unit
loads. Therefore, it is always a good idea to test packaging systems in a unit load form
to capture these interactions.
REFERENCES
ASTM International. 2012. Annual book of ASTM standards. Section 8: Plastics, Section 15:
General Products, Chemical Specialties, and End Use Products. ASTM International,
West Conshohocken, PA.
Hernandez, R.J., Selke, S.E.M., and Culter, J.D. 2000. Plastics packaging. Hanser Gardner
Publications, Inc., Cincinnati, OH.
ISO 291 – Plastics-Standard atmospheres for conditioning and testing.
ISO 472 – Plastics-Vocabulary.
ISO – 8295–1995 Plastics-Film and Sheeting: Determination of the coefficients of friction.
ISO 6383-2 Plastics—Film and Sheeting—Determination of Tear Resistance—Part 2 Elmendorf
Method 5.
ISO 2233 – Packaging – Complete, filled transport packages and unit loads – Conditioning for
Testing.
ISO 2244 – Packaging – Complete, Filled Transport Packages and Unit Loads – Horizontal
Impact Tests.
ISO 2247 – Packaging – Complete, Filled Transport Packages and Unit Loads – Vibration tests
at Fixed Low Frequency.
ISO 2248 – Packaging – Complete, Filled Transport Packages – Vertical Impact Test by Dropping.
ISO 8318 – Packaging – Complete, Filled Transport Packages and Unit Loads – Sinusoidal
Vibration Tests using a Variable Frequency.
ISO 8611 Part 1–3 – Pallets for Material Handling – Flat Pallets.
ISO 12048 – Packaging – Complete, filled transport packages – Compression and stacking tests
using a compression tester ISO 13355 – Packaging – Complete, Filled Transport
Packages and Unit Loads – Vertical Random Vibration Test.
ISO 13355 – Packaging – Complete, Filled Transport Packages and Unit Loads – Vertical Random
Vibration Test.
Oreski, G. and Wallner, G.M. 2005. Delamination behaviour of multi-layer films for PV encap-
sulation. Solar Energy Materials and Solar Cells, 89, 2–3: 139–151.
Richard, C., Derek, M., Mark, J. and Kirwanm 2006. Food packaging technology. Blackwell
Publishing, Oxford, UK.
Siracusa, V., Rocculi, P., Romani, S. and Rosa, M.D. 2008. Biodegradable polymers for food
packaging: A review. Trends in Food Science & Technology, 19: 634–643.
TAPPI D685 – Conditioning Paper and Paper Products for Testing.
TAPPI/ANSI T804 – Compression Test of Fiberboard Shipping Containers.
UNESCAP. 2007. Regional Shipping and Port Development–Container Traffic Forecast 2007
Update. United Nations, New York.
White, M.S. et al. 1997. Optimizing unit-load design—A new systems approach to improving.
In: Handbook of bioplastics and biocomposites engineering applications. Pilla, S. (ed.),
Wiley-Scrivener, New York, p. 604.
Yoo, J. 2011. Modeling compressive stress distributions at the interface between a pallet deck
and distribution packaging. Doctoral Dissertation. Virginia Tech, Blacksburg, VA.
CHAPTER 5
Permeation Testing of Synthetic Polymers
Ayman Abdellatief and Bruce Welt
CONTENTS
5.1 Introduction...................................................................................................124
5.1.1 Steady-State Permeation Theory.......................................................124
5.1.2 Unsteady-State Diffusion..................................................................125
5.1.3 Temperature Dependence of Permeability........................................127
5.1.4 Permeability Units ............................................................................127
5.1.5 Gas Permeability versus Gas Transmission Rate (GTR)..................128
5.2 Methods for Measuring GTR........................................................................128
5.2.1 Pressure or Volume Increase Methods .............................................128
5.2.2 Isostatic Steady-State Methods .........................................................129
5.2.3 Dynamic Accumulation Methods .....................................................129
5.2.3.1 Oxygen Permeability ........................................................ 131
5.2.3.2 ASTM D3985 ................................................................... 132
5.2.3.3 Sensing Mechanism .......................................................... 132
5.2.3.4 Dynamic Accumulation Method....................................... 133
5.2.4 Measuring OTR of Whole Packages ................................................133
5.2.4.1 ASTM F1307 .................................................................... 133
5.2.4.2 Ambient Oxygen Ingress Rate.......................................... 134
5.3 Methods for Measuring Water Vapor Transmission ....................................134
5.3.1 Gravimetric Methods ........................................................................134
5.3.2 Infrared Sensing ................................................................................135
Nomenclature .........................................................................................................136
References ..............................................................................................................136
123
5.1 INTRODUCTION
5.1.1 Steady-State Permeation Theory
A polymer’s permeability is an important characteristic for packaging applica-

tions. Gas transfers through films or packaging via the process of permeation. Actually,
permeation is a combination of processes involving adsorption, solubility of the permeant
in the material and diffusion of the permeant through the material, and desorption.
A gas will permeate through a polymer in response to a concentration gradient,
which is limited by the solubility and diffusion coefficient of the gas in the polymer.
Once in the polymer, Equation 5.1 shows that diffusive flux, J, of a gas molecule in a
polymer is the amount (Q) passing through a unit area (A) normal to the direction of
flow during time (t), that is,
Q
J= (5.1)
At
The diffusive flux of a gas through a film is directly proportional to the concentra-
∂c
tion gradient, , through thickness (l) and is given by Fick’s first law by introduction
∂x
of the diffusion coefficient, D, as a constant of proportionality. For many thin
film packaging applications, the diffusion coefficient may be assumed to be constant.
However, for polar polymers, such as ethyl vinyl alcohol (EVOH) and polyamide (PA),
the diffusion coefficient is dependent on the water content. For multilayer film con-
structions, each unique material layer may often be assumed to have an associated
diffusion coefficient. Equation 5.2 expresses Fick’s first law of diffusion:
∂c
J = -D (5.2)
∂x
Equation 5.2 may be integrated from the concentration of one surface, c1, to the
opposite surface, c2, across a film of thickness l and arranged to:
Dðc2 -c1 Þ
J= (5.3)
l
The right-hand side of Equation 5.1 can be substituted for the diffusive flux J,
which yields
Q Dðc2 -c1 Þ
= (5.4)
At l
At sufficiently low concentrations, Henry’s law can be applied and is expressed as
c = Sp (5.5)
PERMEATION TESTING OF SYNTHETIC POLYMERS 125
where S is the solubility coefficient, and p is the partial pressure of the gas. Equation 5.6
can be substituted into Equation 5.5, which gives
Q DSðp2 − p1 Þ
= (5.6)
At l
The product DS is the permeability coefficient and is represented by P, yielding
Q PðΔpÞ
= (5.7)
At l
which can be rearranged to
Ql
P= (5.8)
AtðΔpÞ
There are four assumptions made in the aforementioned treatment of permeation:
The diffusion is in a steady-state condition, concentration is a linear function of dis-
tance within the polymer, diffusion takes place in only one dimension, and D and S
are constant (Robertson 1993). Table 5.1 shows the oxygen permeability and water
vapor permeability of common polymers.
5.1.2 Unsteady-State Diffusion
Initially, the polymer is free of the gas being measured unless it is stored in an envir-
onment containing the test gas. The polymer must become saturated with the test gas
before there is a constant flow of the gas. If one face (x = 0) of a membrane is kept at a con-
stant concentration C1 and the other (x = l) at C2, and the polymer initially contains no test
gas, there is a finite interval of time during which the steady-state condition is set up. The
solution for concentration as a function of time in the polymer is given by Equation 5.9.
Table 5.1 Oxygen and Water Vapor Permeability of Common Polymers
Oxygen Permeability Water Vapor Permeability

at 23°C 50% or 0% RH at 23°C 85% RH
Polymer [cm3mm/(m2day atm)] [gmm/(m2day)]
Poly(ethylene terephthalate) (PET) 1–5 0.5–2

Polypropylene (PP) 50–100 0.2–0.4
Polyethylene (PE) 50–200 0.5–2
Polystyrene (PS) 100–150 1–4
Poly(vinyl chloride) (PVC) 2–8 1–2
Poly(ethylene naphthalate) (PEN) 0.5 0.7
Polyamide (PA) 0.1–1 (dry) 0.5–10
Poly(vinyl alcohol) (PVAL) 0.02 (dry) 30
Ethylene vinyl alcohol (EVOH) 0.001–0.01 (dry) 1–3
Poly(vinylidene chloride) (PVDC) 0.01–0.3 0.1
Source: Lange, J., and Wyser, Y., Packaging Technology and Science, 16, 4, 149–158, 2003.
x 2X 1
C2 cos nπ-C1 nπx -Dn2 π2 t=l2
C = C1 + ðC2 -C1 Þ + sin e (5.9)
l π n=1 n l
The rate at which gas or another diffusing substance emerges from the face x = l of
the polymer is given by (-Dð∂C=∂xÞx = l ), which is derived from Equation 5.9. By inte-
grating with respect to t, we obtain the total amount of gas diffusing Qt that has passed
through the polymer in time t (Equation 5.10).
t 2l X
1
C1 cos nπ-C2
f1-e-Dn π t=l g
2 2
Qt = DðC1 -C2 Þ + 2 (5.10)
l π n=1 n2
In the most common experimental setup, C2 (the polymer surface where the test
gas emerges) is zero. Equation 5.10 can be rearranged to
Qt Dt 1 2 X1
-1n -Dn2 π2 t=l2
= 2- - 2 e (5.11)
lC1 l 6 π n = 1 n2
where, because t→∞, Equation 5.11 approaches the line

2
DC1 l
Qt = t- (5.12)
l 6D
The t-intercept l2/6D is known as the lag time (Crank 1975). From the lag time,
the diffusion coefficient can be estimated, as shown in Figure 5.1.
Concentration
Lag time = 12/6D Time
Figure 5.1 Concentration versus time curve of a gas in a polymer.

5.1.3 Temperature Dependence of Permeability
For most simple cases, P, D, and S can be represented with an Arrhenius-type rela-
tionship over small temperature ranges as given in Equations 5.13, 5.14, and 5.15,
PðTÞ = P 0 eð-EP =RTÞ (5.13)
DðTÞ = D0 eð-ED =RTÞ (5.14)
SðTÞ = S0 eð-ΔHS =RTÞ (5.15)
where, P 0 , D0, and S0 are constants, T is the absolute temperature, R is the gas con-
stant, EP is the activation energy for permeation, ED is the activation energy for diffu-
sion, and ΔHS is the heat of solution. Plotting—ln P on the vertical axis and T‐1 on the
horizontal axis will result in a straight line with a slope of E P/R. The diffusion coef-
ficient and solubility coefficient behave in a similar manner. From the relationship
P = DS and Equations 5.13, 5.14, and 5.15, it can be shown that the activation energies
are related to the heats of solution via Equation 5.16 (Strandburg et al. 1990).
EP = ED + ΔHS (5.16)
5.1.4 Permeability Units
The standard unit for permeability, solutes transporting through solvents, is the
area
same as diffusion . However, when describing gas transmission through a poly-
time
mer (Equation 5.8), units are typically expressed as
ðAmount of gasÞðThickness of membraneÞ

ðMembrane of areaÞðTimeÞðDifferential partial pressure of gasÞ
The advantage of these units is their ability to calculate gas flux under different
conditions because the units of practical parameters such as membrane area, thickness,
and applied differential pressure are included in the composite units. The disadvantage
is that it is difficult to compare the value of permeability with other types of transport
such as dissolved solid solutes and miscible liquids in a given medium (Yasuda 1975).
The most commonly used permeability units found in literature are
cm3 ðSTPÞ μm
m2 day atm
and
cm3 mil
100 in2 day atm
Table 5.2 Oxygen Transmission Rate Properties from a Packaging Film Specifica-
tion Sheet for Breathable Film Manufactured by Cryovac Division, Sealed
Air Corporation
OTR at 23°C, 0% R.H. MVTR at 38°C, 100% R.H.
Structure Gauge (mils) cc/m2/day cc/100 in2/day g/m2/day g/100 in2/day
F6227 2.7 1260 80 4 0.2

F6237 3.7 1250 80 3 0.2
ASTM Method D-3985 F-1249
Note: Permeability properties of available gauges (typical values).
5.1.5 Gas Permeability versus Gas Transmission Rate (GTR)
The permeability coefficient, like the diffusion coefficient, is a basic material prop-
erty. When speaking of permeability of oxygen through film, we might use a perme-
ability coefficient. However, industry is usually more interested in a specific film made
from a given batch of polymers with a given thickness, using particular processes and
treatments or multilayer films. In such cases, we wish to describe the rate at which
oxygen permeates through a given film. For this, we use the oxygen transmission
rate (OTR), which is one type of GTR of the film. Units of GTR are often reported as
ðAmount of gasÞ
ðFilm areaÞðTimeÞ
although it is easy to see that GTR may be determined from the permeability coeffi-
cient via Equation 5.17.
P
GTR = Δp (5.17)
l
We typically measure GTR for a given film and then calculate permeability coef-
ficient by rearranging Equation 5.17.
As mentioned, permeability is a fundamental property of the material and does not
vary with thickness. Film manufacturers usually report GTR on the film’s specifica-
tion sheet and not permeability. Table 5.2 shows the OTR on a film specification sheet.
5.2 METHODS FOR MEASURING GTR
5.2.1 Pressure or Volume Increase Methods
A standard for measuring transmission of any gas through a film is ASTM D1434,
Standard Test Method for Determining Gas Permeability Characteristics of Plastic
Film and Sheeting. Within this standard, there are two submethods—a manometric
method and a volumetric method. Briefly, a sample is mounted in a gas transmission
Test gas in Test gas out
Carrier Carrier gas +

gas in Test gas
transmitted to
sensor
Figure 5.2 Isostatic, steady-state method for measuring GTR.
cell to form a sealed semi-barrier between two chambers. One chamber initially con-
tains pure test gas at a specific higher pressure, and the other chamber receives the test
gas at a lower pressure. In the manometric method, the chamber receiving the test gas
is initially evacuated, and transmission of the gas through the film is determined by
measuring increases in pressure. In the volumetric method, the lower pressure cham-
ber is maintained at atmospheric pressure, and GTR is determined by measuring
changes in volume.
5.2.2 Isostatic Steady-State Methods
Measuring GTRs using the isostatic, steady-state method involves a permeation cell
where the sample material separates two chambers. Gases at similar absolute pressures
and flow rates pass on either side of the sample film. A test gas passes on one side while a
carrier gas passes on the other side. The carrier gas stream picks up the test gas permeat-
ing through the fixed sample area and passes through a sensor to measure the amount of
test gas. If oxygen is the test gas, a coulometric sensor is used. An infrared sensor can
be used for molecules containing different atoms such as carbon dioxide (CO2), water
(H2O), nitrogen dioxide (NO2), and methane (CH4). Because the absolute pressure is the
same on both sides, this method is referred to as isostatic. Because the test gas partial
pressure difference is held constant, this method is also referred to as steady state.
This isostatic, steady-state process is depicted in Figure 5.2.
5.2.3 Dynamic Accumulation Methods
Dynamic accumulation methods involve a carrier gas (typically nitrogen) that is

used to purge the sampling or probe side of the permeation cell prior to the test.
Once purged, the chamber valves are sealed. The test gas side may be left open
Sampling port or probe
Initial carrier Initial carrier

gas in Initially test gas free gas purge
Film sample
Test gas Test gas permeating Test gas
flow in flow out
Figure 5.3 Dynamic accumulation apparatus with test gas flowing through bottom chamber.
to the atmosphere enriched with the test gas and flushed with a desired concentra-
tion of test gas. The apparatus for dynamic accumulation is depicted in Figure 5.3.
Over time, test gas in the purged chamber accumulates and asymptotically
approaches the concentration of the test gas in the other chamber. This behavior is
depicted in Figure 5.4. The model used to calculate the GTR for this method was
developed from the permeation relationship (Equation 5.18):
dnA P A amb t
= ðp -pA Þ (5.18)
dt l A
where nA is moles of test gas, P A is the permeation coefficient in molar units, pamb
A
is the partial pressure in the ambient environment, ptA is the partial pressure at any
time in the accumulation chamber, A is sample area, l is sample thickness, and t is
time. Equation 5.18 describes the rate at which test gas permeates through a sample
of known area and thickness under a driving force defined by the partial pressure
difference on either side of the sample.
C_Amb
Concentration
Time (t)
Figure 5.4 Oxygen accumulation over time in purged chamber.

Dynamic accumulation is an inexpensive method for measuring OTR. Instruments

are commercially available (Oxysense, Inc., Dallas, TX; PreSens, Regensburg, Germany;
MOCON, Minneapolis, MN). With oxygen as the test/permeant gas and nitrogen as the
accumulation chamber purge gas, studies have shown that it may safely be assumed that
the volume of the permeation chamber is constant throughout the test. This assumption
relies on the fact that the permeation rates of oxygen and nitrogen are sufficiently close
so as not to stretch the sample during testing. This assumption would need to be validated
or corrections introduced for gases with significantly different permeation rates.
5.2.3.1 Oxygen Permeability
Next, we proceed with the specific example of determining OTR via dynamic
accumulation. With volume and pressure constant, oxygen partial pressure is directly
related to moles of oxygen via Equation 5.19:
nA RT
pA = (5.19)
Vtot
where V is total chamber volume, R is ideal gas law constant, and T is absolute tem-
perature. Substitution of Equation 5.18 into Equation 5.19 provides:
dpA RT P A amb t
= ðp -pA Þ (5.20)
dt Vtot l A
Integrating Equation 5.20 from the beginning of the experiment (t = 0) to time, t,
yields:
amb t
ðp -pA Þ nA RT P A
ln A = t (5.21)
ðpA -pA Þ
amb 0 Vtot l
Equation 5.21 suggests that plotting the natural logarithm of accomplished test gas
accumulation versus time should yield a straight line whose slope is proportional to
the GTR via Equation 5.21 once the permeation coefficient is converted from molar
units to volumetric units:
P A amb t jslopejVtot amb t

OTR = ðpA -pA Þ = ðpA -pA Þ (5.22)
l A
Equation 5.22 provides actual OTR under any conditions of driving force. There-
fore, standardized OTR is determined by multiplying slope by chamber volume and
dividing by sample area.
Actual data from a dynamic accumulation OTR experiment are shown in Figure 5.5.
The slope of this curve multiplied by the volume of the accumulation chamber and divided
by sample area yields OTR. The relative humidity of dynamic accumulation measure-
ments can be adjusted by leaving the test gas chamber open to an environment with the
desired oxygen concentration and relative humidity. Incorporating a soaked sponge
into the test gas chamber would saturate it with water vapor or 100% relative humidity.
0.06
y = 1.591E-01x-5.488E-04
0.05 R2 = 9.996E-01
pambient - p0
0.04
pambient - pt
0.03
-ln
0.02
0.01
0
0 0.1 0.2 0.3 0.4
Time (days)
Figure 5.5 Typical data trace for dynamic accumulation test (OTR = 794 mL/m2/day). (From
Abdellatief, A., and Welt, B. A., Packaging Technology and Science, 26, 5, 281–288,
2012. With permission.)
5.2.3.2 ASTM D3985
The steady-state method for measuring OTR is the most common method for
measuring OTR and is defined by ASTM D3985, Standard Test Method for Oxygen
Gas Transmission Rate Through Plastic Film and Sheeting Using a Coulometric Sensor.
ASTM D3985 specifies a coulometric sensor for oxygen detection and measurement.
Such sensors are extremely sensitive to oxygen. They are therefore relatively expen-
sive to acquire and maintain. Most coulometric sensors have a limited life span that
depends upon overall exposure to oxygen. Additionally, to minimize interference
from oxygen-contaminated process gasses, a special nitrogen/hydrogen mixture is
required in order to catalytically remove trace amounts of oxygen in test gasses.
Such gas mixtures tend to be more expensive than unmixed nitrogen by a factor of
about 10, and the sensor should be constantly bathed in a stream of oxygen-free
gas for longevity. Costs of process gasses and sensor replacements add considerably
to OTR testing. Use of coulometric sensors below 10˚C is difficult due to the potential
damaging effect of condensation. This can be problematic in modified atmosphere
packaging, which often requires OTR measurements below this temperature as
demonstrated by Kim et al. (2004). The relative humidity of the test can be controlled
with a humidifier and input pressures of the test gas and carrier gas. As the input pres-
sures increase, the relative humidity decreases.
5.2.3.3 Sensing Mechanism
ASTM D3985 specifies a coulometric oxygen sensor. The coulometric sensor is

essentially a fuel cell that generates an electric current in proportion to the amount
of oxygen entering the sensor. It contains a cadmium anode and a graphite cathode.
The cathodic and anodic reactions are, respectively,
½ O2 + H2O + 2e‐→2OH‐ (5.23)
Cd + 2OH‐→Cd(OH)2 + 2e‐ (5.24)

The electrons create an electrical current that flows across a scaling load resistor
from which voltage is measured. This voltage corresponds to the amount of oxygen
transmitting through the film to the sensor.
5.2.3.4 Dynamic Accumulation Method
This method or those similar to it have been documented in the literature (Abdellatief
and Welt 2009; Ghosh and Anantheswaran 2001; Kim et al. 2004; Moyls 2004; Siro et al.
2010). Each study, however, uses different methods for measuring oxygen concentration.
Some studies withdrew gas from the chamber and measured accumulated oxygen concen-
tration using a gas chromatograph. In one study (Moyls et al. 1992), relatively small sam-
ples were withdrawn compared to the chamber volume, but only a few samples could be
taken. In another study (Ghosh and Anantheswaran 2001), the cell was repurged after each
measurement, resulting in exceedingly long test times.
Recently, fluorescence-based oxygen measurement was applied to the dynamic
accumulation method for measuring OTR (Abdellatief and Welt 2009; Siro et al.
2010). The oxygen measurement technique is based upon the fluorescence quenching
of an organo-metallic ruthenium-based fluorescent dye immobilized in a gas perme-
able hydrophobic polymer. The dye absorbs light in the blue region and fluoresces
within the red region of the spectrum. The presence of oxygen quenches the fluores-
cent response from the dye, which can be measured via light intensity or decay time.
The quenching process depends on the number of collisions oxygen molecules have
with the dye—where the energy from the excited fluorescent dye is transferred to oxy-
gen molecules during a collision—and therefore reducing emission intensity as well as
the fluorescent decay time of the dye. Because this energy transfer mechanism does
not consume oxygen, the oxygen content of the enclosed space is not changed by
the measurement. Therefore, the OTR measurement is not affected. Changes in emis-
sion intensity and decay time are related to the oxygen partial pressure and can be cali-
brated to determine the oxygen partial pressure. The measurement is passive, totally
reversible, and no oxygen is consumed in the process.
5.2.4 Measuring OTR of Whole Packages
5.2.4.1 ASTM F1307
ASTM F1307, Standard Test Method for Oxygen Transmission Rate Through Dry
Packages Using a Coulometric Sensor, uses a coulometric oxygen sensor and asso-
ciated equipment in an arrangement similar to that described in ASTM D3985.
OTR is determined after the package has been mounted on a test fixture and has
reached an equilibrium with the test environment. The package is mounted in such
a way so that the inside of the package is slowly purged by a stream of nitrogen at
a known constant flow rate throughout the duration of the test. The flow rate is enough
so that the inside concentration of the package is less than the ambient concentration
but not zero. The outside of the package is exposed to a known concentration of
oxygen. The package may be exposed in ambient room air containing 20.9% oxygen
or immersed in an atmosphere of 100% oxygen. As oxygen permeates through the
package walls into the nitrogen carrier gas, it is transported to the sensor. The OTR
in volume per unit time can be determined from the equilibrium oxygen concentration.
This is a steady-state method for measuring OTR.
5.2.4.2 Ambient Oxygen Ingress Rate
The ambient oxygen ingress rate is an unsteady-state method for measuring the
oxygen transmission rate of whole packages. The package is mounted in the same
way as in ASTM F1307; however, the package is initially purged free of oxygen.
Oxygen then accumulates in the package over time, and the oxygen concentration
is measured periodically. The OTR can be determined from the rate of oxygen accu-
mulation (Larsen et al. 2001).
5.3 METHODS FOR MEASURING WATER VAPOR TRANSMISSION
5.3.1 Gravimetric Methods
A common way to measure water vapor transmission rates (WVTRs; see ASTM
E96, Standard Test Methods for Water Vapor Transmission of Materials, and BS
3177, Method for Determining the Permeability to Water Vapour of Flexible Sheet
Materials Used for Packaging) is to place some desiccant in an impermeable (usually,
metal or glass) dish or jar. The sample is placed in a humidity- and temperature-
controlled environment (typical conditions include 25 ± 0.5°C and 75 ± 2 relative
humidity [RH] for temperate conditions or 38 ± 0.5°C and 90 ± 2 RH for tropical
conditions). The weight of the sample increases and is plotted as a function of time.
Because the difference in partial pressure, Δp, of water vapor between the ambient
environment and inside the jar is constant, the weight of the sample versus time
should fall on a straight line
Q slope g H2 O
WVTR = = = (5.25)
At area day m2
Disadvantages of this method include the length of time to make the measure-
ment (typically, 2–14 days) and the lower practical WVTR limit for this method
(approximately 1 g/m2/day). The gravimetric method for measuring water vapor is
depicted in Figure 5.6.
Water vapor
transmitting through
film
Film
sample
Jar
Desiccant
Figure 5.6 Gravimetric method for measuring water vapor transmission.
5.3.2 Infrared Sensing
A faster and more accurate way of determining the WVTR of polymer films using
an infrared sensor is described in ASTM F1249, Standard Test Method for Water
Vapor Transmission Rate Through Plastic Film and Sheeting Using a Modulated
Infrared Sensor. A sample is sealed between two chambers. One chamber contains
a sponge soaked in High-performance liquid chromatography (HPLC) water, which
ensures that the air in this chamber is saturated with water vapor. The other chamber
has nitrogen gas circulating through it and carrying the water vapor transmitted
through the film to the infrared sensor. This is depicted in Figure 5.7.
Infrared light at 6.3 µm (the wavelength at which water vapor absorbs infrared
radiation) is directed through an optical filter (which blocks light of all other
Sponge soaked with HPLC grade water
Chamber saturated with

water vapor
Film sample
Nitrogen gas +
Nitrogen gas transmitted
flow in water vapor flow
to sensor
Figure 5.7 WVTR determined with modulated Infrared sensor.

wavelengths) through the water vapor and nitrogen gas mixture. The amount of infra-
red light detected corresponds to a water vapor concentration that corresponds to a
WVTR.
NOMENCLATURE
A area of gas transmission
c area points across the film
concentration at different
D diffusion coefficient time
GTR gas transmission rate of gas through
a film

J diffusive flux of gas through amountarea
time
l thickness of film
nA number of moles of test gas
OTR oxygen transmission rate
p partial pressure of gas
P permeability coefficient of polymer
PA test gas permeability of film
pamb
A partial pressure of test gas in ambient environment
ptA partial pressure of test gas at a particular time t
Q amount of gas passing through film (mass or volume)
R universal gas constant
S solubility of gas in film
t time (days)
T absolute temperature
Vtot total volume chamber
REFERENCES
Abdellatief, A., and Welt, B. A. 2009. Method for measuring the oxygen transmission rate of
perforated packaging films. Journal of Applied Packaging Research 3, 3: 161–171.
Abdellatief, A., and Welt, B. A. 2012. Comparison of new dynamic accumulation method for
measuring oxygen transmission rate of packaging against the steady-state method
described by ASTM D3985. Packaging Technology and Science, 26, 5, 281–288.
ASTM D-1434 Standard Test Method for Determining Gas Permeability Characteristics of
Plastic Film and Sheeting.
ASTM D-3985 Standard Test Method for Oxygen Gas Transmission Rate Through Plastic Film
and Sheeting Using a Coulometric Sensor.
ASTM E-96 Standard Test Methods for Water Vapor Transmission of Materials.
ASTM F-1249 Standard Test Method for Water Vapor Transmission Rate Through Plastic Film
and Sheeting Using a Modulated Infrared Sensor.
ASTM F-1307 Standard Test Method for Oxygen Transmission Rate Through Dry Packages
Using a Coulometric Sensor.
BS 3177:1959 Method for determining the permeability to water vapor of flexible sheet materials
used for packaging.
Crank, J. 1975. The Mathematics of Diffusion (2nd edn.), Clarendon Press, Oxford. viii,
pp. 44–68.
Ghosh, V., and Anantheswaran, R. C. 2001. Oxygen transmission rate through micro-perforated
films: Measurement and model comparison. Journal of Food Process Engineering 24,
2: 113–133.
Kim, J. G., Luo, Y. G., and Gross, K. C. 2004. Effect of package film on the quality of fresh-cut
salad savoy. Postharvest Biology and Technology 32, 1: 99–107.
Lange, J., and Wyser, Y. 2003. Recent innovations in barrier technologies for plastic packaging –
A review. Packaging Technology and Science 16, 4: 149–158.
Larsen, H., Kohler, A., and Magnus, E. M. 2001. Ambient Oxygen ingress rate method – An
alternative method to ox-tran for measuring oxygen transmission rate of whole packages.
Packaging Science and Technology 13, 6: 233–241.
Laties, G. G. 1978. The development and control of respiratory pathways in slices of plant sto-
rage organs. In: Biochemistry of wounded tissues, G. Kahl (ed.), Walter de Gruyter & Co,
Berlin, German, pp. 421–426.
Moyls, L. 2004. Whole bag method for determining oxygen transmission rate. Transactions of
the American Society of Agricultural Engineers 47, 1: 159–164.
Moyls, L., Hocking, R., Beveridge, T., and Timber, G. 1992. Exponential decay method for
determining gas transmission rate for films. Transactions of the American Society of
Agricultural Engineers 35, 4: 1259–1265.
Robertson, G. L. 1993. Food Packaging Principles and Practice. Marcel Dekker, Inc.,
New York, pp. 75–77.
Siro, I., Plackett, D., and Sommer-Larsen, P. 2010. A comparative study of oxygen transmission
rates through polymer films based on fluorescence quenching. Packaging Technology
and Science 23, 6: 302–315.
Strandburg, G., De Lassus, P. T., and Howell, B. A. 1990. Diffusion and sorption of linear esters
in selected polymer films. Barrier Polymers and Structures 423: 339.
Yasuda, H. 1975. Units of gas permeability constants. Journal of Applied Polymer Science 19,
2529–2536.
CHAPTER 6
Testing Glass as a Food Packaging Material
Khalid Gul, Haroon Maqbool Wani, Preeti Singh, Idrees Ahmed Wani,
and Ali Abas Wani
CONTENTS
6.1 Introduction...................................................................................................139
6.2 Composition of Glass ...................................................................................141
6.3 Parts of a Glass Container ............................................................................ 141
6.3.1 Dimensions .......................................................................................142
6.3.2 Verticality .........................................................................................143
6.3.3 Testing the Verticality of Glass Bottles for Aerated Water..............145
6.3.4 Capacity ............................................................................................145
6.3.5 Ovality ..............................................................................................146
6.4 Physical and Chemical Properties................................................................. 146
6.4.1 Measurement of Pressure Resistance................................................147
6.4.1.1 Internal Pressure Breakage ............................................... 148
6.4.2 Vertical Load Strength Test ..............................................................148
6.4.3 Impact Strength and Testing .............................................................149
6.4.3.1 Tests for Impact Breakage ................................................ 149
6.4.3.2 Resistance to Abrasion and Scratching............................. 149
6.5 Thermal Shock Resistance............................................................................ 150
6.5.1 Thermal Shock Breakage..................................................................150
6.6 Fracture Diagnosis ........................................................................................153
6.7 Defects in Glass Containers..........................................................................154
References ..............................................................................................................154
6.1 INTRODUCTION
As a packaging material, glass has an extremely long history. The first glass
objects used for holding food are believed to have been developed around 3000 BC
(Moody 1963). Glass is defined as “an amorphous inorganic product of fusion that
139
has been cooled to a rigid condition without crystallizing” (Scholze 1991). Although
there are variations in the composition of glass, typically it is made by cooling a
heated mixture of silicates, limestone, and soda ash to the point of fusion. In general,
the glass for packaging is a variant of sodium or calcium salt. Silica (SiO2) from sand
acts as a verifying agent, sodium oxide (Na2O) from sodium carbonate acts as a melting
agent, and small quantities of sodium sulfate as a refining agent (Hugel and Pajean 1996).
Calcium oxide (CaO), magnesium oxide (MgO), and aluminum oxide (Al2O3) act as sta-
bilizing agents; cobalt (Co) and selenium (Se) are found in trace quantities as decolorants;
iron oxides, chrome, manganese, cobalt, and so on act as coloring agents; and sulfates,
carbon, and sulfides either act as colors and or as filtering properties. The production of
glass containers involves preparation of vitrifiable raw material composition by heating a
mixture of silica, sodium carbonate (the melting agent), and limestone/calcium carbonate
and alumina (stabilizers) to high temperatures (1400°C–1450°C) until the materials melt
into a thick liquid mass in the melting furnace. The mass is then poured into molds,
followed by chemical conditioning of the glass and surface protection treatment. The
glass containers then move for heat treatment and re-annealing in ovens to relive the
stress generated by machine forming. Finally, each container is inspected for defects
by appropriate equipment before being packed in a box or on a pallet.
Glass is an inert packaging material with an absolute barrier to gases and moisture,
which makes it versatile for retaining the flavor and freshness of delicate food products.
Glass can withstand high thermal processing, provides good insulation, can be formed
into different shapes, and can be supplied in different colors with an optical transmission
between nearly opaque and nearly transparent. Additional oxide coatings help to improve
mechanical properties and provide a barrier against chemical attack. Heavy weight and
fragility when exposed to internal pressure, impact, and thermal shock are some of the
limitations for the extensive use of glass in the food industry (Wani et al. 2014). Bottles,
jars, and pots are the main types of glass containers used in the food industry. Bottles
have narrow openings, while as jars and pots have wide openings. Wide mouth contain-
ers are used for packing jams, jellies, marmalades, pickles, processed fruits and vegeta-
bles, and so on. Products such as wine, beer, healthy oils, squashes, cordials, fruit juices,
carbonated beverages, ketchups, sauces, and vinegar are packed in narrow neck contain-
ers. The glass containers used in food packaging are often surface-coated to provide
lubrication in the production line, which eliminates the chances of scratching or surface
abrasion and line jams. Glass coatings also increase and preserve the strength of the
bottle, reducing scratches and/or breakage.
The use of glass containers for packaging food materials has the following
advantages:
• They are impervious to moisture, gases, odors, and microorganisms.

• They are inert and do not react with or migrate into food products.
• They are suitable for heat processing when hermetically sealed.
• They are hygienic and are easy to wash and to sterilize.
• They can be formed into different shapes.
• They can withstand the high internal pressures caused by some liquids such as
champagne, cider, and so on.
TESTING GLASS AS A FOOD PACKAGING MATERIAL 141
• They are reusable and recyclable.

• They are transparent when displaying the contents and may be colored.
• They are rigid—to allow stacking without container damage.
• They are widely used for both single and multi-trip packaging.
• They allow passage of microwaves and can be used to heat food in conventional
or microwave ovens.
6.2 COMPOSITION OF GLASS
Although there are variations in glass composition that produce different types of
glass with varied properties, composition of a typical commercial glass container is
as follows:
Silica (SiO2) 72%

Lime (CaO) 11%
Soda (Na2O) 14%
Alumina (Al2O3) 1.7%
Magnesia (MgO) 0.3%
Potash (K2O) 0.3%
Minor ingredients such as fining agents, colorizers, and de colorizers are added to the
typical container glass composition. The most commonly used fining agents are sulfates in
combination with carbon. Of the sulfates used, sodium sulfate, or salt cake, is the most
common.
When the major raw materials used for the production of glass are pure and Fe2O3 con-
tent is less than 0.04%, the glass obtained is colorless. Sometimes, selenium is used, which
acts as decolorizer. Colored glass is produced by adding the following coloring agents:
Amber Carbon and sulphur compounds

Blue Cobalt oxide
Green Ferrous sulfate, chromic oxide
Yellow Ferric oxide, antimony oxide
Blue green Cobalt oxide and chromium oxide
Opal Calcium oxide
Bottles that are meant for thermal processing and subsequent cooling have to with-
stand shocks. If breakage from thermal shock is a problem, high-silica, low-alkali
glass helps to overcome shock. However, this may lead to cord problems; cords are
strains that are not relieved by annealing.
6.3 PARTS OF A GLASS CONTAINER
The parts of a glass container are illustrated in Figure 6.1. Shoulder, heel, side
wall, label space, body diameter, and finish are all considered to be important parts
Bore
Sealing surface
Ring/finish Bead
Neck
Upper Roof of neck
shoulder
Shoulder
Recess to
take lable
Mold seam
Body
Insweep heel
Bearing surface
(sometimes
Bottom base Push up grooved)
Figure 6.1 Parts of a glass container.
of a glass container. The part of the glass container that contains the closure is called
the finish because in the days of handmade glass, the neck was made last. Wide mouth
containers have an opening almost as large as the body of the bottle. Liquids are
usually put into narrow neck containers for convenience in pouring. The neck may
be threaded or rounded for a screw cap or crown cork, respectively. Screw caps
and crown corks are those most commonly used. Ketchup bottles are designed to
take both crown corks and screw caps. Metal caps may be made of tinplate or alumi-
num and are usually coated with organic compounds. Screw caps are made of tinplate
with a liner of cork or pulpboard laminated with a layer of plastic films, vinylite, and
other plastics or with a vacuum seal (rubber gasket). The quality control criteria for
screw caps are given in Table 6.1.
Glass containers used for packaging should have specifications that include: (i) a
description of the container finish and (ii) the dimensions—capacity, height, diameter,
weight, and tolerances. The correct choice of shape and dimensions is extremely
important and should be in accordance with production possibilities. The dimensional
requirements are needed for acceptance or rejection of a glass container consignment.
6.3.1 Dimensions
Glass container production technology also influences the choice of dimensions

for glass containers. The containers are shaped in cast iron molds while they are
still in a plastic condition. It is important that the glass should be sufficiently hardened
Table 6.1 Quality Control Criteria for Screw Caps
Critical Defects Major Defects Minor Defects

AQL 0.6% AQL 1.5% AQL 4%
Incorrect liner facing Cocked liner Incomplete decoration

Incorrect liner backing Incomplete threads Smeared decoration
Liner thickness Liners improperly glued in cap Poor registration of
decoration
Notched liner Scratched or chipped surface Dirt
Short shots (plastic) Cracked or broken caps Soft finish
No liner Dents in metal caps Glue on threads
Wrong color or copy Mold flash, if sharp
Sharp points or edges Incomplete cure of plastic
Wrinkled facing (delaminated) Breakage when applied to
bottle
Source: Adapted from Hanlon, J.F., et al., Handbook of Package Engineering, 3rd ed.,
CRC Press, Boca Raton, FL, 1998.
Note: AQL, acceptance quality level.
by the mold before leaving it, having absorbed a portion of heat so that dimensional
discrepancies will not occur afterward. The specified dimensions need to be set so as
to ensure that the volume and the neck are suitable for upright sealing and that the
dimensional discrepancies are minimal. The high-speed filling used nowadays has
necessitated a tighter tolerance.
The optimal dimensions and ratios of different sizes of glass containers that are
produced in fully automated plants is shown in Table 6.2, and Table 6.3 lists the
admissible tolerances.
6.3.2 Verticality
A bottle should stand perfectly upright if the mold used is accurate and the bottle
has retained the shape of mold during annealing and cooling. During annealing, if the
neck bends slightly or the base wraps, the bottle may be “out of true.” Obvious defects
are visible, but slight deviations require measurement. The distance, measured horizon-
tally, by which the bottle finish departs from its intended position in relation to the base
of the bottle is referred to as the verticality. It is also appropriate to refer to this as a
bottle’s “obliquity.” In a cylindrical bottle, it is always intended that the center of finish
is always in the vertical plane through the joining faces of the body mold, the position
of which is marked by vertical seams on the sides of the bottle. This center of finish is
always intended to be vertically above the center of the base. An empirical limit for
tolerance of verticality that is found satisfactory is 0.13 mm/cm of bottle height.
Indirect measurements are used to measure verticality. The distances A1 and A2
and B1 and B2 are the horizontal distances between the sides of the top of the bottle
neck and the lowest vertical part of the body. For symmetrical bottles, the devia-
1 1
tion from the verticality in the two directions is (A1 − A2) and (B1 − B2).
2 2
144
Table 6.2 Optimal Dimensions and Ratios of Glass Containers Produced in Fully Automated Plants
Mean Wall
Thickness Ratio of
Diameter of
Diameter Height to Light Heavy Variations in Body to Minimum
of Width, Height, Diameter Containers, Containers, Wall Thickness, Diameter of Curvature of Maximum
Container mm mm Ratio mm mm mm Neck Radius Weight, g
Small 19–50 25–75 3:1 1.5 2.5 ±25 3:1 3 85

Medium 50–100 75–150 3.5:1 2.0 3.0 ±25 4.5:1 6 450
Large 100–165 150–300 3:1 3.0 4.5 ±25 6:1 9 1600
Table 6.3 Admissible Tolerances for Glass Containers
Permissible
Height, Tolerance, Diameter, Tolerance, Degree of Ovalness
mm mm mm mm (greater axis minus smaller axis)
Up to 101.6 ±0.762 Up to 50.8 0.762 0.02

101.6–152.4 ±0.889 50.8–76.2 1.016 0.02
152.4–203.2 ±1.016 76.2–114.3 1.270 0.02
203.2–254.0 ±1.143 114.3–152.4 1.524 0.0175
254.0–304.8 ±1.270 – – –
Source: Adapted from Moody, B. E., Packaging in Glass, Hutchinson & Co. Ltd., London; Petristic, A.,
Packaging and Packaging Materials with Special Reference to the Packaging of Foods,
Food Industry Studies No. 5, United Nations Industrial Development Organization, Vienna.
For unsymmetrical bottles, the design values of A1, B1, and so on are measured and the
deviations are calculated.
6.3.3 Testing the Verticality of Glass Bottles for Aerated Water
The sealing surface of a bottle is parallel to the base when it is kept on a flat
surface. The vertical line formed by the inside neck opening through the center of
the circle should pass through the circle described by the bottom or resting surface.
To test the verticality of a bottle, fill it with water and place it on its base on the flat
surface (plate) of the test assembly. The “V” block on the pillar is to be mounted in
such a way that it is in contact with the outer diameter of the bottle while its measuring
point comes in contact with the outer edge of the neck of bottle. Now the bottle is
rotated such that the body is always in contact with the “V” block. The maximum
deflection on the indicator should be noted. Half of the total deflection shown by
the indicator is the measure of the variation in the verticality of the bottle. The verti-
cality of the bottle should not vary more than 2.5 mm if tested by this method.
6.3.4 Capacity
Containers are designated based on their capacity. The relationship between UK

and U.S. liquid measures are as follows:
Imperial System American System
Ounce 28.413 ml 29.57 ml

Pint 20 fl. oz 16 fl. oz
Quart 2 pints 2 pints
Gallon 8 pints 8 pints
160 fl. oz 128 fl. oz
The capacity of a bottle is defined either as the brimful capacity or the capacity
to a stated filling weight. A bottle is brimful when it is standing on a level surface
and is filled with water until the center of the surface of the water is level with the
top of the bottle.
Bottle capacities can be measured simply by filling bottles with water. A measured
volume of water is delivered into a bottle; the water level is checked in the bottle to see
if it reaches an expected height range. It is important to know how much the bottle will
hold when filled to a stated level. To determine this, a test may be carried out by simply
filling the bottle to the required height and then emptying the contents into a graduated
cylinder. However, this method is not suitable for measuring brimful capacity. A more
accurate method for determining how much a bottle will hold is to measure the weight
of the empty bottle and then reweigh the bottle after filling it to a stated level. Pure
distilled water should be used in this case; however, ordinary cold tap water can
also provide sufficient accuracy. The brimful capacity of a wide mouth bottle is deter-
mined by filling it with water and removing the excess with a strike plate. The capacity
measured will not be more than 0.9 ml above the brimful capacity.
Capacity tolerances in simple cylindrical bottles or nearly cylindrical bottles are
approximately proportional to the square root of their nominal capacity (i.e., 0.988
probability limits).
Tolerance “T ” can be calculated as:
pffiffiffiffi
T = 0:078 C
where C is the nominal capacity. If the nominal capacity of the bottle is 650 ml, then
tolerance will be:
pffiffiffiffiffiffiffiffi
T = 0:078 650
= 1:99 ml
6.3.5 Ovality
Ovality of a glass bottle is denoted by how far a nominal cylindrical bottle shows
deviation from a perfectly circular cross section. A bottle with a diameter of, for exam-
ple, 7.7 cm with a tolerance level of ±0.05 cm, normally would be said to have an oval-
ity of 0.1 cm. Too much ovality in bottles that are labeled in automatic machines by
rolling them on their sides can cause trouble. Specifications for ovality should be more
stringent in such cases. However, advanced systems accommodate slight differences
in ovality of glass bottles with no detrimental effect on the labeling quality.
6.4 PHYSICAL AND CHEMICAL PROPERTIES
Finished product strength and ability to withstand force are the most important
physical properties of glass containers. Force can be applied externally, by impact
loads, or by the pressure of the external atmosphere when it is higher than the internal
pressure. Alternatively, force may be applied internally by the pressure of the gas or
liquid a bottle contains. In order to ensure the best possible performance of glass bottles,
it is desirable to minimize the stresses incurred by developing an appropriate design

and by proper handling during the processing and distribution of the bottles. With the
development of new techniques of glass surface treatment, the surface strength of
glass bottles has increased throughout the life cycle.
6.4.1 Measurement of Pressure Resistance
This procedure involves filling a bottle with water and then applying pressure to it
by a pump or a direct ram. The applied pressure is generally raised at the rate of 50 psi
(1.76 to 3.5 kg/cm2) at intervals of 30 to 60 seconds. The bottle filled with water that is
to be tested is held by a split collar in a hydrostatic pressure tester. The design of the
collar is such that the bottle is not clamped but is suspended from the bed of the finish.
The tester should provide a seal that has to be watertight at the applied pressure. The
equipment should also have a built-in timing mechanism so that the bottle is under
pressure for not less than 1 minute ± 2 seconds. Mechanized automatic incremental
pressure testers raise the pressure continuously at a fixed rate, which is adjusted intern-
ally to be equivalent to a 60-second interval test.
The bottles that are meant for packaging aerated waters should be able to with-
stand a pressure of 15 kg/cm2 for 1 minute ± 2 seconds. Bottles that withstand the
pressure without bursting are considered as having passed the test. The internal pres-
sure resistance of a glass bottle has a considerable relationship to its shape. A bottle’s
shoulders and base usually have a stiffening effect if the cylinder does not have more
length than its diameter. In practice, bottles are oval rather than cylindrical. Practical
investigations suggest that the amount of ovality in bottles could reduce the bursting
pressure by 25%. It is also important to know that the shoulder should be reasonably
streamlined and the base joined to the sidewall by a smooth curve in order to obtain a
good glass distribution that directly increases the pressure resistance.
In practice, when determining the bursting pressure, it is more appropriate to use
the weight by capacity (w/c) ratios of the container than the wall thickness. For
the relationship between w/c ratio and the bursting pressure for different diameters,
see Table 6.4, which indicates that the theoretical and practical values match well
for larger diameter bottles. For bottles with a smaller diameter, the theoretical value
is lower than the practical value.
Table 6.4 Internal Pressure Ratios of Specific Glass Bottle Shapes
Ratio of
Shape Pressure Resistance
Cylinder 10
Ellipse (major axis twice the minor) 5
Square with well round corners 2.5
Square with sharp corners 1
Rectangle with length equal to twice the width 1
and with rounded corners
6.4.1.1 Internal Pressure Breakage
Breakage due to internal pressure usually occurs midway from the top to the bottom
of a bottle. The origin of the break may be on the outer surface or on the surface contain-
ing a scratch. The development of breakage due to pressure initially is slow. The internal
pressure leaves a mirror surface on the broken glass and the fissures move up and down,
forking as they move. The origin of breakage near the shoulder is primarily due to weak-
ness in design, while breakage near the bottom is due to damage done to a bottle during
handling. Resistance to pressure handling includes homogeneity of the glass, annealing,
and fabrication defects. Thick-walled glass is more resistant to internal pressure;
however, it has a poor thermal shock resistance. A round or spherical shape has greater
resistance to thermal shock, and the resistance decreases with an increase in bottle size.
6.4.2 Vertical Load Strength Test
Glass has the ability to resist severe compression when external forces applied on
the bottle only develop compression. In most designs, the highest stress occurs in the
shoulder region of a bottle; the average bearable loads differ for bottles with a cham-
pagne shape (5000 kg), a shoulder shape (4000 kg), a Winchester shape (2000), and
square shoulders (2500 kg). Interestingly, glass thickness is not important in compar-
ison to bottle shapes—especially the design of the shoulder (e.g., nonreturnable, light-
weight champagne bottles have as much vertical load strength as heavier reusable
bottles of a similar design). A vertical load strength test (also known as head load,
compression, and axial-load testing) is carried out using a compression tester to deter-
mine a product’s resistance to vertical load forces. The load resistance of different
glass bottle shapes is given in Figure 6.2.
5000
Mean bearable load - kg
4000
“Champagne” shape “Shoulder” shape 3000

5000 kg 4000 kg
2000
1000
0 25 50 75
“Winchester” shape Square shoulder Radius of vertical curvature
2000 kg 2500 kg of shoulder mm
Figure 6.2 Vertical load resistance of different glass bottle shapes.

6.4.3 Impact Strength and Testing
When an impact is applied on a contact surface of a bottle, the contact surface is

compressed, which produces a tension in the surrounding zone that develops further
inside the bottle at the contact point. Also, shock waves traveling through the glass
may occasionally produce tension some distance away from the impact contact
point. An active impact or a series of small impacts are enough to cause breakage
of a glass bottle. There are basically two types of impact: (1) when the bottle strikes
a stationary object or (2) when a stationary bottle strikes a moving object. In the first
case, the amount of damage can be minimized by design features of the bottle and by
surface treatments to reduce the impact stress when hitting a stationary surface or
object during the bottle’s fall. In the second case, the impact damage depends on
the hardness of the striking object and on its kinetic energy (i.e., on its weight and
speed).
The impact breakage resistance is influenced by the damage to the bottle’s outer
and inner surfaces and is due to fabrication or annealing defects. Thick-walled con-
tainers are too rigid and have poor resistance to impact breakage. Impact breakage
occurs when a moving object strikes a stationary bottle or vice versa. If the bottle is
filled with liquid, the momentum of the liquid is converted into a momentary internal
pressure. The extent of the pressure rise depends upon the rapidity with which bottle is
brought to a halt.
6.4.3.1 Tests for Impact Breakage
Impact testing is used to determine impact resistance, strength, and breakage char-
acteristics of a range of glass items in order to ensure that they are fit for their intended
use. For example:
1. Fill a bottle with water, seal it, and drop it on a rigid surface. Repeat with
progressive increases in height until the bottle breaks. Find the mean height
required to produce the breakage. It is not necessary to drop bottles at all
possible angles, dropping them either on their bases or flat on their sides is
sufficient.
2. A rigid pendulum with a hardened steel ball as a bob can be used to strike a
bottle at exactly the same position any number of times. The vertical height
from which the striker falls is a measure of the impact energy. However, this
method may not be appropriate as a good guide for general performance because
it gives information only about one point on a bottle.
6.4.3.2 Resistance to Abrasion and Scratching
The longevity of a glass bottle depends on its resistance to abrasion and scratching.
Design features that can minimize the contact area are helpful to increase the life cycle
of a bottle. In general, the effectiveness of applied surface treatments lessen over time and
the strength may fall from 50 MN/m2 to 40 MN/m2 or further without a surface treatment.
The longevity of a coating’s performance occurs in the filling line due to bottle to bottle
abrasion, during the transportation, or during cleaning and washing.
6.5 THERMAL SHOCK RESISTANCE
Thermal shock resistance is the resistance of glass containers to sudden tempera-

ture changes. Glass containers that are used for packaging products that undergo
thermal processing have to withstand high pressures, temperatures, and shocks.
Poor thermal shock resistance will result in cracks or breakage, which is a hazard
inviting loss in product quality. Thermal shock is measured by the difference
between the higher temperature (T1) to which the product is heated and the lower
temperature (T2) to which the product is finally cooled.
Hot water baths and cold water baths, which are thermostatic in nature, have a
range of 0 to 100 ± 1°C and are equipped with a device that agitates the liquid in
the bath, which is used for the thermal shock determination. Additionally, wire baskets
are used to hold the sample. Water is filled in the hot and cold water baths, and the tem-
perature of the cold bath (T2) is noted. The temperature of the hot water bath (T1) is
adjusted such that the difference between two temperatures (T1 − T2) is 43°C. As the
water bath attains the desired temperature, the wire basket containing the bottles is
placed in the bath while the bottles are filled with water. The bottles are allowed
to remain in the bath for around 15 minutes. The wire basket containing the filled
bottles is then transferred to the cold bath. It should be noted that the transfer process
occurs in about 10 ± 2 seconds. The bottles are to be immersed completely in water;
however, care should be taken that no cold water enters the bottles. The bottles are
allowed to remain in the cold water bath for not more than 2 minutes and then are
removed from the bath. The bottles are then examined for any visible cracks or
damage. The bottles used in this test should not be used for any other test or even
for packaging of foods. If there are no visible cracks or damage, the bottles are con-
sidered to be satisfactory. Ice can be used to vary the temperature of hot and cold water
by 100°C. Glass containers, prior to receiving hot products, should be conditioned and
cooled carefully after being filled and sealed. The temperature differential between the
inner and outer surfaces of the bottles should not be greater than 44.4°C. However,
some glass containers may withstand temperature differences of up to 83.3°C and
not break.
6.5.1 Thermal Shock Breakage
A glass container is subjected to expansion and contraction, when one of its

sections is at one temperature and the other is at different temperature. This leads to
breakage due to thermal shock by mechanical stress and strain. Breakage may be
due to internal or external pressure (Figure 6.3). As the temperatures are equalized,
the tendency for breakage decreases. The temperature difference in glass bottles
occurs during (i) hot to cold immersion, (ii) cold to hot immersion, and (iii) when
hot liquid is poured into a cold bottle or vice versa. Among all, the thermal shock
Origin
Origin
(a) (b)
Figure 6.3 Depiction of a thermal shock (a) and internal pressure (b) breakage in glass containers.
Table 6.5 Relationship of Weight/Capacity Ratio to Thermal Shock Resistance
Limiting Sudden
Type Weight/Capacity Ratio Temperature Drop, °C
Medium size multitrip bottles 0.8–1.2 30–40

Medium size single-trip bottles 0.6 45–60
Medium size lightweight jars 0.5 50–70
for jams and other foods
caused by pouring hot liquid into cold bottle is most severe. The thermal shock usually
originates in the bottom and travels slowly with little violence. The point of injury to
the surface locates the origin. The factors that influence thermal shock are glass homo-
geneity, annealing conditions, fabricating defects, and the thickness of the glass. The
greater the thickness, the greater is the stress—and hence, more breakage potential.
Round or oval shapes, uniform thickness, and smaller bottle size reduce the potential
for thermal shock.
ASTM C149-86, Standard Test Method for Thermal Shock Resistance of
Glass Containers, and BS EN 1183:1997, Materials and Articles in Contact
with Foodstuffs, are approved methods for measurement of thermal shock resis-
tance. Table 6.5 gives a general indication of thermal shock resistance. Wall
thickness is not an adequate measure of how the thickness varies in the critical
zone of a bottle, but weight by capacity ratio is a useful criterion. The values
Table 6.6 Relationship of Weight/Capacity Ratio and Minimum

Bursting Pressure of New Bottles
W/C Ratio
2 15 1.0 0.75
Estimated Thickness t in cm
0.406 0.305 0.203 0.152 0.1020.5
Diameter d in cm Bursting Pressure (kg/cm3)
Theoretical
10.106 28.17 21.13 14.08 10.56 7.04
7.62 37.32 28.17 16.20 14.08 9.15
5.08 56.34 42.25 28.17 21.13 14.08
2.54 112.70 84.50 56.34 42.25 28.17
Practical
10.106 28.17 23.24 16.90 12.68 7.04
7.62 31.69 26.76 20.42 15.49 9.86
5.08 35.92 30.99 24.65 19.72 14.08
2.54 41.55 37.32 30.99 26.06 19.72
Origin
Not the origin
(a) (b)
Figure 6.4 Fracture diagnosis with origin (a) and not in the origin (b) in the glass containers.
given in Table 6.6 indicate the average performance throughout the life of a
glass bottle.
Because thermal treatment is significant for glass packaging materials, glazing is
used when energy conservation is important. In this case, the thermal transmittance
(U-value), light transmission (%), solar factor (g-value), and light reflectance proper-
ties of a glass and its coatings should be specified.
Table 6.7 Defects in Finished Glass Containers
Remarks
I. Critical defects
1. Unfilled finish A depression on the surface above a thread not filled out.
2. Check A shallow surface crack usually wavy and generally in a straight
line. Groups of checks are called crizzled finish. Bruised checks
occur near the shoulder or hell areas. Mold checks are deep and
run from the bottom to the sides. Panel checks are found on the
flat areas of the bottle.
3. Filament Hairline strings inside the bottle
4. Split Open crack starting at the finish and extending downwards
5. Spikes Long thin strands inside the bottle which would break when the
bottle is filled
6. Overpress A rim inside the finish which may be sometimes sharp
7. Freaks Odd shapes which render the bottle unusable
8. Soft blister A thin blister near the sealing surface or anywhere in the bottle
9. Cracks Partial fracture in the heel or shoulder
10. Cord A strain not relieved by annealing
11. Finish marks Lines on the sealing surface
II. Major defects
1. Chipped finish Broken edge
2. Stone Nonglass material in the container
3. Rocker bottom A sunken center portion in the base
4. Fin A seam on the top surface along the parting line
5. Flanged bottom A run of glass around the bottom at the parting line
III. Minor defects
1. Hard blister or droplet A projection on the glass
2. Sunken shoulder Improper blowing
3. Long neck Taken out from mold when too hot and leaving
4. Heel tap Heavy glass on one portion of the base
5. Mark Caused by oil accumulating in the mold
6. Dirt Nonglass material like oil, carbon, rust, and so on coming from
the mold
7. Seeds Small bubbles in the glass
8. Wavy bottles Irregular surface on the inside
9. Stuck bottles Two bottles sticking when hot and leaving a rough spot on
pulling apart
Source: Adapted and modified from Hanlon, J.F., et al., Handbook of Package Engineering,
3rd ed., CRC Press, Boca Raton, FL, 1998.
Note: AQL, acceptance quality level.
6.6 FRACTURE DIAGNOSIS
When glass containers are subjected to loads, they deform in a specific manner and
can be analyzed by finite computer stress analysis. The deformation creates strain,
which in turn generates stress in the glass. The stress can be tensile, compressive, or
shear in nature. In brittle components such as glass, the shear component determines
the direction and magnitude of the principle stresses. The tension component (σi) is
the main concern because glass only breaks in response to stress. This implies that
only the areas where tensile stresses are created need to be considered. Glass breaks
when the tensile stress magnitude exceeds the surface strength at any given point
and can be summarized as:
σi ≥ Strength
The magnitude of tensile is affected by load type, glass thickness and distribution,
load magnitude, design elements, permanent stresses, and combined loads. Fracture
origin is defined as the specific point from which the cracks originate. Fracture
patterns emanate due to internal pressure, impact, vertical load, and thermal shock
(Smay and Davis 2011). Fracture analysis is required to avoid failure in the product
and distribution system. A brief depiction of fracture diagnosis is given in Figure 6.4.
6.7 DEFECTS IN GLASS CONTAINERS
Glass containers often contain defects that may be minor, major, or critical in
nature. Defects that are critical in nature are those hazardous to the user, major defects
reduce the usability of the container, and minor defects do not affect the usability, but
the container is rendered unattractive. Many of the defects are rare but others may
be prominent. Quality concerns demand rigorous testing for defects in glass from
compositional inclusions, stones, cords, knots, and blisters to delamination, misting,
bloom, and so on (Table 6.7).
REFERENCES
Hanlon, J. F., Kelsey, R. J. and Forcinio, H. 1998. Handbook of package engineering, 3rd ed.,
CRC Press, Boca Raton, FL, pp. 299–327.
Hugel, R. and Pajean, G. 1996. Glass used for packaging, In Food packaging technology,
Volume 1, G. Bureau and J. L. Multon (eds.), VCH Publishers Inc, New York, pp. 183–202.
Moody, B. E. 1963. Packaging in glass, Hutchinson & Co. Ltd., London.
Scholze, H. 1991. Glass: Nature, Structure and Properties, Springer-Verlag, New York, pp. 3–4.
Smay, G. L. and Davis, M. W. 2011. Fracture analysis… rely on science, not guesswork. Glass
Worldwide, 35: 80–85.
Wani, A. A., Singh, P. and Langowski, H.-C. 2014. Food Technologies: Packaging, In
Encyclopedia of Food Safety, Volume 3, Y. Motarjemi (ed.), Academic Press, Waltham,
MA, pp. 211–18.
CHAPTER 7
Metal Packaging
Testing and Quality Assurance*
Heinz Grossjohann, Alex Grossjohann, Thomas Duve, and Maura Marcks
CONTENTS
7.1 Introduction to Metal Packaging...................................................................156

7.2 Quality Control and its Benefits (Economics, Performance, Safety)................... 157
7.2.1 Quality Control Measures on Tinplate .............................................157
7.2.2 Testing of Coatings on Steel.............................................................158
7.2.3 Tinplate Can Making: Three-Piece and Two-Piece Methods...........159
7.2.3.1 The Three-Piece Can-Making Process and Gauging
and Testing in the First Step, the Can Body..................... 160
7.2.3.2 Food Cans from a Welded Can Body............................... 163
7.2.3.3 Aerosol Cans from a Welded Can Body .......................... 165
7.2.3.4 Vacuum-Resistant Cans from a Welded Can Body.......... 165
7.2.3.5 Shallow Drawn Cans ........................................................ 167
7.2.3.6 Draw/Redraw Cans ........................................................... 167
7.2.3.7 Making DWI Cans, also Two-Piece Aerosol Cans .......... 168
7.2.4 End Making from ETP or TFS .........................................................169
7.2.4.1 Sanitary Ends .................................................................... 170
7.2.4.2 Easy Open Ends................................................................ 171
7.2.4.3 Aerosol Tops and Bottoms ............................................... 172
7.3 Aluminum in Can Making............................................................................ 173
7.3.1 Aluminum Can Making ....................................................................173
7.3.2 Double Seams on Cans .....................................................................176
7.3.2.1 Double Seam Measurements on Filled versus
Empty Cans..................................................................178
7.3.2.2 Destructive versus Nondestructive Inspection Methods ........178
* All pictures of gauges were sourced from the archives of CMC-KUHNKE, where you can find most of
them on the website: http://www.cmc-kuhnke.com.
155
7.3.2.3 In-line Monitoring to Control External Seam Dimensions....179

7.3.2.4 Enamel Rating on Cans .................................................... 180
7.4 Quality Control in the Can-Making Industry ...............................................182
7.4.1 Why Do We Need SPC? ..................................................................182
7.4.2 Is Zero-Defect Production Possible? ................................................182
7.4.3 Data Storage as Assurance/Defense Against Product
Liability Claims .........................................................................183
7.1 INTRODUCTION TO METAL PACKAGING
Food preservation has been a key to man’s survival from the beginning. Today’s
explosive population growth would be impossible to sustain without increases in agricul-
tural production and food preservation techniques as well as efficient distribution systems.
Metal packaging plays a major role in food packaging and preservation. It is light, low-
cost, and offers a long shelf life. Metal packaging prevents microorganisms from entering
and spoiling the contents. Because metal packaging is by far the most important food
packaging material, it is the focus of this chapter. In 1795, the French military offered a
cash prize of 12,000 francs for a new method to preserve food. Nicolas Appert suggested
canning, and the process was first demonstrated in 1806 in tests with the French navy. The
French military awarded the prize in 1810. Unfortunately, the full development of the pro-
cess came too late to be used during Napoleon’s 1812 march to Moscow where the lack of
field rations was a major reason for his defeat in Russia. Since the early twentieth century,
metal packaging of preserved foods has been a staple for armies around the globe.
Although individual rations for combat soldiers are produced in flexible pouches today,
the metal can still remains a favorite for food processors and beverage fillers worldwide.
During the nineteenth century and midway into the twentieth, steel was the only
available material used for cans. Initially, only black plate was available. Quickly
hot-dipped tin-coated steel later was introduced for corrosion protection. Today electro-
lytic tinplate (ETP) coating or organic coating on tin free steel (TFS) is used. New
materials, such as Toyo Ultimate Can (TULC), use polyethylene terephthalate (PET)
coextruded onto aluminum (Al) or TFS, are more environment friendly, and are
being used more and more.
The development of Al in beverage cans emerged in the late 1940s. Initial trials
of impact extruded cans proved to be too expensive. Efforts toward material reduc-
tion resulted in a process called drawing and wall ironing (DWI). Here, a cupping
press blanks and draws cups from a coil of Al, and a punch in a body maker reduces
the wall thickness in one or more stages (the ironing process); 330 ml Al cans now
weigh as little as 12 g and have a sidewall thickness of about 0.1 mm (0.06 mm at iron
[Fe] beverage cans). From its humble beginnings in the nineteenth century, the metal
can for food, beverages, aerosols, and specialty packaging today is produced at speeds
up to 3,000 cans per minute (cpm). Worldwide about five billion cans are used every
year. Quality control measures are an integral part of every can-making and filling
plant. The Canmaker, an industry publication, has in-depth information on the can-making
process and its history as well as further details on manufacturers of cans.
METAL PACKAGING 157
7.2 QUALITY CONTROL AND ITS BENEFITS (ECONOMICS,

PERFORMANCE, SAFETY)
In order to minimize material use, an ever-progressing effort goes into the

“lightweightening” of both Al and Fe cans. Material thickness control has become
a key factor in the performance characteristics of metal cans. Using electronic gauging
and advanced statistical process control (SPC), thickness measurements of the
raw material and force measurements of the finished container, are performed to
maintain specified characteristics. Aside from producing cigarettes, few manufac-
turing processes are as fast as the can-making process. Al can lines are now reaching
3,000 cpm speeds. Ends are produced in even higher speeds of up to 10,000 ends
per minute (epm). The control parameters on the parts produced are very narrow.
Without quality control measures, these high speeds in the can industry would not
be possible.
As materials are lightweightened, safety in the use of containers has to be main-
tained. It is easy to understand that the high pressure in aerosol cans might make
them burst if materials are thinned too much. The same is true with carbonated bev-
erage containers. If a beer can bursts, it is messy; if an aerosol can bursts, it can be
quite dangerous. The highest concern though is for the double seam on cans. This
is the part where the can body is joined with the top or bottom of the can. The flange
of the can is rolled into the curl of the lid and pressed together, creating a hermetic seal.
On food cans, this seal has to withstand pressure and the vacuum during the proces-
sing, without allowing any entry of microorganisms into the can. On beverage cans,
it has to stop any gases from leaking to maintain product quality and to prevent cans
from collapsing due to reduced inside pressure.
7.2.1 Quality Control Measures on Tinplate
The raw material for steel food cans is cold rolled steel, shipped to the can maker in
coils or already cut into sheets. The steel mill measures the thickness continuously.
Laser displacement sensors measure the coil thickness in various places because the
coils tend to be thicker at the edges than in the middle. Specifications have to limit
the difference. Some can makers have their own coil cutting lines. Sometimes the
same laser sensors find an application here, or off-line thickness gauges are used.
In a manual thickness gauge (Figure 7.1), a small square (1–2 cm2), will be introduced
into the holder and measured with a contact gauge. The measurement result is com-
pared with the company specifications and visualized. Out of spec or out of control
measurements alert the operator to take corrective action.
The material hardness of cold rolled steel can vary, depending on the kind of
annealing process used. Batch annealing processes can be controlled to reduce the
hardness and allow for easier forming of tin cans. Forming or shaping of cans is
increasingly used to differentiate the cylindrical can into a variety of shapes. Tops
and bottoms of the cans may be necked-in to allow for the nesting of cans in transit
and on retail shelves. Other cans are shaped like a barrel to attract consumer attention.
The hardness of steel is measured with a Rockwell hardness tester.
Figure 7.1 Plate thickness gauge tester.
7.2.2 Testing of Coatings on Steel
Steel is too corrosive to be used without coatings. The most commonly used coating
is tin, which acts as a sacrificial anode and will corrode first, before the steel does. This
effect was commonly used in tomato cans to reduce the acidity of the tomato. Although
the acids in tomato products reacted with the tins, improving the products’ taste, the
health effects were called into question. Today, all food cans—ETP or TFS— have
an inside coating. The amount of tin on steel can be analyzed or measured in a coulo-
metric appliance. A given area (usually 1 or 4 inch of ETP area) is electrolytically
detinned. The appliance measures the energy needed to detin the area and converts it
to a weight measurement per area. A can maker will thus talk about so many pounds
of tin coating on his tinplate. It is not unusual to have different tin coatings on the inside
versus the outside of the can, depending on the products to be packed in the can. Inside
can coatings are measured routinely for porosity and thickness (also referred to as “film
weight”). For the coating thickness, a gauge with induction sensors is normally used. In
case of a sheet, multiple measurements are taken, and an average thickness is calculated.
A specialized gauge is used to measure the coating thickness inside cans (Figure 7.2).
This may be required when the coating is sprayed into the finished can, such as for a bev-
erage can. (The section on Al can making later in this chapter will provide more infor-
mation on this topic.)
Organic coatings are expensive, and their use has to be minimized. As coatings
become thinner, they tend to allow small pores to form during the curing cycle and
become porous. Porosity will create metal exposure and has to be reduced to a minimum.
To test for porosity of the coating, an electrode is inserted into the can, and it is filled
with an electrolyte. A second electrode is attached to the outside of the can, and a low
voltage is applied (Figure 7.3). The two electrodes are connected, and a flow of electricity
indicates metal contact on the inside of the can (the porosity of the coating). The measure-
ment in milliamperes will determine the quality of the coating.
An additional material used in food cans is TFS. Here, the expensive tin is replaced
with a combination of a flash chromium coating, electrolytically applied, and an organic
coating. Bare steel does not have the lubricity of tinplate, so TFS has to have an exterior
coating as well. This eliminates some of the cost savings and adds to emissions problems.
METAL PACKAGING 159
(a)
(b)
Figure 7.2 Coating thickness measurement tools with ezProbe for (a) flat sheets and
(b) can probe.
A promising new material for tinplate is a PET-bonded layer onto TFS. The layer
can be either bonded or co-extruded onto the steel and does not require post curing;
thus, there are no emissions to worry about. The material is called TULC and is
primarily available in Japan. There, the Toyo Seikan company claims to be able to
use their process to even make DWI beverage cans. It would make sense to measure
for porosity, though, in any case.
7.2.3 Tinplate Can Making: Three-Piece and Two-Piece Methods
The oldest method of making cans is referred to as three-piece can making. For
almost 200 years, these cans have been made of a cylinder rolled from a blank of
steel and seamed on its side. A top and bottom end are double seamed to form a
hermetically sealed container.Two-piece cans, made of one can body and a seamed
end, first appeared as blank/drawn cans, such as fish cans and other shallow drawn
containers. In a next step, single drawn cans were drawn again, or redrawn, to form
taller cans. As the DWI Al can-making process was refined, the same method was
Figure 7.3 Enamel porosity tester for a tin can.
applied for ETP materials. Today, Fe and Al materials can be made into thin-walled
beverage containers or aerosol cans, and tinplate finds its main application in food
cans. In many countries, ETP is still used in beverage cans, depending on local
circumstances, availability, and cost.
7.2.3.1 The Three-Piece Can-Making Process and Gauging

and Testing in the First Step, the Can Body
After ETP coils are cut to length, they are periodically inspected. Dimensions of
the sheet are very important as is the squareness. This inspection is done at the cut to
length line at the steel service center or by the can maker directly. Both squareness and
dimensions are measured on sheet measurement gauges (Figure 7.4).
If a sheet is too long or wide, it still could be used, but that wastes material and the cut
to length line should be adjusted. If a sheet is too short or wide, the blanks for can body
making will be too short in at least one direction, and these blanks have to be eliminated.
The same is true if a sheet is not cut square. Measured sheets are then introduced to the
duplex slitter, which is so named because the sheet is cut first into strips and the strips
are cut into blanks in the second cutting operation. A blank measurement gauge will
from time to time measure the blanks for correct size and squareness (Figure 7.5).
Stacks of body blanks (the can cylinder is called the body) are fed into the maga-
zine of a side seam welder. It picks up one blank at a time, flexes it, and roll forms
it into the can body. A pair of welding rolls next forges a seam with approximately
0.5-mm overlap. To prolong the life of the welding rolls, their circumferences are
covered with a profiled copper wire that picks up tin and oxides during the welding
(forging) process. One wire is used and threaded first around one weld roll and then
the other one. The now-contaminated wire is chopped up and collected for recycling.
METAL PACKAGING 161
Figure 7.4 Sheet gauge measurement tester.
Figure 7.5 Body blank gauge.
Next, the welded can body is checked for the correct diameter at the beginning and
the end of the seam using a plug diameter gauge (Figure 7.6). A difference in diameter
is an indication of a different overlap of the weld seam from the top to the bottom of
the can. Another gauge used to measure the overlap cuts off a piece of the end of the
weld and presents it to a microscope for measurement (Figure 7.7).
Figure 7.6 Plug diameter gauge.
Figure 7.7 Microscopic gauge measurement.
If a nonsquare blank were introduced into the welder, a weld offset on one or
both sides of the can would result. This, in turn, would create a potentially bad
seam. A phenomenon called “spike” or “weld nose” can be the result of too much pres-
sure between the weld rolls or too much weld current at the beginning of the weld.
It could also be the result of the can spacing being too small or too large. Much of
the past experience of can makers has been transferred into the software used by mod-
ern can welders. The many possible machine adjustments, especially the ones produ-
cing upward of 800 cpm, have been automated. From time to time though, the can
body has to be checked using the gauging mentioned previously. The weld seam
also has to be tested for resistance to deformation. A destructive test incorporating
a steel ball in a track is used for that purpose. During manual testing, the ball stresses
the weld seam to the breaking point. Results from this testing are good indication of
whether the weld was too hot, too cold, or just right.
Except for cans that are to be used for dry products, the weld seam has to be
protected from corrosive products. Sometimes there are different coatings for different
applications, but the can maker often does not know the eventual use of the cans being
made. Thus, the weld seam coatings are either a wet-applied organic coating or are
applied in powder form and heat cured. The ball tester will indicate the strength of the
METAL PACKAGING 163
Figure 7.8 Side seam enamel rater.
adhesion of the powder coatings to the seams. An enamel rater, similar to that already
discussed for coatings, can be tooled specifically for testing the porosity of side
seam coatings (Figure 7.8). After testing, the welded can bodies are ready for further
processing into the various can types.
7.2.3.2 Food Cans from a Welded Can Body
Low-acid foods have to be sterilized after filling to prevent microbial development.

Microbes spoil the food and may also develop toxins, which are deadly when consumed.
Food cans are not completely filled; they have a headspace of about 0.25 to 0.5 in. of
space between the top of the filled good and the top of the can. This head space
aids product agitation inside the can during the process cycle, reducing the sterili-
zation time (conduction versus convection of heat) and allowing for steam in the
head space to collapse during cooling, which creates a vacuum inside the can.
This means the can has to stand up to inside pressure and a vacuum. To compensate
for increased pressure caused by the inside temperature and corresponding expan-
sion of the vapor, the ends of the can are designed to flex outward into a convex
shape. This increases the inside space and reduces overpressure. During the cooling
cycle, the steam in the head space collapses and the ends flex back into a concave
shape. At that point, the sidewall of the can is in danger of being pulled in (or of panel-
ing). To resist this, the sidewall of food cans are beaded. Beads are corrugated areas,
mostly used in groups. Depending on the materials used, the beads have a certain num-
ber, can be grouped, and have a certain depth. To make the beaded can, the can body is
first flanged, then beaded, and then one end is seamed on. In many cases, the top or the
bottom of the can body, or both, are necked in (diameter reduced). This allows the use
of smaller ends (material savings), and cans can be nested during transport and on
supermarket shelves. As the cans are shaped, they are measured and tested after each
operation or, in cases where a combination machine is used, the finished can is mea-
sured either with individual gauges or with a combination gauge.
Figure 7.9a and b show manual gauges used to measure the flange width (all mea-
surements are taken at three points on the circumference of the can), the factory-finished
can height (in this case, “factory” means can-making plants), and the bead heights.
Figure 7.10a and b shows a combination gauge used to measure bead depths, can height,
and flange width in one gauge that also rotates the cans automatically (Figure 7.10).
The dimensional measurements give an idea of the expected performance of the cans.
To be certain, though, finished cans are also subjected to an axial load test and an
(a)
(b)
Figure 7.9 Manual flange with (a) gauge tester and (b) manual can height gauge tester.
METAL PACKAGING 165
(a) (b)
Figure 7.10 (a) Bead depth gauge tester and (b) bead height flange gauge tester.
implosion (paneling) test. If the beads are too deep, they might cause the cans to collapse
below the specified axial load. If the beads are too shallow (only one has to be bad), or if
the beads are in a spiral configuration, the can sidewall could implode (panel) during the
sterilization process (Figure 7.11).
7.2.3.3 Aerosol Cans from a Welded Can Body
Aerosol cans are subject to high internal pressures and have to be made to hold
certain overcaps. The basic material has to be much thicker for the can body and the
top and bottom; thus, the double seams are larger as well. Two-piece cans have been
developed for extra high pressures. The bodies of aerosol cans are not beaded
because they have inside pressure only. The exterior dimensions of the completed
assembly of the can body, top, and bottom are measured. Either manual gauges
or an aerosol can measuring bench (Figure 7.12) are used to measure the various
dimensions.
One of the most important tests for the completed aerosol can is burst testing.
Here, the can is subjected to a high internal pressure, and various events during
the pressure increase are measured and reported: buckle at the can’s top end, buckle
and reverse at the concave bottom, and bursting of the can. At each level, the pressure
has to be held for a specific time. The test procedure mimics possible environmental
conditions to which the cans may be subjected. Failures in any of the tests may make
the containers unsafe to use (Figure 7.13).
7.2.3.4 Vacuum-Resistant Cans from a Welded Can Body
Traditional coffee cans are sealed after filling in a vacuum, which creates a
vaccum in the sealed container. This is due to the out-gassing of ground coffee
after roasting and grinding. To counteract a potential increase in inside pressure
Figure 7.11 Combination panel for implosion and axial load.
Figure 7.12 Aerosol measurement bench.

METAL PACKAGING 167
Figure 7.13 Aerosol burst tester.
due to these gases, a vacuum is created. Beads on vacuum cans are more pronounced
than on food cans, and bead gauges may have to be modified or at least slowed down
in order to be used. Here too, testing for implosion and axial load is important to determine
the ideal combination of bead depth, number of beads, and material thickness.
7.2.3.5 Shallow Drawn Cans
Fish are most often packed in shallow drawn ETP cans. These cans use the blank and
draw process. Cans are blanked from either coils or sheets in multi-die presses. In certain
cases, the trimming step of the flange of the can is done in the same die (blank/draw/trim).
As an alternative, the trimming is done in a separate operation. The material used is
normally ETP, single reduced, and annealed. (For more information on tin mill products,
see Arcelor/Mittal at www.arcelormittal.com.) Annealed ETP is more malleable for the
drawing process. The dimensional accuracy is given by the dies, so routine measure-
ments are limited to flange width and bottom beads of the can. Axial load and panel
testing are not done.
7.2.3.6 Draw/Redraw Cans
If a deeper two-piece ETP can is required, a second or multiple draw operation is

necessary—the so-called redraw process. During this operation, the initial draw step
produces a cup—literally drawing material from the blank into the cylindrical shape.
The depth of the draw is limited by the dimension of the eccentric part of the crankshaft
of the press. Using a transfer system in the press tooling, a second draw can be actuated,
drawing the material into a taller can. Multiple tools in the same press can thus keep
reducing the diameter of the prior cup (by up to 25%) and lengthening the can body.
The design of fish cans, which rarely exceed a 50-mm can height and a 99-mm
diameter, does not require sidewall beading. Like other food cans, the ends and the
bottom of the can have to be designed to compensate for increased pressure and
vacuum inside the can during the sterilization process. A challenge can be the even
drawing process of the cup. Uneven tool wear or differing grain structure of the
(a) (b)
Figure 7.14 (a) OEG Punchmaster and (b) OEG Ringmaster.
material can cause uneven draw. If the can is lithographed (in the flat with distorted
printing), an uneven draw will manifest itself in distorted print on the finished can.
The draw rings and the punch of the tooling can be measured very accurately with
video gauges. Under magnification and high-resolution cameras, the edges of the
punch or ring can be identified and compared with the measurement of a certified
master. The difference is then calculated and results in the actual measurement of the
tooling (Figure 7.14). This being the most important variable, good tooling should pro-
duce an even draw. Of course, other components of the process, such as the blank holding
force and the material, have to be to specification. The draw/redraw (DRD) process has
also found application in high-pressure two-piece aerosol cans. Here, either hydraulic
presses with a longer stroke are used or multiple step presses, as described earlier.
Therefore, it is possible to design tooling to make the can body and the top, or the
body and the bottom, in one piece. For quality assurance (QA) purposes, it is important
to maintain flange width control to guarantee a safe double seam. Gauges for that have
been discussed previously. The inside pressure control is equally important and a legal
requirement in many countries. Aerosol burst testers are used to determine the pressure
control (see Figure 7.13).
7.2.3.7 Making DWI Cans, also Two-Piece Aerosol Cans
Much the same as in the DRD process, the DWI process starts with making a cup
(blank and draw), mostly in multi-die presses from coils. The base material can be
single-reduced ETP or Al. The DWI process was designed for cans with internal pres-
sure only, such as for carbonated beverages or beverages with an addition of some
liquid nitrogen to expand and create internal pressure after closing of the can. For this
METAL PACKAGING 169
Figure 7.15 Wall thickness gauge meter.
application, the sidewall thickness of the can be reduced to a minimum, below 0.005 in.
For structural reasons, the wall thickness at the top of the can is thicker than the mid-wall
area. Specifications for material thickness vary slightly from one can maker to another
based on their experience or on the material used in the manufacturing process. Shaped
cans need a heavier gauge and a lower hardness to stand up to stresses.
Accurate gauging is crucial for maintaining the specifications for these types of
cans (Figure 7.15). The results of the process, the actual cans, usually are measured
after the trimming operation. In order to attain the desired thickness, the punch and
die of the tooling have to be matched accurately. High-resolution optical measurements
are used to match the right punch with a ring. Lacking such gauging with sub-micron
resolution forces the can maker to try out the perceived best combination of punch and
ring, which takes time, wastes material, and reduces run time (see Figure 7.14a and b,
punch and ring gauges).
7.2.4 End Making from ETP or TFS
The material used to make can ends can be the same as that used for the can body.
The coating also usually is the same as that of the can body because it has to stand up to
1
7
4 5
9
2
8 6
(a) (b)
Figure 7.16 (a) End measurement station and (b) can end measurement graph. (1: curl diameter,
2: curl height, 3: countersink depth, 4: curl opening, 5: curl width, 6: curl length (brim
width), 7: inside curl diameter, 8: chuck fit, 9: option of first bead height.)
the same requirements of the content. Coatings can be tested for thickness but are
mostly subjected to a porosity test, which is referred to as enamel rating.
Machinery used for end making ranges from single die presses making ends from
strips of ETP to multiple die presses stamping ends from a coil. A popular modern
press uses a single die (for larger ends) or a row of dies. To effect the most efficient
material usage, the sheet (or coil) is moved in a zigzag pattern. The end curl is started
during the end stamping process. In the next operation, the curl is finished, and lastly,
the sealing compound is injected into the outer edge of the end. Two dimensions on
ends have traditionally been checked with go/no-go fixtures, the chuck fit and the pin
fit. During the double-seaming process, the curl of the end and the flange of the can are
rolled together in the first operation and pressed tight in the second. The exterior force
is applied by seaming rolls. The interior counterforce is provided by the seaming
chuck, acting as an anvil.
The chuck has to fit properly into the countersink of the ends. If the fit is too tight,
the end with the can seamed onto it may get stuck to the chuck. If the chuck is too
loose, the end might not be seamed properly, and the seaming rolls might skid. In
the past, this chuck fit was measured with a go/no-go set of fixtures. The pin fit checks
the space where the flange of the can needs to be pushed into the end curl. In the past,
this gap was tested with a pin, which was guided along the gap of the end curl, the curl
opening. If it did not get stuck, the end was acceptable. If not, the curler had to be
adjusted. Today, both chuck fit and curl opening can be measured with contact gauges
(Figure 7.16).
7.2.4.1 Sanitary Ends
Can ends for food cans are called sanitary ends. To test their expected perfor-
mance during the sterilization process, ends are subjected to one-sided pressure.
In a test called pressure of no return (PNR), ends are placed into a holder and air
pressure is applied to one side (Figure 7.17). The end passes the test if it flexes into
a convex shape at a predetermined pressure and reverses back to the original shape
METAL PACKAGING 171
Figure 7.17 Pressure no return tester.
after the pressure is released. The end fails if it does not return to the original position.
The dimensional parameters are measured manually or automatically.
7.2.4.2 Easy Open Ends
The convenience of easy open (EO) ends has spread their use to most cans in use
today. A pre-scored break line in the end, along with an affixed tab to break the
score line and pull out the partial end, makes up the EO end. Scoring steel to enable
trouble-free breaking at the score line requires excel-
lent tooling and constant QA on the depth and the
configuration of the score groove. Various gauges
have been designed to do this—from X-ray to laser
to optical methods. To date, the ideal design has
yet to emerge to measure the depth at the micron
level reliably and repeatable. Because score measure-
ment is not yet completely reliable, end makers also
rely on testers that mimic the break and pull forces
a user would have to apply during the opening
process. So-called pop and tear (break and pull)
testers establish a force curve during the opening
process that the ends have to meet (Figure 7.18).
Much like the sanitary ends, EO ends have to be tested
Figure 7.18 Pop and tear tester. for their ability to withstand pressure within the can.
Figure 7.19 PNR tester for easy open ends.
A special holding device will accept the EO ends, and pressure from the inside is applied.
The deep countersink and the convex shape of the EO ends will buckle (outward exten-
sion) at the end. Due to the countersink, the end deforms during the test and cannot return
to the original position. The buckled EO end will form a V-shaped deformation—a
“nose.” If it does that below the specified pressure, it has failed (Figure 7.19).
During the same test, an EO end with a bad score (not enough residual score
thickness) may blow out the internal removable part of the end. A particular problem
with steel EO ends is rusting—on the inside (break of the coating) and the outside.
These ends thus need to be “repair” coated. The means to do this is either with
a spray method or an electro coating system. While the spray lacquer is solvent
based and requires thermal curing, the electro coating process uses a water-based
lacquer, also requiring thermal curing. The e-coating covers all raw or exposed
metal edges, also those of the tab, and is the better solution overall.
7.2.4.3 Aerosol Tops and Bottoms
Aerosol tops and bottoms may be the most challenging to make and to measure.
Aerosol cans have to stand up to high pressures. The material used is thicker and
thus more difficult to form. The parameters are difficult to measure, as the sketch
in Figure 7.20 illustrates. Manual measurements are not very reliable, suffer from
METAL PACKAGING 173
2.
1. 3.
4.
2.
5.
1. 6.
7.
4.
Figure 7.20 Aerosol drawing. (1: curl height, 2: curl diameter, 3: panel depth, 4: curl opening, 5:
contact height, 6: countersink depth, 7: height.)
poor repeatability, and are labor intensive. The solution is an automatic gauge, as
shown in Figure 7.20. In this particular gauge, tops and bottoms can be measured
automatically, without tooling changes.
7.3 ALUMINUM IN CAN MAKING
Today, aluminum is the most widely used material in food packaging. It is

estimated that close to 20% of the available Al worldwide is used for can making,
particularly for beverage cans. Added to that is its use in flexible packaging, from
Al trays to a variety of foils. For this discussion, we will only look at cans.
7.3.1 Aluminum Can Making
Aluminum coils can be measured similarly to ETP coils. Normally, this is done
at the rolling mill. At the can maker, the Al coils are fed directly into the multi-tool
cupping press or the end stamping press. The thickness of the manufactured can is
then measured because the material is thinned down during the production process
(DWI). The beginning of the beverage can production line is called the front end.
Manual, semiautomatic, or automatic gauges are used here to measure wall thick-
nesses (mid wall and top wall), the trimmed can height, and the dome depth. The
thickness measurement normally uses highly accurate contact gauges, as shown in
the semiautomatic gauge depicted in Figure 7.21.
As with ETP cans, the DWI process is followed by the trimming, necking (some-
times multiple necking), and flanging processes. Front end (Figure 7.21) and back end
gauges (Figure 7.22) are the same as used on ETP cans. The same is true with axial
load (Figure 7.23) and buckle with dome growth (Figure 7.24).
Figure 7.21 Front-end station tester.
Figure 7.22 Back end gauge tester.

METAL PACKAGING 175
Figure 7.23 Axial load tester.
Figure 7.24 Buckle tester with growth measurement.

Reduction in material thickness may require changes in the design of the

package so it will survive the process and transportation to market of which
axial load and internal pressure resistance are a part. Marketing efforts strive to
differentiate packages. Preferred changes involve shaping of the can sidewall.
The thinned sidewall of cans made with standard Al is very hard and can barely
be expanded (under 1% expansion). For shaping, either the thickness has to be
increased, the alloy changed, or an annealing step needs to be introduced. Any
changes need to be subjected to appropriate testing with the gauges shown in
Figures 7.21 to 7.24.
A recent phenomena is the so-called dome growth. During an increase in internal
pressure of a filled can and prior to the buckle value (reversal of bottom dome to the
outside), some cans will experience a deformation in the bottom dome, referred to
as dome growth. This will not greatly influence the performance of the can, but this
means that the internal coating has cracked, thus creating metal exposure—an unac-
ceptable condition for any beverage filler. Today, the buckle tester with dome growth
measurement is increasingly used by beverage can makers. Increased production
speed in can making and filling demands tighter specifications on dimensional confor-
mity of the package. Can-making lines are now approaching speeds of 3,000 cpm.
The trend is therefore to increase inspection rates off line, apply SPC, and apply
more and more sophisticated monitoring systems. Off-line measurements can utilize
very high resolution tools, such as optical projections with on-screen measurement,
contact gauging, capacitor systems for coating thickness, sensitive pressure sensors,
and the like. The available in-line monitoring systems can compare and even read
(OCR [Optical Character Recognition]) at speeds of 64 images per second. Many
deviations from a given norm can be detected and eliminated from the line. Optical
systems are already used to inspect for damages to the exterior of cans, look for inside
contamination, check for correct color and print copy, and so on. A combination of in-
line monitoring and off-line measurements brings us closer to the goal of zero-defect
manufacturing. Safety and regulatory requirements for the integrity of the package
demand specific testing of the double seams of cans.
7.3.2 Double Seams on Cans
Joining a can body with a lid is done with a double (or triple) seam. The body
flange is rolled into the curl of the end—the first operation of the process. In the second
operation, cover hook and body flange are rolled firmly into the finished double seam.
Many variables contribute to the quality of the double seam, such as:
• The design and the position of the seaming rolls

• The profile of the seaming roll and the pressure of the seaming rolls against
the chuck
• The design and the condition of the seaming chuck
• The number of rotations of the can and end in the first and second operation
• The advance of seaming rolls via a cam or servo motors (in trials) during the
seaming process
METAL PACKAGING 177
• The position of the seaming roll in vertical axis versus that of the seaming chuck
• The pressure in vertical direction exerted by the can lifter against the can/chuck
• The bearings used and their condition in the seaming rolls, the cam followers,
and the seaming arm levers
The list goes on. Considering the many possible adjustments, it is surprising that
the majority of can seams produced actually create a hermetic seal. The source of the
problems in double seaming is the forming of the cover hook during the seaming pro-
cess. In sheet metal roofing, a similar seam is formed between two sheets of steel, but
the seam is linear, not circular, as in the case of most cans. In order for the circular
seam to work, the edge of the cover hook has to be reduced in length during the form-
ing process (first operation). This does not work without wrinkling of the excess mate-
rial. If this wrinkling is done evenly with as many small wrinkles as possible, the
pressing cycle of the second operation rolls will flatten out these wrinkles, avoiding
the creation of many tunnels or Vs in the final double seam. Therefore, the setup of
the seamer within the aforementioned variables is critical to the quality of the seam.
A good double seam creates a hermetic seal, preventing microbes from entering the
can and preventing product leakage. Measuring the can flange, the beads and can height,
and all the criteria on the end qualifies the can components prior to seaming. During the
first operation, most can makers still rely on the experience of operators to determine a
good performance. “Good” means a reasonable overlap of cover hook and body hook
(the former can flange), an inward pointing cover hook edge, and even spacing of as
many wrinkles as possible. It is difficult to visualize the inside of the seam except via
a cross section on a seam saw. This is frequently done and then judged by experts. It
could also be measured by a seam inspection system. This does take place in some
cases but mostly only during the setup of the seamer, not in production.
During production, all cans destined to be packed with low acid products, but also
most other food and beverage cans, are inspected using U.S. Food and Drug Admin-
istration rules and regulations as outlined in the Code of Federal Regulations Title 21,
Part 113. In addition to the length of the cover hook and body hook (bent can flange),
the overlap and percent overlap measurement (or calculation), and the percent body
hook butting, the external dimensions of countersink, seam thickness and seam height
have to be listed. Figure 7.25 shows all required measurements for the double seam.
80% 70% 60% 50%

100% 90%
Figure 7.25 Illustration for tightness measurement.

Figure 7.26 X-ray diagnosis image for cover hook wrinkle.
In the past, the seam dimensions were taken manually for the individual components
of the double seam. Today, the vast majority of processors use a computerized system,
where the seam is sectioned with a double-bladed saw and the cross section is viewed
with a video camera. The image is enlarged on a screen and software analyzes it, mea-
suring all the values discussed, and calculates the remainder. Following that, the seam
is stripped, the cover hook is inspected by the operator, and the wrinkles are inter-
preted. Because the strength of a chain is determined by its weakest link, the hermetic
properties of a double seam are determined by the largest wrinkle. Large refers to the
wrinkle with the longest extension from the edge of the cover hook and the bend mak-
ing up the lower part of the outside double seam. Comparisons of operator evaluations of
this most important feature (the tightness of the double seam) show a measurement uncer-
tainty from 30% to 50% (Figure 7.25). Thus, there are many ongoing efforts to develop
alternatives to subjective evaluation. One of the most promising is an X-ray method.
Here, the density of the cover hook material gives a good representation of the wrinkles.
With computer visualization methods, comparable to computed tomography scan
methods, cover hook wrinkles can now be displayed and measured better than with
human interpretation (Figure 7.26).
7.3.2.1 Double Seam Measurements on Filled versus Empty Cans
There are differences in the seam construction in a filled versus an empty can.
In a beverage can, which is normally subject to internal pressures, one can expect the
“gap” of the can seam to be quite small—sometimes so small, that it cannot be mea-
sured. A cover hook that is short may pass the inspection (X-ray) as being good. On an
empty can, though, it might not pass because of the gap, which may now be too large.
The opposite observation applies to food cans that are subject to a vacuum in their nor-
mal state of use. If a vacuum enlarges the gap in the seam, the overlap may be reduced
below the accepted minimum and the seam may fail. Measuring cans in the condition
of actual use reflects reality, but it means that the existing specifications of can makers
and fillers might have to change—an arduous process in an industry that does not like
change. But a number of filling plants are already using the new X-ray methods
and progress cannot be stopped.
7.3.2.2 Destructive versus Nondestructive Inspection Methods
Traditional seam inspection requires destruction of the double seam, as described

earlier. The disadvantages are high labor cost, the need for experienced QA inspectors
METAL PACKAGING 179
Figure 7.27 Fully and semi-automated X-ray double seam inspection systems.
to evaluate the seam and can components, loss of product and cans during inspection,
and measurements that do not reflect the condition of the seam in the active use of
the can. Today, the only nondestructive methods for full seam inspection are X-ray
systems. They are available as semi- or fully automatic systems and are normally
paired with gauges to measure countersink and seam thickness—features that are dif-
ficult to measure with existing X-ray systems (Figure 7.27).
7.3.2.3 In-line Monitoring to Control External Seam Dimensions
High-speed cameras can take and process upward of 45 images/second. As such,

they are being used for in-line monitoring of a number of can parameters. At the
can maker, cans are monitored for physical changes and inside coating condition.
The label (print) is checked for color, bar code, production code, and so on. The ends
are scrutinized just as thoroughly. The motivation is the high cost of returned shipments
and potential customer loss. The inspection process costs a small amount compared to a
legal claim by the filler.
7.3.2.4 Enamel Rating on Cans
To protect ETP and Al cans from high-acid foods and to protect taste-sensitive
foods from metal pickup, cans are coated with various types of protective coatings.
Coatings are applied in liquid form, either rolled on (coated) or sprayed on. These coat-
ings need to be thermally cured, which can create minimal bubbles that, in turn, may
burst, exposing small areas of metal to the product. The quality of coatings (enamels)
is rated by the amperage created from the inside of the can, filled with an electrolyte,
to the outside of the can. An electrode is submerged into the electrolyte and an elec-
trode on the outside of the can, piercing any coating or lithography there. If electricity
flow is measured (normally in milliamps) at a certain voltage and over a specific time,
it is an indication of metal exposure inside the can. Specifications of the can maker will
determine acceptable quality.
The enamel rating is commonly performed on finished DWI cans, DRD and
three-piece cans, aerosol cans, and on all ends (Figure 7.28). With special fixtures,
it is possible to measure circles of flat sheets (Figure 7.29), the edges of crown
corks (Figure 7.30), or the coating of welded side seams on can bodies.
Figure 7.28 Fully automated enamel rater.

METAL PACKAGING 181
Figure 7.29 Enamel rater for crowns.
Figure 7.30 Enamel rater for flat sheets.

7.4 QUALITY CONTROL IN THE CAN-MAKING INDUSTRY
This chapter explains in some detail the process of measuring and testing for many
variables and characteristics of can-making materials and those products made from it.
Each gauge is capable of delivering thousands of data points, drowning the operator
or supervisors in data. Data need to be reduced to graphs or easily comprehensible
statistics allowing the personnel to react—in the extreme, even to shut down the line.
The data gathered have to be qualified as reliable so SPC can be applied to the data
to gather reliable information. On the way to that goal, the first step has to be to qualify
the data, which have to be generated with operator-independent gauges because no
subjective input can replace an objective value. Because mistakes often occur during
data entry, it is best for the gauges to interface directly with the computer with a USB,
Ethernet, or RS232 connection. In this scenario, it is important for the computer to be
able to filter for unreasonable values, such as wrong decimal places, incorrect units,
and corrupt data, by having plausibility limits. The possibility of gauge malfunction
is another factor that needs to be taken into consideration. Care has to be taken to vali-
date gauges periodically (at least once per year) to ensure the gauges are accurate and
precise and that the operators are properly trained.
An easy way to make the overwhelming amount of data easy to react to is by using
colors to indicate breach of limits. For instance, in the case of poor but still acceptable
data, they can be colored in yellow and points outside of the specifications can be colored
red. Thus, the operator or manager can quickly spot data that need to be reviewed.
The system is not advanced enough to allow trending to proactively predict when
the process will go out of specification; however, it does let personnel react to
immediate issues.
7.4.1 Why Do We Need SPC?
SPC, ridiculed in the early 1950s when Professor Deming introduced it to General
Motors and other carmakers, distills good data into manageable information. It pro-
vides the ability to qualify suppliers or production processes or even one machine
or a station within it as sources of good products. In this case, good means the product
is of acceptable quality, has few if any defects, and that its production runs under
controls required to change or adjust it if the production parameters tested start to
deviate from the standard. The development of programs to express the “capability”
of the process keep inventing new means of visualizing the control parameters, such as
how well the production is controlled or how capable it is. When Professor Deming
was not heard in Detroit, he went to Toyota in Japan; they listened. The fact is that
today, without SPC, the efficient production of quality products is unthinkable.
7.4.2 Is Zero-Defect Production Possible?
Using all the available test methods and monitoring systems, in theory, it is pos-
sible to reach zero-defect production. But accidents happen, and there still is the
human factor to consider. Cost is another factor because there is a point of limited
METAL PACKAGING 183
return when trying to find the one bad can in a million. There is a need to grade defects
for acceptability. As long as the safety of the consumer is not at stake, common sense
should prevail.
7.4.3 Data Storage as Assurance/Defense Against Product

Liability Claims
Today data storage is cheap and can hold millions of data points for decades. Any
reasonable data collection system will be able to trace the can or lid from a bad can to
the can line used to make it, to the shift and operator who supervised its production,
and to the material used to make it. As such, a can maker or filler can pinpoint the
source of a problem and the party responsible for it. Although proof of innocence is
valuable for any potential claims in court, the primary goal is to prevent that day in
court and to ship only top quality products. This chapter was written based on
40 years of experience in can making and filling. Examples were taken from many
samples in the industry.
CHAPTER 8
Testing of Paper as Packaging Material

for Food Industry
Shabir Ahmad Mir, Haroon Maqbool Wani, Idrees Ahmed Wani,

Preeti Singh, and Ali Abas Wani
CONTENTS
8.1 Introduction...................................................................................................186
8.2 Types of Paper ..............................................................................................187
8.2.1 Kraft Paper........................................................................................187
8.2.2 Sulfite Paper......................................................................................187
8.2.3 Greaseproof Paper.............................................................................187
8.2.4 Glassine Paper...................................................................................187
8.2.5 Parchment Paper ...............................................................................188
8.2.6 Waxed Paper .....................................................................................188
8.3 Testing of Paper ............................................................................................188
8.3.1 Basis Weight .....................................................................................188
8.3.2 Thickness ..........................................................................................189
8.3.3 Folding Endurance............................................................................189
8.3.4 Puncture Resistance Test ..................................................................189
8.3.5 Bursting Strength ..............................................................................190
8.3.6 Tensile Strength ................................................................................190
8.3.7 Tear Strength.....................................................................................191
8.3.8 Density ..............................................................................................191
8.3.9 Water Vapor Permeability ................................................................191
8.3.10 Moisture Analysis .............................................................................192
8.3.11 Coefficient of Friction.......................................................................192
8.3.12 Edgewise Compressive Strength.......................................................192
8.3.13 Flat Crush (Slow Rate of Loading)...................................................193
8.3.14 Flat Crush (Impact Loading).............................................................193
8.3.15 Bending Stiffness ..............................................................................194
185
8.3.16
Shear Test .........................................................................................194
8.3.17
Vibration Transmissibility ................................................................194
8.3.18
Peel Test............................................................................................195
8.3.19
Water Absorptiveness .......................................................................195
8.3.20
Water Resistance Tests .....................................................................195
8.3.20.1 Cantilever Test ................................................................ 196
8.3.20.2 Shear Tests...................................................................... 196
8.3.21 Abrasion Toss ...................................................................................196
8.3.22 Stiffness.............................................................................................197
8.3.23 Blocking Resistance..........................................................................197
8.3.24 Air Permeance...................................................................................198
8.3.25 Adhesion Strength.............................................................................198
8.3.26 Vertical Impact Test by Dropping Corrugated Containers ...............198
Bibliography...........................................................................................................199
8.1 INTRODUCTION
Paper is one of the most important packaging materials. Paper and paperboard
have been used both as primary and secondary packaging for a wide range of
foods for many years. The weight of paper and board used in packaging is approxi-
mately equal to the weight of all other packaging materials combined. Paper consists
of a porous cellulose structure made up of microfibrils, which are composed of long
chain cellulose molecules in a crystalline state with amorphous regions regularly
disrupting the crystalline structure. The hydrophilic nature of cellulose, due to the
hydroxyl sites in the basic unit of cellulose (C6H10O5) and fiber network porosity,
affects its paper.
Paper and paperboard are sheet materials made from an interlaced network of
cellulose fibers derived from wood by using sulfate and sulfite. The fibers are then
pulped or bleached and treated with chemicals and strengthening agents to produce
the paper product. Paper is produced by beating wood chips to break them down to
a pulp that contains the wood fibers and then treating the fibers with alkali or acid.
After treatment, the fibers are pressed through a series of rollers to form paper. The
sizing is also done by the chemicals that are added to the pulp during preparation to
give particular properties to the final paper.
Paper and paper-based packaging are essential components of modern life. Paper
is widely used in packaging applications and is biodegradable and therefore perfectly
safe for the environment. Paper-based packaging is a versatile and cost-efficient method
to transport, protect, and preserve a wide array of items. Methods have been developed
for testing paper and its products for the evaluation of properties under general packaging
conditions. The application of these testing methods with the standardization of instru-
ments and processes to be used in individual laboratory tests will contribute toward
providing an ever-improving guarantee of the specific characteristics of paper and cor-
rugated board and will engender increasing confidence in the use of such material in
the packaging industry.
TESTING OF PAPER AS PACKAGING MATERIAL FOR FOOD INDUSTRY 187
8.2 TYPES OF PAPER
Plain paper is not used to protect foods for long periods of time because it has poor
barrier properties and is not heat sealable. When used as primary packaging (i.e., in
contact with food), paper is almost always treated, coated, laminated, or impregnated
with materials such as waxes, resins, or lacquers to improve functional and protective
properties. Different types of paper used in food packaging are as follows:
8.2.1 Kraft Paper
Kraft paper is typically coarse and is produced by a sulfate treatment process. This
paper is available in several forms, including natural brown, unbleached, heavy duty,
and bleached white. The natural kraft is the strongest of all paper and is commonly
used for bags and wrapping. It is also used to package flour, sugar, dried fruits, and
vegetables.
8.2.2 Sulfite Paper
This type of paper is lighter and weaker than kraft paper. Sulfite paper is glazed to
improve its appearance and to increase its wet strength and oil resistance. It can be
coated for higher print quality and is also used in laminates with plastic or foil. It is
used to make small bags or wrappers for packaging biscuits and confectionery.
8.2.3 Greaseproof Paper
Greaseproof paper is made through a process known as beating, in which the cel-
lulose fibers undergo a longer-than-normal hydration period that causes the fibers to
break up and become gelatinous. These fine fibers then pack densely to provide a sur-
face that is resistant to oils but not wet agents. The satisfactory performance of grease-
proof papers depends on the extent to which the pores have been closed. Provided that
there are few interconnecting pores between the fibers, the passage of liquids is diffi-
cult. Greaseproof paper is used for packaging of butter and similar foods because it
resists the penetration of fat for a reasonable time period.
8.2.4 Glassine Paper
Glassine paper derives its name from its glassy, smooth surface, high density, and
transparency. It is produced by further treating greaseproof paper in a supercalender
where it is carefully dampened with water and run through a battery of steam-heated
rollers. The extreme further hydration produces a very dense sheet with a highly
smooth and glossy finish. The transparency can vary widely depending on the degree
of hydration of the pulp and the basis of the paper. It is used as a liner for biscuits,
cooking fats, fast foods, and baked goods.
8.2.5 Parchment Paper
Parchment paper is made from acid-treated pulp (passed through a sulfuric acid
bath). The acid modifies the cellulose to make it smoother and impervious to water
and oil, which adds some wet strength. The cellulosic fibers swell and partially dis-
solve, filling the interstices among the fibers and resulting in extensive hydrogen bond-
ing. Thorough washing in water, followed by drying on conventional paper-making
dryers, causes precipitation and consolidation of the network, resulting in a paper
that is stronger wet than dry; free of lint, odor, and taste; and resistant to grease and
oils. Unless specially coated or of a heavy weight, it is not a good barrier for gases.
Because of its grease resistance and wet strength, parchment paper strips away
easily from food material without defibering, thus finding use as an interleaver
between slices of food such as meat or pastry. Labels and inserts in products with
high oil or grease content are frequently made from parchment.
8.2.6 Waxed Paper
Waxed papers provide a barrier against penetration of liquids and vapors. Many
base papers are suitable for waxing, including greaseproof and glassine papers. The
major types are wet-waxed, dry-waxed, and wax-laminated. The wet-waxed papers
have a continuous surface film on one or both sides, which is achieved by shock chil-
ling the waxed web immediately after application of the wax. This also imparts a high
degree of gloss on the coated surface. Dry waxed papers are produced using heated
rollers and do not have a continuous film on the surfaces. Consequently, exposed
fibers act as wicks and transport moisture into the paper. Wax-laminated papers are
bonded with a continuous film of wax that acts as an adhesive. The primary purpose
of the wax is to provide a moisture barrier and a heat-sealable laminate.
8.3 TESTING OF PAPER
The increasing diversity of end-use applications of paper and paperboard requires

rational assessment of their properties in various aspects. Many of the recent develop-
ments in testing have been directed to more sophisticated methods for the evaluation
of properties under general packaging conditions.
8.3.1 Basis Weight
Basis weight is the actual weight per unit area of the paper or paperboard. The
details of this test method are found in the Technical Association of the Pulp and
Paper Industry’s standard TAPPI T410 (ASTM D646, Standard Test Method for
Mass Per Unit Area of Paper and Paperboard of Aramid Papers [Basis Weight]).
Test specimens of a given area, taken from a representative sample of paper or corru-
gated fiberboard, are brought into equilibrium with a standard atmosphere and are then
weighed on a suitable accurate balance. Test results (basis weights) are expressed in
grams per square meter (g/m2). A balance with a sensitivity of 0.5 g or better, over the
entire measuring range, should be used to make the determinations. The basis weight
can be calculated by the formula given in Equation 8.1.
g 106
G= (8.1)
ab
where G = basis weight in g/m2, g = weight of test specimen in g, a = length of test

specimen in mm, and b = width of test specimen in mm.
8.3.2 Thickness
Thickness is one of the important parameters of paper. Thickness affects the var-
ious properties of paper and paperboard, including stiffness and permeability. The
thickness is the perpendicular distance between the two outer surfaces of material.
The method for determining the thickness is given in TAPPI T411. Generally, thick-
ness is measured at different locations of the sample, and the mean is calculated. The
thickness is measured by using a micrometer. The use of a micrometer for combined
board or for dial gauge and comparator stand will give overall thickness values. Thick-
ness values of paper and paperboard are reported in millimeters (mm).
8.3.3 Folding Endurance
A folding endurance test is the best available criterion for testing the serviceability
of paper that is creased or folded repeatedly. This test gives information about certain
properties of paper, such as durability, that cannot be obtained by other tests. A strip of
paper is continuously folded till it breaks, with the number of double folds giving the
folding resistance. The double-fold testing machine is mostly used for this test. The
machine is driven by a motor or countershaft with the help of a friction pulley effecting
90 to 120 double folds per minute. When the machine runs, the allotted folding blade
slides back and forth in a reciprocating motion between the creasing rollers. The
clamps are under spring tension, which can be varied. The number of times the paper
goes through each double fold (back and forth) is counted on a rotating disc known
as counter that is designed to count up to 10,000 double folds.
8.3.4 Puncture Resistance Test
The puncture test, also known as the Beach puncture test, measures the resistance
of paper or corrugated fiberboard to damage that may occur if the material comes in
contact with a corner of another container or with other hazards of lading—hence, the
triangular pyramid shape of the puncture point. The method for evaluating the punc-
ture resistance of corrugated fiberboard is given in TAPPI T803. A representative
sample of corrugated fiberboard is subjected to puncture by a triangular pyramid punc-
ture head attached to a pendulum. The energy required to force the puncture head
completely through the sample (i.e., to make the initial puncture) and to tear and bend
open the fiberboard is measured.
The test instrument measures the energy, in joules, required to force the puncture
pint completely through the corrugated fiberboard. The puncture value is dependent
upon the resistance to puncture and the stiffness of the fiberboard, which in turn is
affected by the tear strength of the component linerboards and medium, the quality
of the adhesive, and the thickness of the combined board.
8.3.5 Bursting Strength
The popularity of the bursting strength test depends not only on the ease with
which the test is conducted but also on the combination of strength and toughness
that measures, and serves as a measure of, the serviceability of paper in various appli-
cations. Bursting strength is measured by the pressure developed behind a circular
rubber diaphragm when it is forced through the paper so as to burst it. The maximum
pressure sustained by the specimen is recorded.
The burst test is the most common evaluation test used for paper and corrugated
fiberboard. The TAPPI method is T81. The test is conducted using a bursting tester
and, in essence, consists of forcing a rubber diaphragm through a hole approximately
25 mm in size using hydraulic pressure. The resultant upward bulge of the diaphragm
causes it to puncture the specimen. The hydraulic force required to burst the specimen
is recorded on a dial or an electronic digital readout device.
8.3.6 Tensile Strength
The most common strength test for paper is that of tensile strength. The limiting
resistance of a test piece of paper or board is submitted to a breaking force applied to
each of its ends under the conditions defined in the standard method of test. The tensile
strength is generally expressed as breaking length. The most common method is to
use gripping devices that are attached to a testing machine. The grips are tightened
mechanically or pneumatically, compressing the paper through the thickness, and a
load is applied by a shearing action as the grips are driven apart. This leads to a shear-
ing action across the faces of the paper. In addition, natural lateral contraction, which
takes place during tensile loading, is restrained, and an in-plane lateral tensile stress is
imposed near the grips. In the vicinity of the grips, the paper is in a rather complex
state of stress. The dominant resultant force acting on the sample, however, is the
tensile force pulling it apart.
The tensile specimens for most materials are dog-bone shaped. In this way, a large
tensile force can be transmitted to the sample through a larger transfer area, which
minimizes stress concentrations near the grips. The “neck-down” portion of the sam-
ple magnifies the uniform tensile stress through the narrow section. To obtain a pure
tensile stress–strain curve for the material, the strain is measured over the portion of
the specimen that is under pure tension. The tensile strain is computed by dividing the
elongation of a preselected gauge length by the original gauge length.
8.3.7 Tear Strength
A tear test is a classic example of test methods developed for evaluating a parti-
cular kind of paper strength. Tearing of paper consumes energy, and the force needed
to continue the tearing is assumed to correlate with important end-use properties. This
test method involves applying an impact load to pull paper apart perpendicular to its
faces. The energy absorbed by the sample from a swinging pendulum is used as an
index of tear strength. The tear test is a useful index of paper performance.
8.3.8 Density
Density is an important parameter for paper and paperboard. Density is defined as

the mass per unit volume of the tested material. Elevated density values imply high
transportation and storage costs. Implementation of the material also becomes much
easier and less hazardous when lighter. Density is often used for the calculation of
“specific properties” (i.e., dividing mechanical properties by the appropriate density).
It is often expressed in units of g/cm3, but the preferred SI units are kg/m3.
8.3.9 Water Vapor Permeability
Water vapor permeability is the most important characteristic of any paper. The
permeability of paper must be right for its purpose. The paper for packaging cheese
requires a very different permeability from the permeability of a paper used for
other purposes. Paper permeability is the measure of how strongly it can resist
the passage of a vapor (usually water). The permeability dramatically affects the
physical characteristics of paper, including strength, printability, durability, and
paper handling.
A gravimetric technique is used based on the change in weight caused by passing
water vapor through the material being tested. There is a series of local and interna-
tional standards for these tests that depend on the material being tested. In the
paper regime, a period of conditioning is specified. A cup of water-absorbing material
is covered with the sample and sealed to the cup. The cup is accurately weighed and
placed in a humidity- and temperature-controlled cabinet. The cup is reweighed daily.
In some cases, the test is continued until equilibrium is reached but, in others, the test
is continued for a fixed period or until no more water can be absorbed. In some cases,
water vapor permeability of paper and board are determined under specific conditions
of temperature and humidity. A quantity of desiccant, enclosed in a dish sealed by a
sheet of the material, is stored in a conditioned atmosphere and the rate of water vapor
transmission is computed from the rate of increase in weight of the dish assembly.
Water vapor meters are also used, and they vary considerably in appearance,
mechanism, components, and even in measurement sensor. However, the leading
instruments all work on a similar principle. One side of the sample is exposed to a
humid environment, and the water vapor that passes through is swept to a sensor by
an inert gas. All of the water vapor passing through the sample is swept to the
detector, and an accurate measurement is made. In most cases, when dealing with
water-based coatings, equilibrium is reached within a few hours, although in some

cases, results are obtained in as little as 30 minutes. This compares to days, weeks,
and even months for gravimetric measurements of the same materials.
8.3.10 Moisture Analysis
Moisture content is an important parameter for any packaging material and should
remain below the specified level in the appropriate material standard. The percentage
of water contained in the material is determined by heating to a constant weight
(as specified) in a hot air oven. The conditioned specimen is weighed and heated to a
constant weight to expel moisture. The difference between two weighings gives the
moisture content. This method applies to all papers, paperboards, and paper products.
8.3.11 Coefficient of Friction
The coefficient of friction test is most important for corrugated boxes. The use of
corrugated fiberboard as a container material requires that it not be too slippery, so that
it can be handled in transportation, but slippery enough that it will move down a chute.
To determine resistance to slippage, two TAPPI methods, T815 (ASTM D4521,
Method of Test for Coefficient of Static Friction of Corrugated and Solid Fiberboard
[Inclined Plane Method]) or T816, are used. Both methods will give the coefficient of
friction, or the resistance to slippage, of the material.
Actually, there are two values for coefficient of friction, one static and the other
dynamic (kinetic). The static coefficient of friction, using the incline method, is the
tangent of the angle of inclination at which the sample of corrugated fiberboard begins
to slide. The kinetic coefficient of friction is the tangent of the angle of inclination at
which a sample of corrugated fiberboard will continue to slide once it has started.
Typical static coefficient of friction values for untreated line board average 0.39
and range from 0.23 to 0.67. For kinetic values, the average is 0.26 and the range is
from 0.17 to 0.49. The static values are always higher than the corresponding kinetic
values.
8.3.12 Edgewise Compressive Strength
The edgewise compressive strength crush resistance is calculated based on the

maximum force sustained by a specimen. The details of the test method are given
in TAPPI T811. Edgewise compressive strength is also commonly referred to as
the short-column strength of the combined board because the specimen used to deter-
mine the strength value is short. This test has proven to be one of the most important
because it is the property that influences the compressive strength of a corrugated con-
tainer. The load is applied along the edge of the specimen in the direction parallel with
the flutes.
It is generally recognized that paperboard is weaker in compression than in ten-
sion. This inequality in material strength can have a considerable impact on product
quality, cost, and performance. For example, shipping containers under several
types of loading situations, such as stacking, internal pressure, or both, can develop a
state of combined tensile and compressive stresses.
A square test specimen has been found appropriate for the edgewise compression
test of corrugated board. The bearing ends are waxed and placed in slotted guide
blocks to ensure a fixed end-load condition. It is essential that the edges be cleanly
cut and perfectly parallel. The parallel plate machine is used to deliver the load com-
pression. The maximum load per unit width (N/m, kgf/cm, or lbf/in.) is reported as
short column crush strength. Dividing maximum load by actual cross-sectional bear-
ing area would yield ultimate compression strength (Pa, kgf/cm2, or psi).
8.3.13 Flat Crush (Slow Rate of Loading)
The flat crush test is in essence the application of load perpendicular to the surface
of the combined board. The test method typically used is given in TAPPI T825. A test
specimen of corrugated fiberboard is subjected to a uniformly increasing force applied
perpendicularly to the surface by a compression tester, having two flat and parallel
platens, until the fluting collapses.
A board with a low flat crush resistance will be subject to excessive crushing in
converting equipment, such as in the mechanical handling of containers and their con-
tents in warehousing. Reduced compressive strength can result after exposure to this
handling in the field by virtue of the fact that, as the medium tends to break down, the
cross section of the board is reduced, resulting in reduced compressive strength of the
finished container. Therefore, indirectly, a combined board that has a high flat crush
resistance would have a tendency to have a higher container compressive strength than
a board with low flat crush resistance.
The specimen used for evaluation should be round or square and preconditioned
and tested in controlled atmospheres. It should be also pointed out that, if excess ten-
sion is applied by testing machine to either the singleface or doubleback linerboard
during manufacture, the combined board can end up with leaning flutes; such com-
bined boards will give low flat crush values because the flutes will continue to lean
or roll over when the board is under load. The large range in values for the flat
crush of corrugated fiberboard reflects the fact that flat crush resistance is also a func-
tion of the type of fiber used.
Corrugated fiberboard that has been crushed will have a progressively lower hard-
ness value as the amount of crushing is increased. Thus, the hardness value will relate
to the degree of crushing. The flat crush values obtained are independent of the facing
materials and find their primary significance as indicators of the ability of the medium
to keep the facings in their original relative position.
8.3.14 Flat Crush (Impact Loading)
During fabrication, a compressive load is applied through the liner facings to

attach them to the corrugated medium. Impact loading during handling and shipping
can also cause through-the-thickness compressive loading. Extensive loading can
crush the corrugated design of the composite material and seriously reduce its bending
stiffness. In this test, compressive load is applied perpendicular to the plane coating
the flute tips of the corrugated medium.
Impact loading of flat pads of corrugated fiberboard is accomplished by mounting
the corrugated board on a massive block of concrete and impacting the board with a
loading head suspended as a pendulum. The weight of the pendulum can vary as well
as the contact surface area. The loading head is also equipped with an accelerometer so
that the peak acceleration time pulse can be determined. Then, by varying the weight
of the loading head, a series of peak acceleration tie pulses can be generated. These are
then plotted to give the results that are reported as peak acceleration static-stress
curves and that are primarily used when solving cushioning problems.
8.3.15 Bending Stiffness
Bending stiffness is widely recognized as being an important parameter of carton

board. Bending stiffness is the capability of a structural member to resist bending.
Bending stiffness, like edgewise compressive strength of a combined board, is impor-
tant in terms of the compressive strength of a container.
Bending stiffness is the property of a paper or paperboard to resist an applied bend-
ing force proportional to EI, where E is Young’s modulus and I the moment of inertia.
This test indicates the relationship between the load and deflection that may be used to
determine the modulus of elasticity or stiffness of a given paper product. The tensile
tester is preferably equipped with a recording device that provides a graphic record of
the applied load and deflection.
8.3.16 Shear Test
The flatwise shear of corrugated fiberboard is a measure of combined board rigidity.

The method used is found in ASTM D1037, Standard Test Methods for Evaluating
Properties of Wood-Base Fiber and Particle Panel Materials. The test specimen is
2 in. wide and 8 in. long and glued between two wood blocks. A metal yoke is fastened
to one block and a dial gauge reading to 0.001 in. (0.254 mm) is attached to the other in
order to measure relative displacement of the two faces of the corrugated fiberboard
under load. Obviously, the shear displacement is resisted primarily by the corrugated
medium of the combined boards so that the test should indicate the rigidity of the portion.
8.3.17 Vibration Transmissibility
To determine the vibration transmissibility, specimens of corrugated fiberboard

are placed in a test fixture designed to represent an outer container, with a loading
block that represents the packaged item placed on top of the flat pads. In this prepara-
tion, the loading block is free to move in the vertical axis but is constrained by guides
to keep it in position laterally. The test fixture, consisting of the outer frame, the cor-
rugated pad, and the simulated packaged item, is mounted on a vibration exciter that
produces a sinusoidal vibration in the vertical axis at controlled frequencies and accel-
eration levels. The input vibration acceleration level is measured by an accelerometer
on the base of the test fixture. The vibration transmitted through the test specimen to
the loading block is measured by a similar accelerometer mounted within the loading
block. Vibration transmissibility of the specimen material is computed from the ratio
of the response of acceleration of the loading block to the input acceleration of the test
fixtures.
8.3.18 Peel Test
A more meaningful test in terms of useful information about adhesive bond in

corrugated fiberboard is the peel test. In this test, one facing is slowly peeled from
the fluted medium, one flute at a time. Either facing may be removed, depending
on whether the single-faced or double-back bond strength is of interest. The big
advantage to this method is that it tests the bond one flute at a time and thus is very
sensitive to variations in the bonding of the board. In essence, it will not only provide
an average maximum load value to characterize that board, but it also gives an accu-
rate picture of the variations among the bonds.
8.3.19 Water Absorptiveness
This test is mostly used for paper packaging material and gives the determination
of water sucked up by a strip of material and the rate at which this occurs. One spe-
cified side and a specified area of a corrugated fiberboard test piece are exposed to
a defined column of water for 30 minutes. The water absorptiveness is deducted
from the difference of weightings immediately before and immediately after exposure
to water.
The test pieces are taken from undamaged areas of the samples and weighed. The
cylindrical tank is used for this purpose and is applied to the specified side and the
specified area of the test piece. The water is poured in the cylindrical tank to form a
head of at least 3 mm of water upon the test area of the test piece. After 30 minutes
of exposure to water, the water is poured out quickly and the cylindrical tank is
removed. Blotting paper is placed on the tested area of the test piece, the metal roller
is rolled once forward and once backward, with its axis parallel to the flutes, and
is weighed against the test piece. The water absorptiveness value A to the nearest
g/m2 of each test piece is shown in Equation 8.2:
m2 − m1
A= (8.2)
S
where m1 = mass of the test piece before exposure to water in g, m2 = mass of the test
piece after exposure to water in g, and S = nominal cross-sectional area of the cylind-
rical tank in m2.
8.3.20 Water Resistance Tests
This test used for evaluating corrugated adhesive bonds is primarily concerned
with determining the water resistance of the adhesive. Conventional starch adhesive
is not water-resistant, and combined board exposed to free water will—in a matter of
minutes—literally fall apart, although surface tension will sometimes hold the facing
to the medium. The test method for evaluation of corrugated fiberboard for water-
resistance is TAPPI T812, commonly referred to as the thumb-flick test. In this test,
the corrugated fiberboard specimen is submerged in water for 24 ± 1 hours and
then removed and allowed to drain until the surface no longer glistens and the excess
water has drained from the flutes. Immediately following draining, the specimen is
checked for adhesion among components. The separation of components may
occur spontaneously and freely during soaking; however, surface tension may often
cause the wet components of fiberboard to cling together even though they are not
bonded by adhesive. This condition may be detected by brushing lightly with the
ball of the thumb across the cut edges of the specimen at several points on each of
the four edges using a light touch only sufficient to overcome the surface tension.
The following two methods are used for water resistance evaluation.
8.3.20.1 Cantilever Test
A more meaningful method is a test in which the water-soaked specimen is loaded

as a cantilever beam. Beam bending results in a shear load being applied to the adhe-
sive bond, which determines whether the adhesive is adequate to develop the strength
of the component paperboards. The test has been shown to relate to container perfor-
mance; it stresses the adhesive bond in the same manner as actually occurs in use.
8.3.20.2 Shear Tests
In this test, a sample of the water-soaked corrugated fiberboard that is cut 25.4 mm
in the cross-section machine direction, with the length just sufficient to include 12
gluelines on each linerboard, is positioned by clamping one end of the linerboard.
This floating clamp is attached by a cable to a weighing mechanism or to a conven-
tional tensile tester in which the load can then be applied to the specimen.
The European Federation of Corrugated Board Manufacturers has developed a
standard in which “The water resistance of the glue bond of the corrugated fiberboard
is expressed by the length of time during which a predetermined combination of glue-
lines, immersed in water, resists the pull of a suspended weight in the plane vertical
axis of the board, at a right angle to the gluelines.”
8.3.21 Abrasion Toss
This method provides a measurement of the susceptibility of the surfaces of paper

and paperboard used for packaging to the action of standardized abrasive surfaces,
either wet or dry. The test gives an indication of the surface wear to be expected
when packages are shipped and subjected to prolonged vibration in contact with
each other. It is not applicable to surfaces that are waxed or treated with similar mate-
rials that would fill in the pores of the abrasive wheels.
It consists of a horizontal turntable and center clamp that revolve counterclockwise

at 65 to 75 rpm, upon which the specimen is attached, and two weighted parallel
arms, each carrying a special abrasive-embedded rubber wheel freely rotating on a
ball-bearing horizontal spindle on each arm and each resting on the specimen with a
pressure of 1000 g for the dry test and 500 g for the wet test. The lines of contact of the
wheels on the specimen are at right angles to the parallel supporting arms and are
situated at 2.5 cm from the center of the turntable toward the axis about which the sup-
porting arms turn. The center of the line of contact of the wheel on the arm to which the
turntable revolves is 4.5 cm to the right of the perpendicular line from the axis of the
arms to the center of the turntable. The center of the contact line of the wheel on the arm
from which the turntable revolves is 39 mm to the left. In this manner, when in contact
with the turning specimen, the two wheels revolve in opposite directions and exert a
combined abrasive, compressive, and twisting action over a circular path, approxi-
mately 10 cm2 in area, twice during each revolution of the specimen.
8.3.22 Stiffness
Stiffness is the ability of paper or paperboard to support its own mass. The mea-
surement of stiffness helps in predicting the performance of a packaging material in
actual use. Two methods have been prescribed for the determination of stiffness.
Method A is meant for paper or lightweight paperboard and Method B is for paper-
board only.
Method A: The apparatus consists of a clamp formed by a pair of flat jaws or rollers
adapted to grip the end of a 50-mm-wide strip of material to be tested along a horizon-
tal axis at right angles to its length. The jaws or rollers are mounted on a spindle to
enable the clamped end of the strip to be rotated about that axis, and means are pro-
vided for indicating when the clamped end of the strip has been rotated axially through
a right angle from any initial position. The edges of the clamping surfaces should be
coincident.
Method B: The apparatus consists of a pendulum supported in antifriction bear-
ings, carrying a vice that has two clamping screws for holding and centering the
test specimen. The lower edge of the vice should coincide with the center of the pen-
dulum bearing. The pendulum is balanced; at its lower end is a stud, to which weights
may be attached, that loads the pendulum at a distance of 100 mm from its center;
without added masses of counter masses, the loading is 10 g. A line, coinciding
with the center line of the vice jaws and the weight stud, is engraved at the upper
end of the pendulum.
8.3.23 Blocking Resistance
Blocking is defined as the degree of cohesion or adhesion between contiguous

layers of similar or dissimilar materials in rolls or sheet form that prevents their satis-
factory and efficient use. This method covers the test for rating the blocking resistance
of flexible types of packaging materials wherever the tendency to block is important.
The blocking resistance is determined by observing the adhesion or cohesion between
the contiguous surfaces of the specimens when they have been subjected to a pressure
of 35 g/cm2 for a period of 24 hours.
8.3.24 Air Permeance
This method provides a measurement of air permeance of paper and paperboard.

The method is applicable to papers and boards having air permeances between
0.35 and 15 m (Pa˙s). The method is unsuitable for rough-surfaced papers and
boards, such as creped and corrugated papers that cannot be securely clamped to
avoid leakage. The apparatus consists of a compressor and pressure-stabilizing reser-
voir to supply air, a flow meter with a pressure controlling device, and a measuring
head.
8.3.25 Adhesion Strength
Because corrugated fiberboard is a composite structure with the components

bonded together, a principal concern is to evaluate the adhesive method. The most
widely used bond test is the pin adhesion method. The test is performed by the appli-
cation of a tension force perpendicular to the linerboard through a series of pins that
are placed in the flutes. The load is applied to the ends of the pins stressed in tension.
However, because the pins are on the facings between the bonds, the stiffness of the
facings can play a part in the results because the actual mechanism of loading is not
direct tension but a combination of tension, bending, and peel. This mixture of forces
and the flexibility of the metal pins themselves can lead to test variability. The results
of the test are reported in terms of total load at failure, load per length or glueline
tested, or load per unit area.
Two assemblies of metal pins are introduced into spaces between the flutes of the
adhesive joints to be tested in such a way that, by means of a holder and a crush tester,
the sets of joints are separated by the application of a force applied perpendicularly to
the surface of the board. The force needed to separate the liner from the fluting is mea-
sured and reported. A power-driven crush tester is used. When a tester operating on the
principle of beam deflection is used, results are valid only if they occur between 20%
and 80% of the normal range of deflection. This will ensure that the cut edges are
clean, straight, and perpendicular to the facings of the board. The apparatus to be
used should be of any suitable type permitting the perpendicular force to be applied
selectively to the liner/flute lines to be tested.
8.3.26 Vertical Impact Test by Dropping Corrugated Containers
This test is one of a series of performance tests for corrugated fiberboard contain-
ers and may be selectively applied as specified—either singly or in combination with
other tests. The test is applicable to all types of corrugated containers complete with
internal fitments and the actual or dummy contents. A test specimen should consist of
a container (with normal or dummy contents) that is filled, closed, and sealed in the
manner intended for normal usage. A specimen container complete with actual or
dummy contents is caused to fall freely in a predetermined attitude and from a speci-
fied drop height on to a solid plane horizontal surface. On completion of the test cycle,
which may consist of a number of drops with the container in differing attitudes, the
specimen and its contents are examined and results reported.
BIBLIOGRAPHY
Back, E. L. 1995. Autodispersible waxes for recyclable packaging papers. Part 1: Principles for
wax removal after alkaline hot dispersion. TAPPI Journal 78: 161–68.
Bandyopadthay, A., Romarao, B. V., and Ramaswamy, S. 2002. Transient moisture diffusion
through paperboard materials. Colloids and Surfaces A 206: 455–67.
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pp. 1819–1886. Wiley, New York.
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package engineering, 3rd edn., eds. J. F. Hanlon, R. J. Kelsey, and H. Forcinio, pp. 31–57.
Technomic Publishing, Lancaster, PA.
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packaging materials. Comprehensive Reviews in Food Science and Technology 9:
82–91.
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R. Coles, D. McDowell, M. J. Kirwan, pp. 241–48. Blackwell Publishing, London.
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Vol. I. Marcel Dekker, Inc., New York.
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Journal of Food Science 72(3): R39–R55.
Robertson, G. L. 2006. Food packaging: Principles and practices. 2nd edn., CRC Press,
Boca Raton, FL, pp. 103–120.
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Smook, G. A. 2002. Handbook of pulp and paper technologists. 3rd edn., Angus Wilde
Publications, Vancouver, BC.
Summerfield, W. and Cooper, I. 2000. Investigation of migration from paper and board into
food – Development of methods for rapid testing. Food Additives and Contaminants
18(1): 77–88.
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crush study-committee Assignment No. 689. TAPPI Journal 44(9): 614–619.
Thykeson, E. 1970. A wet shear test for water resistance of corrugator adhesive bonds. TAPPI
Journal 53(7): 1286–1288.
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paper industry. Wiley, New York.
CHAPTER 9
Testing and Quality Assurance

of Bioplastics
Manzoor Ahmad Shah, Markus Schmid, Ankit Aggarwal,

and Ali Abas Wani
CONTENTS
9.1 Introduction...................................................................................................202
9.2 Testing Methods ...........................................................................................205
9.2.1 Testing of Physical Properties ..........................................................205
9.2.1.1 Thickness .......................................................................... 206
9.2.1.2 Density .............................................................................. 206
9.2.1.3 Mass .................................................................................. 206
9.2.2 Testing of Mechanical Properties .....................................................207
9.2.2.1 Tensile Tests ..................................................................... 207
9.2.2.2 Impact Tests...................................................................... 208
9.2.2.3 Compression Tests............................................................ 208
9.2.2.4 Puncture Tests................................................................... 209
9.2.2.5 Hardness Tests .................................................................. 209
9.2.3 Testing of Optical Properties ............................................................211
9.2.3.1 Refractive Index................................................................ 211
9.2.3.2 Refractometric Method ..................................................... 212
9.2.3.3 Microscopical Method ...................................................... 212
9.2.3.4 Luminous Transmittance and Haze .................................. 212
9.2.3.5 Color ................................................................................. 213
9.2.4 Permeability Testing .........................................................................215
9.2.4.1 Water Vapor Permeability Test ........................................ 215
9.2.4.2 Oxygen Permeability ........................................................ 216
9.2.5 Rheological Measurements ...............................................................217
9.2.5.1 Viscosity Tests .................................................................. 218
9.2.5.2 Melt Index Test................................................................. 218
201
9.2.6 Environmental Stress Cracking.........................................................219

9.2.6.1 Environmental Stress-Cracking Resistance ...................... 219
9.3 Compositional Analysis ................................................................................220
9.3.1 Molecular Weight Using Gel Permeation Chromatography.............220
9.3.2 Analytical Tests ................................................................................221
9.3.2.1 Water Absorption.............................................................. 221
9.3.2.2 Moisture Analysis ............................................................. 222
9.3.2.3 Solubility Test................................................................... 222
9.4 Biodegradability Testing...............................................................................222
9.4.1 Standards for Compostability ...........................................................222
9.4.2 Biological Degradability (Laboratory Tests) ....................................224
9.4.3 Methods for Biodegradation .............................................................224
9.4.3.1 Soil Burial Method ........................................................... 224
9.4.3.2 Pure Culture Method......................................................... 224
9.4.3.3 Compost Method .............................................................. 225
9.4.3.4 Anaerobic Degradation in the Presence
of Sewage Sludge ............................................................. 225
9.5 Thermal Analysis Techniques.......................................................................226
9.5.1 Differential Scanning Calorimetry....................................................227
9.5.2 Thermogravimetric Analysis.............................................................227
9.5.3 Thermomechanical Analysis.............................................................228
9.5.4 Dynamic Mechanical Thermal Analysis...........................................228
References ..............................................................................................................229
9.1 INTRODUCTION
Plastics have become an indispensable part of human life. These are high molecu-
lar weight polymers that can be molded into desired shapes such as films, trays, bot-
tles, and jars using heat and pressure. These are now rivals to metals in breadth of use
and in severity of applications because of their flexibility, toughness, excellent barrier
and physical properties, and their ease of fabrication (Fang and Fowler 2003; Orhan
et al. 2004). The use of fossil fuels such as naphtha and natural gas for producing plas-
tics accounts for about 4% to 5% of the world’s oil consumption, with the demand
increasing in the future. Society has challenged this demand in order to reduce the
exploitation of fossil fuel and to protect the climate through the reduction of carbon
dioxide (CO2) released as well as to preserve the environment from the harmful effects
of indiscriminate plastic disposal. These issues, especially the disposal of plastic
wastes in the environment, stimulated a demand for harmless, eco-friendly, and
biodegradable materials. This then evolved into the adoption of the recycling
concept through mechanical recovery and composting of wastes or energy pro-
duction by plastic incineration, which directly contribute toward a reduction in
the consumption of fossil raw materials in industry (Yulianaet al. 2012). How-
ever, the focus then began to shift to plastic production using natural biopolymers
as replacements for petrochemical substances. Biopolymers derived from various
TESTING AND QUALITY ASSURANCE OF BIOPLASTICS 203
natural resources have been regarded as alternative materials to petroleum plastic

because they are abundant, renewable, inexpensive, and biodegradable (Liu et al.
2005).
Bioplastics, as biodegradable plastics, are plastics that can be derived from plant-
and animal-based materials or from other renewable resources through a fermentation
process. This process requires low energy input and produces plastics with the ability
to degrade when being composted, yielding CO2 and water as end products. In fact,
bioplastics have become among the most innovative materials answering the
ever-increasing demand for more environmentally friendly solutions. Around the
world, especially in the leading industrialized nations, there is a great awareness in
the search for new raw materials or polymers to improve the quality and functionality
of bioplastics so that they can replace conventional plastics that are produced by pet-
rochemical industries.
During the last two decades, an increased interest in the use of natural biopolymers
has been apparent. Starch, cellulose, sugar, vegetable oil, and wood are the natural and
renewable raw materials most frequently used in the direct manufacturing of biode-
gradable plastics/ bioplastics or their bio-intermediaries. Queiroz and Collares-Queiroz
(2009) reported that starch-based bioplastic production comprised about 20% of the
total world production of bioplastics. But the utilization of bioplastics only contributes
to sustainability if the protection of the packed goods can be ensured because the value
of the resources put into and tied up in the packed goods is far higher than the value of
the packaging. This can be seen clearly using the example of roasted coffee. Here, the
total energy put into and tied up in coffee represents 90%, while the energy put into and
tied up in the packaging is only 10%. Naturally, this varies from product to product.
Nevertheless, we can conclude that a product loss resulting from the use of unsuitable
packaging materials cannot be compensated by savings in packaging material costs
(Schmid and Agulla 2012).
The first priority in the development and application of new, more sustainable
packaging concepts must therefore be adequate protection of the product. A reduction
in material only contributes to sustainability if the protection of the product remains
ensured. If, for example, an existing packaging material satisfies precisely the mini-
mum requirements with respect to the permeation properties, a further reduction in
the material is only possible by optimizing the material properties. A further possibi-
lity and additional opportunity of improving the sustainability of packaging systems is
offered by material substitution where, for example, petrochemical-based materials
are replaced by biopolymers such as the substitution of a whey protein-based barrier
layer for ethyl vinyl alcohol (Schmid et al. 2012).
The term “biopolymer” often causes confusion. According to the most commonly
used definition, a biopolymer is a polymer material that either consists of bio-based
(renewable) raw materials or that is biologically degradable, or both (Endres and
Siebert-Raths 2011). Although this definition is accepted by experts as being generally
valid, it is neither regulated by law nor standardized. The industrial association, European
Bioplastics, also takes the view that this definition is appropriate for the term biopolymer.
Taken at face value, the term biopolymer implies sustainability. Biopolymers do have
weaknesses, however, also—and particularly when—it comes to their use as a packaging
204
Table 9.1 Material Properties of Some Conventional and Bioplastics Available in the Market
Conventional Plastics Bioplastics
Property Polyethylene Films Polypropylene PVC PET PLA PGA PHB PCL
3
Density (g/cm ) 0.91–0.97 0.89–0.91 1.35–1.41 1.29–1.40 1.21–1.25 1.50–1.70 1.18–1.26 1.11–1.14
Tg (°C) −120 −10 75–100 73–80 45–60 35–45 5–15 −60 to −65
Tm (°C) 105–138 160–175 212 245–265 150–162 220–233 168–182 58–65
Tensile strength (Mpa) 8–45 31–240 10–55 48–270 21–60 60–99.7 40 20.7–42.0
Tensile modulus (Gpa) 0.2–1.1 1.1–2.4 0.4–4.1 2.8–4.1 0.35–3.5 6–7 3.5–4 0.21-0.44
Elongation % 10–1200 30–650 14–450 30–3000 2.5–6.0 1.5–20.0 5–8 300–1000
Note: Tg, glass transition temperature (°C); Tm, melting temperature (°C).
material for sensitive foodstuffs (Schmid and Agulla 2012). Although biopolymers can
completely cover the whole range of conventional film materials with respect to their
mechanical properties, their barrier properties are still very limited. Their barrier proper-
ties generally are not sufficient to adequately protect products particularly as a packaging
material for delicate sensitive foodstuffs such as butchery products.
This chapter will describe the most important measurement methods for detecting
the physical, mechanical, and optical properties of biopolymer films (Table 9.1).
9.2 TESTING METHODS
A test may be generally defined as the act of determining a given property or char-
acteristic of a product (plastic material) by taking one or more measurements qualita-
tively or quantitatively, according to a prescribed procedure. With the advent of science
and technology, the concept of testing became an integral part of research and devel-
opment, product design, and manufacturing. The manner in which things were done
in the past has changed with time. Nowadays, the emphasis is on automation, high
production, and cost reduction. There is a growing demand for intricately shaped,
high-tolerance parts. Consumer awareness, a subject totally ignored by the manufac-
turers once upon a time, is now a major area of concern. Along with requirements,
our priorities have also changed. When designing a machine or a product, the first
order of priority in most cases is safety and health. Manufacturers and suppliers are
now required to meet a variety of standards and specifications. Obviously, relying merely
on past experience and quality of workmanship is simply not enough (Shah 2007).
The following are some of the major reasons for testing:
1. To prove design concepts

2. To provide a basis for reliability
3. Safety
4. Protection against product liability suits
5. Quality control
6. To meet standards and specifications
7. To verify the manufacturing process
8. To evaluate competitors’ products
9. To establish a history for new materials
9.2.1 Testing of Physical Properties
The important physical properties of bioplastics are mass, density, and dimensions.
The obvious connection among mass, density, and dimensions, is that density can be
derived from knowledge of dimensions and mass. However, they have been grouped
together largely for convenience, and also because they are measurements that are
essential parts of other physical tests. For example, density is used to calculate volume
loss in an abrasion test, mass is an intrinsic factor in water absorption tests, and there are
very few tests that do not in some way involve the measurement of dimensions.
Mass, dimensions, and density are also important factors in the costing of products.
In quality control, checking dimensional accuracy of components is one of the most
basic quality control procedures, while mass is an essential consideration in controlling
the quantity of ingredients and so on. Density can also be a useful control measure to
monitor variation in materials (Brown 2002).
9.2.1.1 Thickness
Thickness is the perpendicular distance between the two outer surfaces of a mate-
rial. Many physical properties of plastic materials are dependent upon thickness. In the
case of films, the resistance to gas transmission increases directly with an increase in
thickness. Strength properties such as stiffness are also influenced by thickness. Film
thickness is measured by using a micrometer (Rhim et al. 2007). Generally, thickness
is measured at different locations on the sample, and the mean is calculated. Typical
micrometers reading in one-ten-thousandth of an inch (0.0001 in.) or even fifty-
millionth (0.00005 in.) increments are simply not sensitive enough. The thickness
can also be measured via a microscope (microtome cut) or also via a scanning
electron microscope when it comes to very thin films (<1 μm). Mean thickness
for control soy protein isolate (SPI) and polylactic acid (PLA) films were 78.8 μm
and 89.5 μm, respectively (Rhim et al. 2007).
9.2.1.2 Density
Density can be a very important design parameter because elevated density values
imply high transportation costs (e.g., light car parts reduce energy consumption).
Implementation of material also becomes much easier and less hazardous when the
material is lighter. Density is often used for the calculation of “specific properties”
(i.e., dividing mechanical properties by the appropriate density). These specific prop-
erties consequently give a better notion of the intrinsic strength of the construction one
wants to build (Van de Velde and Kiekens 2002).
The International Standards Organization’s ISO 2811-1:2011 specifies a method
for determining the density of paints, varnishes, and related products using a metal or
Gay-Lussac pycnometer. The method is limited to materials of low or medium visc-
osity at the temperature of test. The Hubbard pycnometer can be used for highly vis-
cous materials. ISO 2811-2:2011 specifies a method for determining the density of
paints, varnishes, and related products using balls or other round bodies as immersion
bodies (plummets). The method is limited to materials of low or medium viscosity,
and is particularly suitable for production control.
9.2.1.3 Mass
Mass is used to produce a force in test methods. Mass is measured by weighing the
test piece or object in question using an appropriate balance or scales. As the magnitude
and the accuracy needed varies, the weighing instrument has to be selected accordingly.
Accuracies required are often written in terms such as accurate to 1 mg, whereas
balances may be quoted as reading to 1 mg. The two are not the same, and the standards
are not always clear (Brown 2002). ISO 536:2012 specifies a method for determining
the grammage of paper and board.
9.2.2 Testing of Mechanical Properties
Mechanical properties are often the most important among all the properties of
plastic materials because virtually all service conditions and the majority of end-use
applications involve some degree of mechanical loading (Shah 2007). The mechan-
ical properties of biopolymers can be tailored by changing the material formulation
(i.e., particularly the blend composition) and by compounding with additives. In
addition, mechanical properties—as well as various other properties (e.g., barrier
properties)—are influenced to a significant extent by the manufacturing parameters
during film generation (e.g., draw ratio), which is analogous to film manufacturing
with conventional plastics. Just as with conventional plastic films, biopolymer films
exhibit strongly anisotropic material behavior that depends on manufacturing and
processing parameters (Endres and Siebert-Raths 2011). The important mechanical
tests performed on bioplastics are tensile tests, impact tests, and compression and
puncture tests.
9.2.2.1 Tensile Tests
Tensile test analyses are made to determine the tensile strength (MPa), the percent
of elongation at yield (%), the percent of elongation at break (%), and the elastic mod-
ulus (GPa) of a bioplastic material. These values are important to obtain mechanical
information for bioplastic materials that are to be compared with commercial
nonbiodegradable materials, according to ASTM D882, Standard Test Method for
Tensile Properties of Thin Plastic Sheeting (Siracusa et al. 2008).
A tensile test, in a broad sense, is a measurement of the ability of a material to with-
stand forces that tend to pull it apart and to determine to what extent the material
stretches before breaking. Tensile modulus, an indication of the relative stiffness of
a material, can be determined from a stress–strain diagram. Different types of plastic
materials are often compared on the basis of tensile strength, elongation, and tensile
modulus data. Many plastics are very sensitive to the rate of straining and environmen-
tal conditions. Therefore, the data obtained by this method cannot be considered valid
for applications involving load time scales or environments widely different from this
method. The tensile property data are more useful in preferential selection of a parti-
cular type of plastic from a large group of plastic materials, and such data are of limited
use in the actual design of a product. This is because the test does not take into account
the time-dependent behavior of plastic materials (Shah 2007).
Although tensile strength behavior is similar, the impact strength behavior of
biopolymers is quite the opposite. The highly rigid and high-strength PLA materials, cel-
lulose derivates, and polyhydroxyalkanoates exhibit the weakest Charpy impact strength
among biopolymers. Thus, they are best compared with polyethylene terephthalate (PET)
as a less impact-resistant material. On the other hand, the biopolyesters, starch, and PLA
blends exhibit the highest Charpy impact strength values and are most similar to high-
density polyethylene (HDPE). Moreover, the relationships between stiffness and impact
strength, and tensile strength and impact strength, show a similar tendency to modulus of
elasticity as a function of elongation at break. That means that modulus of elasticity and
tensile strength in biopolymers decrease with increasing impact strength, just as they do
in conventional plastics (Endres and Siebert-Raths 2011).
In this example, tensile strength and elongation at the break of each film tested
were determined with an Instron Universal Testing Machine (Model 5565, Instron
Engineering Corporation, Canton, MA) according to ASTM Method D882. Rectan-
gular specimens of 2.54 × 15 cm were cut using a precision double blade cutter
(Model LB.02/A, Metrotec, S.A., San Sebastian, Spain). Initial grip separation was
set at 50 mm and the cross-head speed was set at 50 mm/min. Tensile strength was
calculated by dividing the maximum load to break the film by the cross-sectional
area of the film, and elongation was calculated by dividing film elongation at rupture
by the initial gauge length of the specimen and multiplying by 100. Tensile strength of
SPI film was 2.8 MPa and of PLA was 17.2 MPa. These values are comparable to
those of widely used plastic films such as low-density polyethylene (LDPE) and
HDPE. Elongation for SPI and PLA was 165.5% and 203.4%, respectively (Rhim
et al. 2007).
With their wide range of stiffness and impact toughness characteristics, biopo-
lymers cover the field of conventional plastics. The modulus of elasticity of various
polyesters, including polyhydroxyalkanoates and some PLA and starch blends, cor-
responds to the modulus of elasticity of comparable conventional petrochemical
HDPE and polypropylene (PP). In addition, cellulose derivates and various other
starch and PLA blends even exhibit elastic deformation resistance approximately
as high as that of the highly rigid PET and acrylonitrile butadiene styrene (ABS)
grades. In fact, PLA materials actually exhibit the highest elastic deformation resis-
tance. These high stiffness values are achieved by special measures to increase crys-
tallinity in PLA materials (Endres and Siebert-Raths 2011).
9.2.2.2 Impact Tests
The impact properties test is a method utilized to determine the energy that causes
bioplastic to fail under specific impact conditions and is conducted following the
guidelines in ASTM D1709, Standard Test Methods for Impact Resistance of Plastic
Film by the Free-Falling Dart Method (Siracusa et al. 2008).
9.2.2.3 Compression Tests
Compression tests normally are conducted on a thermoformed sample, according

to the ASTM D642, Standard Test Method for Determining Compressive Resistance
of Shipping Containers, Components, and Unit Loads. The compression strength is a
function of the material and of the design (shape and size) (Siracusa et al. 2008).
9.2.2.4 Puncture Tests
In this example, the puncture test (puncture force and puncture deformation) was
conducted using a TAXT2i Stable Micro Systems texture analyzer (SMS). For the
puncture test, circular sample films were fixed in a 40-mm-diameter cell and perfo-
rated using a 3-mm-diameter cylindrical probe moving at 1 mm/s (Gontard et al.
1993) in triplicate. The puncture force was determined directly from the force displa-
cement curves with Texture Expert V.1.15 (SMS) software. The puncture deformation
was calculated using the following equation:

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðD2 + l20 Þ − l0
Δl
PD = =
l0 l0
where lo is the initial disc radius (17 mm), and D is the distance penetrated at the break
point (Araujo-Farro et al. 2010).
9.2.2.5 Hardness Tests
Hardness is defined as the resistance of a material to deformation—particularly per-

manent deformation, indentation, or scratching. Hardness is purely a relative term and
should not be confused with wear and abrasion resistance of plastic materials. Polystyr-
ene, for example, has a high Rockwell hardness value but a poor abrasion resistance.
Hardness tests can differentiate the relative hardness of different grades of a particular
plastic. However, it is not valid for comparing the hardness of various plastics based
entirely on one type of test because elastic recovery along with hardness is involved.
Many tests have been devised to measure hardness. Because plastic materials vary con-
siderably with respect to hardness, one type of hardness test does not cover the entire
range of hardness properties encountered (Shah 2007).
Two of the most commonly used tests for plastics are the Rockwell and the Durom-
eter hardness tests. The Rockwell test is used for relatively hard plastics such as acetals,
nylons, acrylics, and polystyrene. For softer materials such as flexible PVC, thermoplas-
tic rubbers, and polyethylene, a Durometer hardness test is utilized.
9.2.2.5.1 Rockwell Hardness
The Rockwell hardness test (ASTM D785, Standard Test Method for Rockwell
Hardness of Plastics and Electrical Insulating Materials) measures the net increase
in depth impression as the load on an indenter is increased from a fixed minor load
to a major load and then returned to a minor load. The hardness numbers derived
are just numbers without units. Rockwell hardness numbers are always quoted with
a scale symbol representing the indenter size, load, and dial scale used. The hardness
scales in order of increasing hardness are the R, L, M, E, and K scales. The higher the
number in each scale, the harder the material. There is a slight overlap of hardness
scales; therefore, it is quite possible to obtain two different dial readings on different
scales for the same material. For a specific type of material, correlation in the overlap-
ping regions is possible. However, owing to differences in elasticity, creep, and shear
characteristics among different plastics, a general correlation is not possible.
Rockwell hardness is determined with an apparatus called the Rockwell hard-
ness tester. A standard specimen of 1/4-in. minimum thickness is used. The speci-
men can either be molded or cut from a sheet. However, the test specimen must
be free from sink marks, burrs, or other protrusions. The specimen also must have
parallel, flat surfaces.
The specimen is placed on the anvil of the apparatus and a minor load is applied by
lowering a steel ball onto the surface of the specimen. The minor load indents the specimen
slightly and ensures good contact. The dial is adjusted to zero under the minor load and the
major load is applied within 10 seconds by releasing the trip level. After 15 seconds, the
major load is removed and the specimen is allowed to recover for an additional 15 seconds.
Rockwell hardness is read directly off the dial with the minor load still applied.
9.2.2.5.2 Durometer Hardness
The Durometer hardness test (ASTM D2240, Standard Test Method for Rubber
Property—Durometer Hardness; ISO 868) is used for measuring the relative hardness
of soft materials. The test method is based on the penetration of a specified indentor
forced into the material under specified conditions.
The Durometer hardness tester consists of a pressure foot, an indentor, and an indi-
cating device. The indentor is spring-loaded, and the point of the indentor protrudes
through the hole in the base. The test specimens should be at least 1/4 in. thick and
can either be molded or cut from a sheet. Several thin specimens may be piled to
form a 1/4 in.-thick specimen, but one-piece specimens are preferred. Poor contact
between thin specimens may cause results to vary considerably.
The test is carried out by first placing a specimen on a hard, flat surface. The pressure
foot of the instrument is pressed onto the specimen, making sure that it is parallel to
the surface of the specimen. The durometer hardness is read within 1 second after the
pressure foot is in firm contact with the specimen. Two types of durometers are most
commonly used: Type A and Type D. The basic difference between the two types is
the shape and dimension of the indentor. The hardness numbers derived from either
scale are just numbers without any units. Type A durometer is used with relatively
soft material, and Type D is used with slightly harder material.
9.2.2.5.3 Barcol Hardness
The Barcol hardness test (ASTM D2583, Standard Test Method for Indentation
Hardness of Rigid Plastics by Means of a Barcol Impressor) was devised mainly
for measuring the hardness of both reinforced and nonreinforced rigid plastics. The
tester is a portable instrument that can be carried around to measure the hardness of
fabricated parts as well as test specimens. Barcol hardness tests consist of an indentor
with a sharp, conical tip and an indicating device in the form of a dial with 100 divi-
sions. Each division represents a depth of 0.0003-in. penetration. The test specimens
are required to be of 1/16-in. minimum thickness. The test is carried out by placing the
indentor onto the specimen and applying uniform pressure against the instrument. The
pressure is applied until the dial indication reaches maximum. The depth of penetra-
tion is automatically converted to a hardness reading in absolute Barcol numbers.
When measuring the Barcol hardness of reinforced plastic material, the variation in
hardness reading caused by the difference in hardness between resin and filler materi-
als should be taken into account. Generally, a larger sample size is recommended for
reinforced plastic specimens than that used for nonreinforced plastics.
9.2.3 Testing of Optical Properties
Unique properties, such as excellent clarity and transparency, good impact strength,
moldability, and low cost, have made plastics the number one choice of many design
engineers. Successful applications of transparent and translucent plastics include auto-
motive tail-light lenses, safety glasses, window glazing, merchandise display cases,
and instrument panels. Plastics are much more resistant to impact than glass; therefore,
in applications such as street-lamp globes and high school windows, glass has been
replaced by high-impact, vandal-resistant plastic materials such as polycarbonate.
Almost all plastics, below a certain minimum thickness, are translucent. Only a few
plastics are transparent. Plastic materials’ transparency or translucency depends upon
their basic polymer structure. Generally, all amorphous plastics are transparent. Crystal-
linity increases the density of the polymer, which decreases the speed of light passing
through it, and this increases the refractive index. When crystals are larger than the wave-
length of the visible light, the light passing through many successive crystalline and
amorphous areas is scattered, and the clarity of the polymer is decreased. A large single
crystal scatters light at wide angles and thus causes haze. As a rule, crystalline plastics
are translucent. However, the clarity of crystalline plastics can be improved by quench-
ing or random copolymerization (Shah 2007). The primary optical properties are:
1. Refractive index
2. Light transmittance and haze
3. Color
4. Gloss
9.2.3.1 Refractive Index
The refractive index (ISO 489) is a fundamental property of transparent materials.

Refractive index values are very important to an engineer involved in designing lenses
for cameras, microscopes, and other optical equipment. The refractive index, also
known as the index of refraction, is defined as the ratio of the velocity of light in a
vacuum (or air) to its velocity in a transparent medium.
Index of refraction = sin of angle of incidence/sin of angle of refraction
Two basic methods are most commonly utilized to determine the index of refraction.
The first method, known as the refractometric method, requires the use of a refract-
ometer. An alternate method calls for the use of a microscope with a magnification
power of at least 200 diameters. The refractometric method is generally preferred over
the microscopic method because it is much more accurate. The microscopic method,
which is dependent upon the operator’s ability to focus, is usually less accurate.
9.2.3.2 Refractometric Method
The Abbé refractometer is most widely used to determine the index of refraction.
The test also requires a source of white light and a contacting liquid that will not attack
the surface of the plastic. The contacting liquid must also have a higher refractive
index than the plastic being measured. A test specimen of any size may be used as
long as it conveniently fits on the face of the fixed half of the refractometer prism.
The surface of the specimen in contact with the prism must be optically flat and polished.
The test is carried out by placing a specimen in contact with the prism using a drop
of contacting fluid. Contacting fluid must have a higher refractive index than the sam-
ple to be analyzed. Next, looking through the eye piece, the shadowline control knob
is adjusted until the shadowline comes into the field of view. The dispersion correction
wheel is adjusted to remove all the color from the shadowline. The shadowline should
appear black with a sharp boundary, with a white to off-white background. Finally, the
edge of the shadowline is aligned with the center of the crosshairs, and the value of the
index of refraction is read.
9.2.3.3 Microscopical Method
In this method, a microscope having a magnifying power of 200 diameters or more

is used along with a specimen of a convenient size, having a fair polish and two par-
allel surfaces. The test is carried out by alternately focusing the microscope on the top
and the bottom surface of the specimen and accurately reading the longitudinal displa-
cement of the lens tube. The difference between the two readings is considered the
apparent thickness of the specimen. The index of refraction is determined as follows:
Refractive index = actual thickness/apparent thickness
9.2.3.4 Luminous Transmittance and Haze
Luminous transmittance (ASTM D1003, Standard Test Method for Haze and Lumi-
nous Transmittance of Transparent Plastics) is defined as the ratio of transmitted light to
the incident light. The value generally is reported in percentage of light transmitted.
Haze is the cloudy appearance of an otherwise transparent specimen caused by light
scattered from within the specimen or from its surface. Haze is defined as the percentage
of transmitted light that, in passing through a specimen, deviates from the incident beam
by forward scattering. It is generally accepted that if the amount of transmitted light is
deviated more than 2.5° from the incident beam, the light flux is considered to be haze.
Haze is normally caused by surface imperfections, density changes, or inclusions that
produce light scattering. Haze is also reported in percentages.
Light transmittance and haze are extremely important from a practical viewpoint. For
example, a window glazing material must have high light transmittance characteristics
and must be free from haze. In contrast, the housing material for the light fixture must
have maximum diffusion and minimum transparency to conceal the bright light source.
The housing material must also have high light transmittance. In our example, transmit-
tance values of the control SPI and PLA films were 91.3% and 95.1%, respectively
(Rhim et al. 2007).
9.2.3.5 Color
The ability of plastic materials to color with relative ease and the fact that color can
be integrated throughout the entire structure have made plastics one of the most suc-
cessful materials of this century. To comprehend color measurement, specification,
and tolerances, a proper understanding of color theory is essential.
The instrument developed for color measurement is called a colorimeter. A tristimu-
lus colorimeter measures color in terms of three primary colors: red, green, and blue, or
more properly stated, in terms of three tristimulus values. Many different color scales
have been developed to describe color numerically in terms of lightness and hue.
One of the most widely accepted systems is known as the L, a, b tristimulus system.
The coordinate L is in the vertical direction and corresponds to lightness. A perfect
white has an L value of 100 and a perfect black value of zero. The variables aL and
bL identify the hue and the chroma of the material, respectively. A plus value of aL indi-
cates redness and a minus value greenness. For example, a school bus yellow with the
following values describes a color: L = 70.3; aL = 30.3; bL = 23.7. This color can be
described in common terms as fairly light, as indicated by a high L value, and yellowish
red, as indicated by the aL and bL values. The filter colorimeter described thus far is
based on the theory of the standard observer and how the human eye perceives the
color. This approach has been described as a “psychophysical” approach to measure-
ment. There are some problems associated with the design of filters and the filter
material’s ability to retain originality with time.
In recent years, new generations of colorimeters based on spectrophotometers
have been developed. The spectrophotometric colorimeter does not mimic the
human eye. Instead, it makes a spectrophotometric measurement at sixteen 20-nm
intervals over the entire range of the visible spectrum. The percentage reflectance
value obtained by the spectrophotometer is converted into tristimulus values through
the use of a microprocessor. One other useful feature added to these spectrophoto-
metric colorimeters is the ability to select various types of CIE (Commission
Internationale de l’Eclairage) illuminants. Even though the actual light source
remains the same, the microprocessor computes the colors that would be seen if the
samples were viewed under various illuminants. For color development work, a col-
orimeter that provides the tristimulus value and calculates the color difference is sim-
ply not enough. A more sophisticated instrument such as a spectrophotometer
generally is required. A spectrophotometer, when used with a chart recorder or cath-
ode ray tube (CRT), provides a complete spectral reflectance curve covering the entire
range of the visible spectrum from 380 nm to 700 nm. Additionally, it provides the
percentage reflectance value at each 20-nm interval and computes the tristimulus
values, chromaticity coordinates, and color difference values.
9.2.3.5.1 Instrumented Color Measurement
Two basic types of instruments are used for color measurements depending on
what is required. A filter colorimeter or a spectrophotometric colorimeter is utilized
when the user is only interested in tristimulus values, chromaticity coordinates, and
color difference information. Colorimeters are mainly used for production control,
quality control, specification, and color-matching requirements. A spectrophotometer
is normally required for color formulation and other color development work.
The operation of this modern spectrophotometer is very simple. The instrument is
first calibrated using a calibration standard. Next, the desired CIE standard illuminant
is selected. By placing a relatively flat, colored specimen to be measured in a specimen
holder and illuminating a light source, one can instantly obtain percentage spectral
reflectance values at 16-nm intervals over the visible spectrum. The microprocessor
also computes and displays the CIE Lab color space and a spectral reflectance
curve as a function of wavelength. Color matching is carried out simply by exposing
an unknown specimen and a control specimen to the illuminant and then comparing
the two overlapping spectral reflectance curves.
As an added bonus, most available colorimeters and spectrophotometers calculate
the yellowness index (ASTM D1925, Test Method for Yellowness Index of Plastics)
and the whiteness index. ASTM D2244, Standard Practice for Calculation of Color
Tolerances and Color Differences from Instrumentally Measured Color Coordinates,
describes the standard method for instrumental evaluation of color differences of
opaque materials in detail.
There have been many new developments in color measurement systems technol-
ogy in recent years. A major breakthrough is in the area of portable color measurement
techniques. Newly developed portable spectrophotometers now make it possible to
measure and analyze data on the production floor. Some portable spectrophotometers
are also capable of displaying an actual spectral reflectance curve. Bench-top spectro-
photometers have been updated to allow more computer control of the lens, ultraviolet
(UV) filter, and specular port. The ability to calibrate the UV component of the color
spectrum is an important feature for accurately measuring fluorescent colors.
Advances in Windows-based software have improved the capabilities for statistical
analysis of color measurements, color corrections, and color formulation.
Continuous online measurement colorimeters also have been developed. These
units are designed to withstand a harsh industrial environment, allowing continuous
monitoring of the color of compounded pallets and other extruded or molded products.
Color information is received in real-time mode, allowing the user to spot off-color
trends and correct the process.
9.2.3.5.2 Specular Gloss
Specular gloss (ASTM D2457, Standard Test Method for Specular Gloss of Plas-
tic Films and Solid Plastics; ASTM D523, Standard Test Method for Specular Gloss)
is defined as the relative luminous reflectance factor of a specimen at the specular
direction. This method has been developed to correlate the visual observations of
surface shininess made at roughly corresponding angles. A light beam is directed

toward a specimen at a specified angle and the light reflected by the specimen is
collected and measured. All specular gloss values are based on a primary reference
standard—a highly polished black glass with an assigned specular gloss value of 100.
Three basic angles of incidence (20°, 60°, and 85°) are used for specular gloss measure-
ment of plastic parts. As the angle of incidence increases, the value of gloss of any surface
also increases. The glossmeter basically consists of a source-optical assembly, which
houses an incandescent light source, a condenser lens, and a projection or source lens.
An incident beam, created by this assembly, is directed toward the specimen. A sensitive
photodetector collects the reflected light and generates an electrical signal that is
amplified to energize an analog or digital panel meter to display the value in gloss units.
The operation of a glossmeter is very simple. The instrument is turned on and
placed on a black glass primary standard. The control knob is adjusted so that the
meter indicates the value assigned to the primary standard. Next, the sensor is placed
on the specimen surface and the gloss value is read directly from the analog or digital
display. The linearity of the instrument is routinely checked by placing the sensor on a
white secondary standard, which should read within 1.0 gloss unit of the assigned
value of that standard.
9.2.4 Permeability Testing
In contrast to packaging materials made from glass or metal, packages made from
thermoplastic polymers are permeable, in varying degrees, to small molecules such
as gases, water vapor, organic vapors, and other low molecular weight compounds.
A plastic polymer that is a good barrier has a low permeability. The variable blend
components (e.g., in PLA or starch blends) or the different monomer contents in copo-
lymers (e.g., different degrees of hydrolysis and different amounts of ethylene in
PVAL/PVA [polyvinyl alcohols]) lead to a wide range of individual barrier measurement
data within a single group of biopolymer materials (Endres and Siebert-Raths 2011).
The permeability of plastic films to moisture vapor and common gases such as oxygen,
carbon dioxide, and nitrogen has been measured by standardized test methods.
9.2.4.1 Water Vapor Permeability Test
The polar biopolymers, and especially the very hydrophilic biopolymer PVAL/PVA
as well as the starch- and cellulose-based materials, generally exhibit very high water
vapor permeability or, inversely, very low water vapor barrier properties. Water
vapor transmission rates below 100 g/m2d are considered satisfactory and represent suf-
ficiently high water vapor barrier properties. In this respect, only polyhydroxyalkano-
ates (PHAs) and coated PLA materials exhibit high water vapor barrier properties
that lie in the same range as those of conventional plastic packaging materials (Endres
and Siebert-Raths 2011).
In this example, the apparatus and methodology described in ASTM E96, Stan-
dard Test Methods for Water Vapor Transmission of Materials, were used to measure
the water vapor permeability (WVP) of the film. Film specimens were conditioned for
48 h in a chamber at 25°C and 52% relative humidity (magnesium nitrate-saturated

solution) before being analyzed. Films were sealed on cups containing distilled
water. Test cups were placed in a desiccator cabinet maintained at a controlled tem-
perature and relative humidity (lithium chloride-saturated solution). To determine
film thickness and the plasticizer effect on WVP, tests were done at 30°C. To study
the temperature influence on WVP, samples were analyzed in a temperature range
between 5°C and 40°C. A fan was used to maintain uniform conditions at all test loca-
tions over the specimen. Periodical weightings monitored the weight changes. Weight
loss was plotted over time and, when steady state (straight line) was reached, 6 h more
were registered. The WVP was calculated from the slope (G) of a linear regression of
weight loss versus time
Gx
WVP =
A Δp
where x is the film thickness, A is the area of exposed film, and Δp is the differential
water vapor partial pressure across the film. This method uses Fick’s first law and
Henry’s law to calculate film WVP and assumes that film solubility and diffusivity
are constant (Bertuzzi et al. 2007). WVP measured values were corrected for the air
gap distance between the water level and the film position according to procedures
outlined in Gennadios et al. (1994). The WVP of the SPI films was 268.30 × 10−14
kg m/m2s Pa and, for the PLA films, 4.66 × 10−14 kg m/m2s Pa (Rhim et al. 2007).
9.2.4.2 Oxygen Permeability
Polar materials such as biopolymers are poor barriers to polar water but, on the
other hand, they exhibit high barrier properties against nonpolar oxygen and nitrogen.
In this respect, PVAL/PVA exhibits excellent barrier properties against oxygen, simi-
lar to those of ethylene vinyl alcohol (EVAL). Besides their good water vapor barrier
properties, PHAs also exhibit excellent oxygen barrier qualities. All in all, PHAs make
excellent packaging materials. Unfortunately, it is quite difficult to process PHAs into
films, and the process has not yet been satisfactorily optimized. The oxygen barrier
properties of PLA are comparable to those of other packaging materials such as
PET, PE, and PP, and PLA also exhibits good barrier properties for aromas. Only
EVAL and PET exhibit oxygen barrier properties superior to those of the other packa-
ging materials and the biopolymers mentioned (Endres and Siebert-Raths 2011).
The oxygen permeability tests were performed using an Oxysense 4000B device
equipped with a film permeation chamber. All experiments were performed at 23°C
and 50% relative humidity. The permeation chamber consists of a cylinder divided
in two parts by the investigated film. One of these is instrumented with a UV sensor
sensitive to the oxygen ratio. This last chamber is purged with nitrogen while the other
is kept open to air. The experiment thus consists of monitoring the oxygen uptake with
time. Oxysense OTR software uses this oxygen evolution to determine the oxygen
transmission rate (OTR). Because the OTR value is relative to both thickness and
partial pressure between rich and poor oxygen atmospheres, results were normalized
using the following equation (Robertson 2009):
OTR e
OP =
Δp
where OP is the oxygen permeability coefficient (mL m−1 s−1·Pa-1), OTR is the oxy-
gen transmission rate (mL m−2 s−1), e is the film thickness (m), and Δp is the oxygen
partial pressure difference (Pa). In our experimental setting, the oxygen Δp was 0.21
atm, that is, 2.127 × 104 Pa (Corre et al. 2012).
9.2.5 Rheological Measurements
Rheology is defined as the study of flow, and viscosity is the measure of resistance to
flow due to internal friction when one layer of fluid is caused to move in relationship to
another layer. The force required to cause this movement is called shear. Shearing occurs
whenever the fluid is physically moved or disturbed such as in pouring, mixing, and
spraying. Highly viscous fluids, therefore, require more force to move than less viscous
materials. The velocity gradient is a measure of the speed at which the intermediate layers
move with respect to each other. It describes the shearing the liquid experiences and is
thus called shear rate. Shear stress is the stress developing in the polymer melt when the
layers in a cross section are gliding along each other. When the ratio of shearing stress to
the rate of shear is constant, as in case of water, the fluid is called a Newtonian fluid. In the
case of non-Newtonian fluids, the ratio varies with shearing stress or, in other words,
when shear rate is varied, the shear stress does not vary in the same proportion. The visc-
osity of such fluids will change with the change in shear rate. All polymeric materials
exhibit non-Newtonian flow behavior. This information concerning the flow of poly-
meric material is very useful in identification and characterization of polymers.
Rheological measurements are very useful in the determination of molecular, elas-
tic, and physical properties of polymers and as well as in simulation, determination of
large-scale processing conditions, and basic research and development. Instruments
developed for measuring the flow properties of polymers are known as rheometers.
Many different types of rheometers have been developed. Data analysis and interpre-
tation has been simplified with newly developed Windows-based software.
Until recently, rheological measurements were confined to test labs for quality
control, research, and development purposes. New techniques for online rheological
measurements have been developed, bringing the analytical instrumentation to the
production floor. This is accomplished by utilizing a closed-loop instrument that
diverts a portion of the process stream to a measurement head and then returns it to
the process. Within the measurement head, most of the material flows through a
bypass channel, and a fraction of the stream is pumped across a capillary die, using
precision gear pumps. A similar concept, used by another manufacturer, utilizes a
slit die to measure viscosity. An open-loop online rheometer, which does not return
the diverted melt stream to the process after measurement, splits the diverted melt
stream into two capillary dies of different L/D ratios to enable simultaneous determi-
nation of viscosity at two different shear rates (Shah 2002).
9.2.5.1 Viscosity Tests
Viscosity is defined as the property of resistance to flow exhibited within the body
of a material and is expressed in terms of a relationship between applied shearing
stress and the resulting rate of strain in shear. In the case of ideal or Newtonian visc-
osity, the ratio of the shear stress to the shear rate is constant. Plastics typically exhibit
non-Newtonian behavior, which means that the ratio varies with the shearing stress.
There are two different aspects of viscosity: Dynamic or absolute viscosity, best deter-
mined in a rotational type of viscometer with a small gap clearance, is independent of the
density or specific gravity of the liquid sample and is measured in poises (P) and cen-
tipoises (cP). Kinematic viscosity, usually determined in some form of efflux viscometer
equipped with a capillary bore or small orifice that drains by gravity, is strongly depen-
dent on the density or specific gravity of the liquid, and is measured in stokes (S) and
centistokes (cS). The relationship between the two types of viscosity is
Stokes × specific gravity = poises
The measurement and control of rheological properties are usually performed with
simple devices called “viscometers” or “viscosimeters” that do not measure true visc-
osities of either the dynamic or kinematic type but make relative flow comparisons.
Viscosity of plastic materials is measured in three basic ways, utilizing principles
involving liquid deformation due to various forces:
1. Downward rate of gravity flow through capillary bores and small orifices
2. Upward speed of a trapped air bubble
3. Torque developed by the liquid drag between moving and stationary surfaces
The first method is basically used for thermoplastic materials. The latter two are
more commonly used for thermosetting materials, plastisols, and organosols (Shah
2007).
9.2.5.2 Melt Index Test
The melt index, more appropriately known as the melt flow rate, test (ASTM
D1238, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion
Plastometer; ISO 1133) measures the rate of extrusion of a thermoplastic material
through an orifice of specific length and diameter under prescribed conditions of tem-
perature and load. This test is primarily used as a means of measuring the uniformity of
the flow rate of a material. The reported melt index values help to distinguish among
the different grades of a polymer. A high-molecular-weight material is more resistant
to flow than a low-molecular-weight material. However, the data obtained from this
test does not necessarily correlate with the processability of the polymer. This is
because plastic materials are seldom manufactured without incorporating additives
that affect their processing characteristics, such as stability and flowability. The effect
of these additives is not readily observed via the melt index test. The rheological char-
acteristics of polymer melts depend on a number of variables. Because the values of
these variables may differ substantially from those in large-scale processes, the test
results may not correlate directly with processing behavior.
Test Procedures: The melt index apparatus is preheated to a specified temperature.
The material is loaded into the cylinder from the top and a specified weight is placed
on a piston. The material is allowed to flow through the die. The initial extrudate is
discarded because it may contain some air bubbles and contaminants. Depending on
the material or its flow rate, cuts for the test are taken at different time intervals. The
extrudate is weighed and melt index values are calculated in grams per 10 min.
An alternate method for measuring materials with a high flow rate involves auto-
matic timing of the piston travel by some electrical or mechanical device. The melt
index value is calculated using the following formula:
Flow rate = (426 × L × d)/t
where L = length of calibrated piston travel (cm); d = density of resin at test tempera-
ture (g/cm3); and t = time of piston travel for length L (sec) (Shah 2007).
9.2.6 Environmental Stress Cracking
This test gives indications of the influence of some reagents such as soaps, wetting
agents, oils, or detergents on plastics. The procedure is to expose the specimens to
these environments for a specific time and to observe the cracks. The test report con-
sists of the percentage of failure.
9.2.6.1 Environmental Stress-Cracking Resistance
Environmental stress cracking (ASTM D1693, Standard Test Method for

Environmental Stress-Cracking of Ethylene Plastics; ISO 4599) is the failure, in
surface-initiated brittle fracture, of a polyethylene specimen or in a part under polyaxial
stress in contact with a medium in the absence of which fracture does not occur under
the same conditions of stress. Combinations of external and/or internal stresses may
be involved, and the sensitizing medium may be gaseous, liquid, semisolid, or solid.
Several conditions must be present for environmental stress cracking to occur.
First, the presence of a “stress riser” or a “notch” is a very important factor. The need
for some type of stress, “molded-in” or external, is inevitable. Finally, without the pre-
sence of an external sensitizing agent, environmental stress cracking is impossible.
Environmental stress cracking describes the tendency of polyethylene products to
prematurely fail in the presence of detergents, water, sunlight, oil, or other active
environments, usually under conditions of relatively high strain. It is a purely physical
phenomenon that involves no swelling or similar mechanical weakening of the
material. Polyethylene products are most susceptible to such cracking or crazing
under load when exposed to certain chemicals and environments. This phenomenon
was first recognized in polyethylene-coated wire, which often was lubricated with
surface-active materials to facilitate installation in conduits. Under these conditions,

polyethylene, which appeared to perform satisfactorily in the laboratory, rapidly
developed severe cracks that propagated completely through to the conductor. The
stress-cracking resistance of polyethylene can be improved by increasing molecular
weight, reducing stresses by proper fabrication practices, and incorporating elasto-
mers in the formulation. It is further observed that narrow molecular-weight distribu-
tions considerably improve the resistance of a polymer of given density and average
molecular weight. Large crystalline structures and molecular orientations appear to
aggravate the problem (Shah 2007).
9.3 COMPOSITIONAL ANALYSIS
9.3.1 Molecular Weight Using Gel Permeation Chromatography
When evaluating the nature of an incoming plastic’s material is important to a pro-

cessor, he must look for a more reliable technique that will provide the necessary
information to allow him to qualify the material, such as the measurement of molecu-
lar weight distribution. The molecular weight distribution is the single most funda-
mental property of a polymer. The molecular weight distribution not only provides
basic information regarding the processability of the polymer but also gives valuable
information for predicting its mechanical properties.
Gel permeation chromatography (GPC) is the method of choice for determining the
molecular weight distribution of a polymer. This technique has gained wide acceptance
among the plastic material manufacturers and processors because of its relatively low
cost, simplicity, and ability to provide accurate and reliable information in a short
time. GPC reveals the molecular weight distribution of a polymer compound. It detects
not only the resin-based molecules, such as polymers, oligomers, and monomers, but
most of the additives used in plastic compounds and even detects low-level impurities.
The molecular weight distribution curve is plotted for a well-characterized standard
material and the profile of the curve is compared with the test sample. In this manner,
batch-to-batch uniformity can be checked quickly as a means of quality assurance.
The separation of polymer molecules by GPC is based upon the differences in their
effective size in solution. (Effective size is closely related to molecular weight.) Separa-
tion is accomplished by injecting the polymer solution into a continuously flowing
stream of solvent that passes through highly porous, tiny, rigid gel particles closely
packed together in a tube. The pore size of the gel particles may vary from small to
very large. As the solution flows through the gel particles, molecules with small effec-
tive sizes (low molecular weights) will penetrate more pores than molecules with large
effective sizes and, therefore, will take longer to emerge than the large molecules. If the
gel covers the right range of molecular sizes, the result will be a size separation, with the
largest molecules exiting the gel-packed tubes (columns) first.
In our example, average molecular weights were estimated by GPC (Waters 1525,
USA) with a combination of four styragel column series (Styragel HR, 5 mm) at
40°C. A 2414 differential refractive index detector and UV detector were utilized.
Chloroform was used as an eluent at a flow rate of 1.0 mL/min. The sample concen-
tration was 1.5 mg/mL and the injection volume was 50 mL. Polystyrene standards
with low polydispersities were used to generate a calibration curve (Wang et al. 2009)
9.3.2 Analytical Tests
9.3.2.1 Water Absorption
The tendency of bioplastics to absorb moisture simply cannot be overlooked

because even the slightest amount of water can significantly alter some key mechan-
ical, electrical, or optical property. Water absorption characteristics of bioplastics
(ASTM D570, Standard Test Method for Water Absorption of Plastics; ISO 62)
depend largely upon the basic type and final composition of a material. Water absorp-
tion characteristics of bioplastic materials are altered by the addition of additives such
as fillers, glass fibers, and plasticizers.
Starch blends and cellulose derivates exhibit particularly high moisture absorp-
tion values. In principle, all biopolymer grades show clearly higher moisture absorp-
tion values than nonpolar PE-HD and PP materials but only slightly higher moisture
absorption than PET or ABS. Thorough drying prior to processing is mandatory,
especially for hydrophilic cellulose derivates as well as for the hydrolysis-sensitive
PLA materials. In PLA, residual moisture should not exceed 0.0l wt.% prior to injec-
tion molding and 0.025 wt.% prior to extrusion. By contrast, there is no need to pre-
dry the aliphatic polyolefins PE and PP. However, the polar, aromatic polymers ABS
or PET also have to be pre-dried prior to thermoplastic processing (Endres and
Siebert-Raths 2011).
The test to determine the water absorption of plastics is relatively simple. Only two
pieces of equipment are required—an analytical balance and an oven capable of main-
taining a uniform temperature. The test specimen may be a molded disk or a piece cut
from a sheet, rod, or tube. Dimensions vary according to the type of specimen. A spe-
cial conditioning procedure must be followed before actual testing.
The specimens are dried in an oven at a specified temperature for a predetermined
time, cooled in a desiccator, and immediately weighed. The percent increase in weight
during immersion is calculated as follows (Shah 2007):
Wet weight − Conditioned weight
Increase in weight percent = 100
Conditioned weight
Water absorption (Ab) was measured according to ASTM D570. Water absorption
was calculated as follows:
ðW1 − W0 + Wsol Þ
Ab = 100
W0
where W1, W0, and Wsol are the weight of the specimen containing water, the weight
of the dried specimen, and the weight of water-soluble residuals, respectively (Jerez
et al. 2007).
9.3.2.2 Moisture Analysis
Moisture content is an important parameter for processing materials and should

remain below the level specified in the appropriate material standard. The hygroscopic
nature of bioplastic materials causes processing as well as dimensional stability problems.
In our example, bioplastic moisture content was gravimetrically determined by
heating samples of bioplastics in a ventilated oven at 110°C for 24 h (Gómez-Martínez
et al. 2011). Usually, the time is not fixed, and weight loss is taken when no further
decrease in weight occurs.
9.3.2.3 Solubility Test
The behavior of bioplastic materials in various organic solvents often indicates the
type of material. A solubility test is very useful in distinguishing among the different
types of the same base polymer. For example, cellulose acetate can be distinguished
from cellulose acetate butyrate because the acetate is completely soluble in furfuryl
alcohol, whereas the butyrate is only partially soluble. The solubility test is best con-
ducted by placing a sliver of the sample in a small test tube, adding the solvent, and
gently stirring it. Ample time should be allowed before passing judgment regarding
solubility of the sample in a particular solvent.
Water solubility of each film was determined as the percentage of film dry matter
solubilized after a 24-h immersion in distilled water (Rhim et al. 1998). Three ran-
domly selected 2 × 2 cm samples from each type of film were first dried at 105°C
for 24 h to determine the weight of the initial dry matter. An additional three pieces
of weighed film were placed in a 50-ml beaker containing 30 ml of distilled water.
Beakers were covered with Parafilm (American National Can, Greenwich, CT) and
stored in an environmental chamber at 25°C for 24 h with occasional, gentle stirring.
Undissolved dry matter was determined by removing the film pieces from the beakers,
gently rinsing them with distilled water, and then oven drying the rinsed films (105°C,
24 h) (Rhim et al. 2007).
9.4 BIODEGRADABILITY TESTING
9.4.1 Standards for Compostability
The legislative framework regulating disposal and the characterization of disposal

properties in particular is necessary to adapt existing standards and/or to develop new
regulations/standards for biopolymers as a new materials group. A number of national,
European, and international standards defining compostability in degradable materials
and/or products made from these materials (e.g., packaging) have been developed.
Following are the important standards of compostability for plastics:
• DIN V 54900
• DIN EN 13432
• DIN EN 14995
• ISO 17088
• BNQ-9011–911
• ASTM D6400
• ASTM D6868
• AS 4736
German standard DIN V 54900 for testing the compostability of plastics

describes the individual test/procedures and evaluation criteria succinctly and
in great detail. This standard has been completely replaced by European standard
DIN EN 13432. Even so, it represents an important foundation for other stan-
dards in this field.
European standard DIN EN 13432 details the special requirements for recycling
packaging by composting and biodegradation. This standard contains test schemes
and evaluation criteria for rating packaging. European standard DIN EN 14995
(2006) (evaluation of compostability–test scheme and specifications) also provides a
framework procedure that can be used to support requirements regarding the compost-
ability of plastics. However, unlike DIN EN 13432, it does not concentrate exclusively
on packaging, but it defines requirements for plastics materials in general that can be
considered organically recyclable.
ISO 17088 (2008), Definition of Compostable Plastics, describes the same test
scheme as DIN EN 13432 or ASTM D6400, Standard Specification for Labeling
of Plastics Designed to be Aerobically Composted in Municipal or Industrial Facil-
ities. However, ISO 17088 does not apply exclusively to plastics packaging but also
to plastics in general. The Bureau de Normalisation du Quebec (BNQ), which is
accredited by the Standards Council of Canada, is an official certification agency
for compostable plastic bags, and it publishes its compostable plastic bags certifica-
tion program (BNQ 9011-911).
ASTM D6400 contains standard specifications for compostable plastics and pro-
ducts produced from these plastics. ASTM D6400, like all other standards, states its
scope of validity, defines its concepts, and defines particular requirements (here for
compostable materials and/or products). Specification ASTM D6868, Standard Spe-
cification for Labeling of End Items that Incorporate Plastics and Polymers as Coat-
ings or Additives with Paper and Other Substrates Designed to be Aerobically
Composted in Municipal or Industrial Facilities, covers biologically degradable plas-
tics and products (including packaging) that have plastic films that are laminated to
carrier materials (either by lamination or by extrusion coating directly onto paper)
or to the entire product and that are intended to be composted in public or industrial
composting plants.
AS 4736 is an Australian standard that also deals with biologically degradable
plastic packaging. This Australian standard also provides a hierarchy of requirements
and processes for determining compostability. It is titled “Biodegradable plastics—
biodegradable plastics suitable for composting and other microbial treatment,
2006” and, just as DIN EN 13432 does, it makes reference to the same subordinate
standards for further testing (Endres and Siebert-Raths 2011).
9.4.2 Biological Degradability (Laboratory Tests)
Different standards that specify testing procedures are applied for testing biologi-
cal degradability (normative references):
• DIN EN 13432: ISO 14851, ISO 14852, ISO 14853 (optional), ISO 14855,
ISO 11734 (optional)
• ASTM D6400: ASTMD6002, ASTM D5338
• GreenPla: JIS K6950/ISO 14851, JIS K6951/ISO 14852, JIS K6953/ISO
14855
• ISO 17088: ISO 14855, ASTM D5338
• DIN EN 14995: ISO 14851, ISO 14852, ISO 14853, ISO 14855
9.4.3 Methods for Biodegradation
The most important factor in determination of biodegradation is the proper selec-

tion of a test procedure based on the nature of the plastic and the climatic conditions of
the study environment. There are wide varieties of methods currently available for
measuring the biodegradability of polymeric materials. Several test methods to assess
the potential biodegradability of plastics have been developed by the ISO and ASTM.
Biodegradation can be characterized by loss of weight, changes in tensile strength,
changes in dimensions, changes in chemical and physical properties, carbon dioxide
production, bacterial activity in soil, and changes in molecular weight distribution
(Singh and Sharma 2008).
9.4.3.1 Soil Burial Method
Soil burial is one of the frequently used methods for the determination of biode-
gradability of plastic (Eya 2002; Yang et al. 2005). In this method, a biodegradation
test is performed under natural or laboratory conditions. A sample with definite weight
and dimension is buried in a specific depth in the soil for different time intervals. After
a specified time, the sample is taken out of the soil, thoroughly rinsed with distilled
water following immersion in distilled water, and then dried at 50°C for 24 h in a
vacuum oven. The sample is allowed to equilibrate to ambient temperature and humid-
ity for at least 24 h before measurement. In one study, starch plastic films buried in a
forest soil developed rapid colonization (15 days later) by fungal hyphae and showed
degradation of the starch granules on the films (Lopez-Llorca andValiente 1993;
Singh and Sharma 2008).
9.4.3.2 Pure Culture Method
In the pure culture method, specific bacteria and fungi can be applied for degrada-
tion of polymers. Preweighed disinfected films are aseptically added to a sterilized cul-
ture medium, and films in the culture medium are incubated with shaking for 24 h
before inoculation to ensure asepsis. The culture medium is inoculated with spores
from a specific microorganism and is incubated with shaking at 125 rpm for 4 weeks at
an optimal growth temperature for the selected microorganism. Four replicates are pre-
pared for each different pretreated film. The sample is weighed after washing with
70% ethanol and drying at 45°C until equilibrated. Each of the different films is
then compared with the corresponding uncultured material (Lee et al. 1991; El-Shafei
et al. 1998). The presence of microbes can be confirmed by using a microscope.
9.4.3.3 Compost Method
In this method, the definite weight of the dry plastic is subjected to a mixture of a
definite amount of mature compost and then incubated at 58°C with moisture content
maintained at 65%. Biodegradation is measured based on the amount of material car-
bon converted to gaseous carbon dioxide (Corti et al. 1992). The nature of the compost
affects the degree of degradation (Pandey et al. 2003; Yang et al. 2004). Unexpected
trends have been reported for the biodegradation of plastics in compost stored at
−20°C, 4°C, and 20°C for different periods. Viable cells in the compost stored at
−20°C are expected to be fewer than those in the compost stored at 4°C and 20°C
because microbes may be under stress or even be killed due to the formation of ice crys-
tals at the subzero temperature. Mesophilic bacteria and mesophilic actinomycetes
(mesophilic microorganisms that live at medium temperatures, 20°C to 45°C) are
fewer in number in the compost stored at 20°C than in the compost stored at the
other two lower temperatures—contrary to expectation. In contrast, as expected, both
thermophilic bacteria and thermophilic actinomycetes (thermophilic microorganisms
that thrive above 45°C—some live at or even above the boiling point of water) are few-
est in the compost stored at −20°C, indicating that thermophilic microbes are more sus-
ceptible to stress in freezing conditions than are the mesophilic ones. Activity of the
extracellular enzymes plausibly excreted by the microbes in the compost decreased
as a result of storage (Yang et al. 2004). The shape of the plastic sample (Yang et al.
2005) and additives (Jang et al. 2002) affect their degradation in the compost.
Vermiculite, a clay mineral, can be activated and used as a solid matrix in place of
mature compost. The composting test method based on activated vermiculite is a com-
prehensive system for the assessment of the environmental impact of biodegradable
plastics. Activated vermiculite affects neither the biodegradation rate nor the final
biodegradation level. On the other hand, possible metabolic intermediates and polymeric
residues left after biodegradation can be recovered more easily from activated vermicu-
lite than from mature compost, a very complex organic matter. Therefore, at end of the
test, it has been possible to determine the carbon balance by taking into account both the
evolved CO2 and a polymeric residue extracted from vermiculite (Innocenti et al. 2001).
9.4.3.4 Anaerobic Degradation in the Presence

of Sewage Sludge
Because of the enriched environment of sewage sludge, the microbes present are
more diverse in composition than in other disposed methods encountered (Ishigaki et al.
1999). In laboratory conditions, samples have been inoculated with sewage microbes.
Gaseous CO2 and methane (CH4) are monitored by headspace analysis using gas
chromatography–mass spectrometry (Ishigaki et al. 2004).
9.5 THERMAL ANALYSIS TECHNIQUES
Thermal analysis (TA) consists of a family of analytical techniques in which a

property of the sample is monitored against time or temperature while the temperature
of the sample is programmed. The properties include weight, dimension, energy take-
up, differential temperature, dielectric constant, mechanical modulus, evolved gases,
and other less common attributes. The application of thermal analysis is widespread
within the polymer and elastomer industries. Thermal analyzers are used to qualify
a material for fitness of use and to troubleshoot processing problems.
The relationships between heat resistance and melting temperature as well as
between glass transition and melting temperature that are well-established in conven-
tional plastics can be transferred to biopolymers because both conventional plastics
and biopolymers are governed by the same physically and materially related principles.
Biopolymers exhibit a relationship between melting temperature and glass transition
temperature similar to that of conventional plastics. When comparing the relationship
between modulus of elasticity and heat resistance, the biopolymers currently available
on the market exhibit somewhat lower heat resistance than conventional plastics. Improv-
ing heat resistance in biopolymers is a focus of current developments because biopoly-
mers are being increasingly used for engineering applications as well as for packaging.
The glass transition temperature of biopolymers should be as low as possible com-
pared to HDPE reference materials. Above the glass transition temperature, the amor-
phous zones exhibit increasing entropy elasticity together with increasing mobility in
the chain segments of these zones. At the same time, the polymer material becomes
more viscoplastic. Below the glass transition temperature, Tg, only energy elastic defor-
mation is possible and the material tends to be rather brittle macroscopically. This is the
case in particular for starch blends and PLA. At room temperature, these materials tend to
be brittle because their Tg still clearly lies above room temperature. For comparable
HDPE materials, a Tg of −90°C and lower can be assumed. Only a few polyesters, includ-
ing poly-D-lactide (PDL), reach these values. The other biopolymer materials, by con-
trast, exhibit glass transition temperatures similar to those of PET and ABS, which
range above room temperature, that is, above their particular use temperatures (Endres
and Siebert-Raths 2011).
Thermal analysis consists of three primary techniques that may be used individu-
ally or in combination:
1. Differential scanning calorimetry (DSC)

2. Thermogravimetric analysis (TGA)
3. Thermomechanical analysis (TMA)
The maximum benefit of thermal analysis can be gained by using a combination of all
three techniques to characterize a polymer (Shah 2007). Another important thermal
analytical method is dynamic mechanical thermal analysis (DMTA), which will be

described later in this chapter.
9.5.1 Differential Scanning Calorimetry
In DSC, the most widely used thermal analysis technique (ASTM D3417,
Standard Test Method for Enthalpies of Fusion and Crystallization of Polymers
by Differential Scanning Calorimetry; ASTM D3418, Standard Test Method for
Transition Temperatures and Enthalpies of Fusion and Crystallization of Polymers
by Differential Scanning Calorimetry), the heat flow rate to the sample (differential
power) is measured while the temperature of the sample, in a specified atmosphere,
is programmed. Because all materials have a finite heat capacity, heating or cooling a
sample specimen results in a flow of heat in or out of the sample. The heat flux DSC
uses a disk containing sample and reference positions that are heated by a common
furnace. The differential heat flow to the sample is proportional to the temperature
difference that develops between the sample and reference junctions of a thermocou-
ple. The power compensations approach controls a temperature enclosure around
the sample and reference individually. Through amplified feedback from platinum
resistance thermometers, it records the differential energy flow necessary to main-
tain the sample on the specified temperature program. With either approach, the out-
put is heat flow, which usually is expressed in milliwatts, watts/gram (normalized),
or watts/gram-degree (specific heat units).
In our example, DSC was performed using a TA-Q100 (TA Instrument, USA)
calibrated with an indium standard. Two to three milligrams of each sample were
weighted. The testing temperature ranged from −80°C to 180°C at a heating rate of
10°C/min under a nitrogen atmosphere of 50 mL/min. After being maintained at
180°C for 1 min, the molten sample was quenched to −80°C at a cooling rate of
80°C/min. Subsequently, the sample was heated again from −80°C to 180°C at a heat-
ing rate of 10°C/min. The second heating round of the DSC curves was used to eval-
uate the thermal properties. The glass transition temperature (Tg), melting temperature
(Tm), and apparent heat of fusion (ΔHm) were recorded. Thermal stability of the PHA
polymer was determined by a TA-Q50 thermogravimetric analyzer (TA Instrument,
USA). Three to five milligrams of each sample were loaded with the temperature ran-
ging from 10°C to 400°C in a nitrogen atmosphere of 50 mL/min (Wang et al. 2009).
Thermal properties of SPI films and PLA films were investigated using DSC with a
glass transition temperature of SPI at 117.7°C and PLA at 29.5°C (Rhim et al. 2007).
9.5.2 Thermogravimetric Analysis
TGA is a test procedure in which changes in the weight of a specimen are mon-
itored as the specimen is progressively heated. The sample weight is continuously
monitored as the temperature is increased either at a constant rate or through a series
of steps. The components of a polymer or elastomer formulation volatilize or decom-
pose at different temperatures. This leads to a series of weight-loss steps that allow the
components to be quantitatively measured (Shah 2007).
TGA is a powerful tool used to monitor the thermal degradation of biopolymers

under inert (pyrolysis) or oxidative (combustion) atmospheres (Barneto et al. 2009).
Thermogravimetric data can be used to study the thermal stability of bioplastics.
Thermo-gravimetric curves, weight loss versus temperature (TG), and time derivative
of the TG (DTG) curves were obtained in a TA Q50 analyzer (TA Instruments, USA).
Pyrolysis and combustion tests, between 40°C and 600°C, were carried out on 5-mg to
10-mg samples under a nitrogen and air atmosphere. Three heating temperature ramps
(5°C/min, 10°C/min, and 20°C/min) were selected ( Gómez –Martinez et al. 2011).
TG analysis has been applied to study the thermal degradation of soy-based bioplas-
tics (Swain et al. 2005; Nanda et al. 2007; Das et al. 2008).
9.5.3 Thermomechanical Analysis
When a sample is heated, its dimensions change because of thermal expansion,

stress reorientation, and deformation under an imposed stress. TMA measures these
properties using a constant force on the sample. Under no-load or a fixed load,
TMA measures the dimensional change in the vertical direction as the sample tem-
perature is controlled. The TMA equipment consists of a probe mechanically connect-
ing three entities: (1) a force transducer to control the force applied to the sample, (2) a
position transducer to measure the displacement, and (3) a temperature-controlled
sample specimen. Samples to be examined are cut to a defined geometry and then
deformed by the TMA probe in a defined manner. Sample deformation includes com-
pression, tension, and bending geometries. Once mounted, the sample is surrounded
by a furnace and monitored by a thermocouple.
Polymer characterization through the use of TMA is accomplished by determining
the glass transition temperature, the coefficient of expansion, and the elastic modulus.
The TMA data also correlate with the Vicat softening point and the heat distortion
temperature (Shah 2007).
9.5.4 Dynamic Mechanical Thermal Analysis
DMTA, also known as dynamic mechanical rheological testing, is probably the

most versatile thermal analysis method available, and no other single test method pro-
vides more information about a sample in a single test. Besides providing important
material property data, DMTA provides a direct link between a material’s chemical
makeup and its mechanical behavior. Materials can be characterized by DMTA
regardless of type, physical state, or the form in which they are used.
DMTA is a laboratory test method in which rheological data for a material are gen-
erated using a rheometer (e.g., Rheometrics Mechanical Spectrometer RMS-800,
Fluids Spectrometer RFS II, or Solids Analyzer RSA II) and sophisticated software.
The material is characterized in terms of its modulus, elasticity, viscosity, damping
behavior, and glass transition temperature, and the changes in these with strain, strain
rate, temperature, and oscillatory frequency.
In our example, DMTA experiments were performed with a Seiko DMS 6100
(Seiko Instruments Inc., Chiba, Japan) on protein/starch based bioplastics (Gonza-
lez-Gutierrez et al. 2010).
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CHAPTER 10
Shock and Vibration Testing of

Packaging Materials
Robert Meisner and Dennis Young
CONTENTS
10.1 Introduction.................................................................................................233
10.2 Testing of Packages ....................................................................................234
10.3 Hazards of the Distribution Environment ...................................................236
10.3.1 Distribution Shock ........................................................................236
10.3.2 Distribution Vibration ...................................................................239
10.3.3 Distribution Compressive Loads...................................................241
10.3.4 Distribution Atmospheric Conditions ...........................................241
10.3.5 Types of Distribution Tests Available ..........................................241
10.3.6 Test Methods Available for Conducting Tests, American
Society for Testing and Materials (ASTM), and International
Standards Organization (ISO).......................................................242
10.3.7 Test Methods Available for Conducting Tests, ISTA ..................244
10.3.8 Testing Equipment Used to Simulate Environmental Hazards.....244
10.3.8.1 Shock .......................................................................... 244
10.3.8.2 Vibration ..................................................................... 246
10.3.8.3 Compression ............................................................... 246
10.3.8.4 Atmospheric Conditions ............................................. 246
References ..............................................................................................................249
10.1 INTRODUCTION
In the progression of humankind over thousands of years of history, consumers of

food and other necessary products and the sources of these products grew farther apart.
Self-sufficiency in production became the distinct exception and today in developed
nations most people purchase food, clothing, and shelter rather than produce it
themselves. The source of such production may be far removed from the demand
233
Flow through a supply chain system
Warehouse Handling Transportation Handling Warehouse
Figure 10.1 A simple supply chain.
for the products. Production is concentrated in geographic areas that are best suited
for specific products, tending to increase the efficiency of product production and
the general quality of the products produced.
With production and demand separated spatially, an accommodation is necessary
to physically put products into the markets where demand exists. In addition, produc-
tion and demand may often be separated temporally. Consumers desire fresh food
products even in seasons when they are not produced, resulting in long time period
gaps. Short time period gaps, hours, or days in length, are functions of delivery and
shopping details at the market level and are also important to success in the market.
Unless these challenges are addressed successfully, supply and demand can be discon-
nected, driving market inefficiencies and the attendant inefficiency and waste.
Clearly, the answer to this challenge is product distribution, or logistics, or supply
chain management. Supply chain management is a broad interdisciplinary business
activity that is critical to successful business operations. Two key elements of supply
chain management are transportation and warehousing. Transportation serves the spa-
tial variability need, moving products around to where they are needed and to where
the demand exists. Inventory and warehousing buffer the uncertainty of production
and consumption, seeking to have a product in the market when consumers demand it.
From a product packaging perspective, transportation and warehousing provide
the environmental background. This is the environment where packages live and
must perform well to protect products and to communicate with potential consumers.
In addition to transportation and warehousing, product/package handling in many
forms is used to provide transitions from one logistical phase to the next. Examples
include moving packages of a product from a finished goods warehouse to a truck,
handling from a vehicle into a retailer’s distribution center, or transferring a product
from a pallet load in the back room of a store to the sales shelf. Simply put and allow-
ing for some gray areas, if the product is moving, call it transportation; if it is sitting
still, it is warehousing; and if it is in between, it is handling. Figure 10.1 shows a sim-
plified product distribution system.
10.2 TESTING OF PACKAGES
During the development of packaging for distribution, many development

teams schedule a series of tests to evaluate the effectiveness of the proposed design
before approval for implementation and production. This preshipment testing
SHOCK AND VIBRATION TESTING OF PACKAGING MATERIALS 235
provides a way of accessing the likelihood of good results in production ship-

ment, including low levels of damage and unsalability and acceptable perfor-
mance at low system cost. Some of these test series are laboratory based and
take advantage of existing standardized test protocols. In other instances, the
developers may elect to test the packaged product’s performance by trial ship-
ments of sample packages through representative distribution systems (Young
lecture notes).
Developers may also elect to implement the new package at production levels
without an established evaluation period in either laboratory or field testing. This deci-
sion may be encouraged by the need for moving quickly from development to produc-
tion. In these cases, the package is still evaluated. The critical difference is in two
aspects of the development process—control of the evaluation process and notifica-
tion of evaluation results.
If the new or modified package proceeds to production without a formal evaluation
of performance, the control of the process is passed to external elements, including
carriers and customers. Accordingly, it is difficult or impossible to tell quantitatively
what happened to packages or when and to what extent the condition of packages on
receipt reflects typical performance and expected distribution situations. The develop-
ment process also suffers with this technique because the customer, not the shipper or
brand owner, is the first to experience the results of this unintended evaluation.
Customers know before brand owners if there is a problem with the packaging. It is
akin to publishing a book without first proofreading it, thus allowing the readers to
discover any mistakes. Clearly, if the new package performs poorly, this can have a
far–reaching effect. New product growth and acceptance, future buying decisions,
and even brand loyalty may be affected.
Laboratory testing and field testing may be used in support of each other, but field
testing (trial shipments) need to be carefully designed. Small sample sizes are usually
indicated by the preproduction nature of the preshipment test. If the new package is
marginal in performance, then the probability of finding a problem may require sig-
nificant sample size.
For example, consider a package development, preproduction, testing by field
test. Suppose that the package performance will be marginal if implemented, for
this example, 10% damaged and unsalable packaged products. In most cases, this
level of damage would be totally unacceptable. However, if the field test as designed
calls for 10 samples, the odds on all samples arriving without damage are about 35%.
All samples in good condition would certainly be interpreted as a successful test,
even though the underlying design is defective—in effect, a false negative result.
To get this example to less than 5% chance of an incorrect result would take about
29 samples.
The use of laboratory test protocols, especially those developed based on actual
distribution hazard measurement, helps minimize this risk. These test protocols typi-
cally represent the degree of danger in a small percentage of shipping situations, lead-
ing to high confidence that a package that passes the test protocol will have a low
incidence of poor performance if implemented at production volumes (Goodwin
and Young 2011).
So, all packages are tested but with various types of control and reporting of
results. Careful design and consideration of preshipment evaluation of new or rede-
signed packaging is a critical element in a successful packaging project.
10.3 HAZARDS OF THE DISTRIBUTION ENVIRONMENT
The period of time that a product is in distribution, usually in a package, differs in

significant ways from the environment of product use after arrival at the point of con-
sumption. The logistical environment, transportation, storage, and handling are in
many ways more risk-filled and capable of causing product and package damage.
The hazards of distribution may be categorized as the following four types:
• Shock
• Vibration
• Load
• Atmospheric
These hazard types can each individually, and in combination, damage products
and damage packages. Types of product damage vary by product characteristics.
Granular, flaked, flowable products may break down and develop “fines.” Suspen-
sions may separate. Solid products can fracture or deform. Fresh products can bruise
or be dented or cut. Any of these and other forms of damage may make the product
unsalable or may be considered unacceptable by consumers. Package damage in
food products is closely linked to product damage. For many food types, an uncom-
promised primary package (carton, pouch, can, jar, and so on) is essential to prevent
product degradation or spoilage. Packages that have breached sterile barriers or that
have leakage, cracks, dents, tears, or other damage typically are unacceptable.
Even packaging cosmetic damage is capable of creating an unsalable condition
and the attendant financial losses. Damage as obvious as carton crushing or as subtle
as label abrasion may be enough to cause a consumer to look elsewhere to satisfy a
need at the point of selection. Figure 10.2 illustrates this point.
The atmospheric hazard applies to all the elements of distribution to some
extent—transportation, handling, and warehousing. The other three hazard types—
shock, vibration, and load—are all associated closely, but not exclusively, with one
of the elements of logistics. Vibration is associated most closely with transportation,
load with warehousing, and shock with handling.
10.3.1 Distribution Shock
Handling of packages in distribution is very large in scope, from manual handling

of individual packages to fully automatic mechanical handling of container loads.
Bumps and bangs, hits and nudges, drops and tumbles are all a part of handling. Manu-
ally handled packages are dropped on purpose and accidently by handlers. When pal-
letizing a load manually, each individual package is placed in position, often with a
Figure 10.2 Example of package damage at retail.
small drop. The same type of action occurs in de-palletizing, in picking up an order in
a warehouse, in manual sorting, or in vehicle loading. Accidental shocks are asso-
ciated with drops—unintended and uncommon but usually more severe than the inten-
tional variety. Larger package units such as crates, pallet loads, machinery bases, and
large shipping boxes may be accidentally dropped during mechanized handling by lift
trucks or in conveyor systems. The result of all of these activities is a shock.
A shock is a sudden, nonperiodic change in velocity. A package dropped from
30 inches (760 mm) will reach a velocity at impact of approximately 152 inches
per second (3.9 m/sec). That velocity goes to zero in a small fraction of a second,
depending on the nature of the object dropped and the surface impacted. This velocity
change generates large deceleration and high forces as a result. Thus the result of the
drop is a severe dynamic event capable of causing damage to products and packages.
Smaller drops tend to occur more often and may generate damage in a more incremen-
tal manner.
Several factors affect the occurrence and severity of shocks seen by packaged pro-
ducts during logistics operations. One of these is the size and weight of the item being
handled. In general, larger package units, such as pallet loads, are handled in ways that
minimize the occurrence of high drops. The high, usually accidental, drop is more
likely to be experienced by small, manually handled packages (Goodwin and
Young 2011). It is possible to use electronic instruments to monitor packages in transit
and from the recorded events estimate the drop heights experienced by those
packages. Figure 10.3 shows a typical instrument.
Studies on manually handled packages show a general distribution of drop heights
that is similar across different logistic systems. Small and medium height drops, under
Figure 10.3 Distribution environment recorder.
approximately 12 to 15 inches (300–380 mm), are fairly common, while drops from
high heights, say above 24 inches (600 mm), are rare. Figure 10.4 shows an example
of the distribution of drop heights for a specific study of small packages shipped in a
parcel delivery system. Cumulative occurrence data show what percentage of all drops
occurred under a specific drop height. In most cases, the highest drops occur less often
that once per trip on the average.
The number of drops per distribution trip is also an important variable. More drops
means more opportunity for a high drop and more drops contribute to the risk of accu-
mulated damage or degradation. Manual handling of small packages in parcel and less
than truckload (LTL) environments can produce 10 to 15 or more drops per trip on the
average. Another variable is the orientation of impact. Corners of packages are more
Drop height distribution

All UPS and FedEx trips combined
Frequency Cumulative %
36 100%
33 90%
95.26%
30 80%
90.15%
27
70%
24
Cumulative
Cumulative
21 60%
18 50%
15 40%
12 30%
9
20%
6
3 10%
0 0%
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 more
Drop height (inches)
Figure 10.4 Drop height distribution data example. (From Meisner, R., Drop Heights in the small
parcel distribution system, Dimensions04 Conference Proceedings, International
Safe Transit Association, Orlando, FL, 2004. With permission.)
Handling drop orientation types
Corner Edge Flat
14%
42%
44%
Figure 10.5 Drop orientation data example. (From Meisner, R., Lecture Notes for Distribution
Packaging Course, University of Wisconsin Stout, Wisconsin, 2007.)
vulnerable to crush damage, while flat drops transmit more shock to the product
inside. Logic and limited data from shipping seem to indicate that bottom drops are
experienced by many packages but that no orientation is immune (Figure 10.5).
Shocks from small package drops are not the only source of shock in distribution.
Handling of unit loads (pallet loads for example) and even vehicles produce potentially
damaging shocks. Pallet load stacking, racking, handling, and marshaling are sources
of shocks and impacts. Speeds are low and damage potential is modest. Vehicle handing
such as backing into a dock is also of limited damage potential. Rail car switching, used in
the makeup and disassembly of trains and the delivery of individual cars, can be quite
severe. Studies have shown impact speeds of 5 to 8 MPH (8–12.8 km/hr) and, rarely,
even more. In addition to the applied shock of impact, longitudinal crushing of packaging
causes damage due to unrestrained packages sliding into each other when the car stops.
10.3.2 Distribution Vibration
Vibration experienced in distribution comes mainly from vehicles. The irregula-

rities of roads, rails, water, and air cause a reaction in the structure and suspension
of the vehicle, initiating vibration. Examples include trucks bouncing down a rough
road, railcars running over a road crossing, a vessel’s response to wave action, and
an aircraft’s reaction to air turbulence. Inside these reactive, vibrating vehicles are
packages. The vehicle vibration is passed to the packaged products through the load-
ing areas and the package reacts to this vibrational input. Unlike shock, vibration is of
a lower intensity but lasts for a longer time.
Vibration is measured in terms of its frequency—the number of vibration cycles in a
period of time—and the intensity of the vibration. Vehicles used to transport packaged
goods input vibrations across a significant range of frequencies, and the specifics vary
by type of vehicle (truck versus air, for example) and other variables (weight of the load,
roughness of road or rail, vehicle suspension, vehicle speed, and so on). Transportation
vibration is especially active in the range of 1 to 300 Hertz (frequency–cycles per sec-
ond) This range can cause damage to products and packages due to excess loading, fati-
gue, abrasion, and internal resonance (Goodwin and Young 2011).
Simple vibration, like a single musical note, occurs at one frequency. Real vibra-
tion as experienced by packaging in transportation is more complex. It is a mixture of
various frequencies and various intensities at any given time that make up the overall
vibration profile. This vibration profile is like soup, a mixture of ingredients, and the
mix is constantly changing. Because of this complexity, it is not possible to take a
snapshot of vibration in one instant and have it represent the entire vibration profile.
These complex vibrations, called random vibrations, are sampled over time and ana-
lyzed statistically to create an accurate description of the occurrence. Figure 10.6 illus-
trates monitoring of a vehicle and the resulting vibration profile, which is made up of a
number of frequency components.
A widely used way to perform this analysis is with power spectral density (PSD),
where vibration is sorted and grouped by frequency and analyzed to determine the
vibration intensity as a function of frequency. An example of a PSD vibration profile
is shown in Figure 10.7.
Amplitude Random vibration result
Data recorder
Time
Frequency 1 + Frequency 2 + Frequency 3 + ...
Figure 10.6 Random vibration illustrations.
Random vibration spectra

Ocean container - highway
1.00E+00
Sort Vertical:
1.00E–01 level ≥ 0.01 grms Overall = 0.134 grms
Power spectral density (G2/Hz)
Time: highway
1.00E–02
1.00E–03
1.00E–04
1.00E–05
1.00E–06
1.00E–07
Data by DYA
1.00E–08
0.1 1.0 10.0 100.0 1000.0
Frequency (Hz)
Figure 10.7 PSD vibration profile example.

Higher peaks in the PSD profile indicate higher intensity vibration at that frequency
and, therefore, a higher risk of vibration-induced product or package damage. This is
especially true if the product, package, or both are especially sensitive to that vibration
frequency. Packages and products actually amplify some ranges of input frequency
due to the mechanical nature of the item. If these product/package frequency sensitivities
match up with a high vehicle vibration intensity then the risk increases significantly.
10.3.3 Distribution Compressive Loads
Warehouse stacking, vehicle stacking, and unit load handling are all sources of com-
pressive loads in distribution. The vertical loads encountered in stacking are common, and
horizontal loads are imposed in handling by clamp trucks and similar equipment.
Warehouse stacking is a common practice to best utilize the space available. Unit
loads (pallet loads) may be stacked two, three, or more loads high. The load applied to
an individual package is often hundreds of pounds force (kilonewtons). The ability of
packages to resist these forces is an important performance factor. Package failure can
result in product and package damage as well as unsafe conditions. In addition, time, atmo-
sphere, package alignment, and other factors will reduce the ability of the package to resist
loads. These environmental factors taken together can reduce a package’s compression per-
formance to 25% or less of its laboratory compression strength (box compression testing).
10.3.4 Distribution Atmospheric Conditions
Distribution warehousing and vehicles expose packaged products to extremes of

temperature and humidity and are a source of potential damage. Temperature ranges
in distribution include freezing conditions in some environments and highs well above
38°C (100°F) in others. Temperatures well above ambient have been documented due
to heating effects. The atmospheric moisture environment that packages experience,
specified in relative humidity, may be very low, causing packaging to dry out and become
brittle. High humidity (up to 100%) as well as condensation also create a performance-
lowering effect, especially in fiber-based packaging materials (Young 2001, temperature).
10.3.5 Types of Distribution Tests Available
Laboratory testing of packages is a valuable tool in the development of protective,

economical, and environmentally responsible package systems. A number of organi-
zations have developed and standardized such tests, and they can be loosely classified
as to their general objective.
• Screening or nonsimulative tests

• General simulations
• Focused simulations
Screening or nonsimulation types of test are not representative of actual hazards

one would expect to encounter in distribution. They are designed to challenge the
capability of a packaged product to withstand transport hazards but do not represent

the actual hazard. One common example is the International Safe Transit Association
(ISTA) 1A test. The test protocol requires the packaged product to be subjected to
shock and vibration hazards only. Atmospheric-related hazards, load, and unusual
handling are not included. The intent is to compare or screen different package
designs. When a package passes a test of this type, the user can have a high degree
of confidence that the package will perform with minimal problems. This confidence
applies only to the hazards included in the test (ISTA 1A).
General simulation tests are more closely related to actual hazards one might
encounter in distribution. These types of tests are meant to challenge the capability
of a packaged product to withstand distribution hazards. They do not use actual,
specific transport hazards but rather use general hazards representative of a wide
range of distribution conditions. One common example is the ISTA 3A test. This
test requires that the package be preconditioned to take into account various atmo-
spheric hazards such as temperature and humidity. The test also requires the appli-
cation of shock and vibration events in various sequences and intensities depending
on the package attributes, such as size and shape, and includes top load compres-
sion testing for stacking simulation. ISTA 3A, like other general simulation tests,
is a four-hazard protocol, addressing the four types of distribution environment
hazards that may damage packages and products in transit (ISTA Guidelines).
Focused simulation tests attempt to replicate the specific hazards a package
will encounter in a narrowly defined or specific distribution environment. Tests are
based on the various levels of intensities of hazards measured and observed in distri-
bution. These types of tests may include temperature cycling, random vibration,
multiple drops at multiple heights, and package loading, depending on the actual
distribution environment being replicated. Developing these types of tests is time
consuming and requires a significant amount of measurement and analysis to simu-
late the hazards in the laboratory. Additionally, the test is specific to a vehicle type,
route, time of year, and load make up so there are no standard tests available.
A focused simulation test protocol may be developed across any range of distribution
variables but, as the variety of conditions increases, the test becomes more like a gen-
eral simulation. Focused simulation is especially useful in researching and addressing
specific problems where a solid definition of the distribution environment can be
developed.
10.3.6 Test Methods Available for Conducting Tests, American

Society for Testing and Materials (ASTM), and International
Standards Organization (ISO)
In order to specify and use any test procedure, standard or customized, the user
must be aware of three aspects of testing:
• Test purpose
• Test method or procedure
• Test level or intensity
Decision making is the foundation for the purpose of running any test. Testing pro-
duces data or information and allows comparisons among alternatives. Before speci-
fying any test, the user should be able to identify what decision will be affected. Using
Package A or Package B, shipping by Mode X or Mode Y, adopting Design P or
Design Q for a package are all examples of decisions that may need testing support.
The test method is the scope, set-up, implementation, and documentation informa-
tion for performing one specific test. It includes the sequence and steps required to
perform the test. Test methods address cautions on test performance, how to avoid
errors, and the sources of bias or imprecision. By definition, test methods explain
how to run a test but not what specific test to run. For example, ASTM D5276,
Standard Test Method for Drop Test of Loaded Containers by Free Fall, documents
how to run a free-fall drop test but does not specify what specific test to run. The
specifics of test performance are included in the test level specification.
Test level specifications usually refer to an established test method and then
detail how to perform that test in order to produce decision-supporting information.
Examples include the various preshipment test procedures that are published by
ASTM International, the National Motor Freight Classification, U.S. Department of
Transportation, International Air Transport Association, ISTA, and others. Such test
standards are arranged in a sequential series format similar to the following:
• Using test method A—perform an 18-inch (450 mm) drop on the package
edge, then
• Using test method A—perform a 24-inch (600 mm) drop on the package
bottom, then
• Using test method C—perform a compression test to 800 lbf (3.56 kN), then
• Using test method V—perform a three-hour vibration test using test profile X.
ASTM International and the ISO also publish a number of testing procedures
related to packaging. ASTM International focuses primarily on packaging materials
and package test methods but also includes preshipment package performance testing.
ASTM Standard D4169 (2003), Standard Practice for Performance Testing of
Shipping Containers and Systems, is the principal performance test.
The different test sequences outlined by ASTM D4169 are meant to be conducted
at intensities representative of actual distribution hazards. Preshipment performance
tests such as ISTA general simulation tests and ASTM D4169 are performed in a
sequence of anticipated hazards. Each test performed refers to a standard test method
for procedures to run that test, and the test levels are specified in the performance test.
The ASTM D4169 test procedure has defined 18 unique distribution cycles based on
modes of transportation expected to be used during distribution activities (ASTM
D4169).
Examples of commonly used ASTM D4169 distribution cycles include:
• DC3: Single package without pallet or skid, LTL motor freight

• DC5: Motor freight, TL, not unitized
• DC6: Motor freight, TL or LTL, unitized
• DC7: Rail, bulk loaded

• DC12: Air (intercity) and motor freight (local), over 150 lbs (68.1 kg) or
unitized
The ISO also publishes package test methods similar to those of ASTM Interna-
tional that are designed to validate the integrity of the package and its ability to contain
and protect the product from the hazards of distribution and the package’s ability to
contain the product and prevent the product from leaking or otherwise damaging or
injuring the distribution environment and those working there. The user is provided
with a range of test intensities and selects the specific test based on the objectives
of the test being performed. ISO 4180 provides a general sequence of tests for a mul-
titest schedule (ISO 4180).
10.3.7 Test Methods Available for Conducting Tests, ISTA
The ISTA publishes a catalog of preshipment performance test standards for

evaluating packaging performance and damage prevention in the laboratory. Testing
in the lab provides the user with control over the level of hazard exposure and the
ability to observe and document the effects of specific tests. This leads to better
designs.
ISTA standards include nonsimulative tests, the A Series, which provide screen-
ing of designs to minimize problems. ISTA 1A is thought to be the most commonly
run package test. It includes a series of package drops in various orientations, from
a height determined by package weight. ISTA 1A also includes a fixed frequency-
vibration ounce test; 1A is for smaller packages and 1B, for larger packages, is
similar.
Other ISTA series incorporate general simulation tests including the widely used
ISTA 3A for small packages in parcel distribution environments. ISTA 3B is similar
but applies to packaged products for LTL shipment. Other ISTA procedures cover uni-
tized loads of the same product (ISTA 3E) and fast-moving consumer goods for the
European retail supply chain (ISTA 3K). In all, ISTA publishes about 20 different
test protocols.
10.3.8 Testing Equipment Used to Simulate Environmental Hazards
A typical package testing laboratory includes equipment and support systems for
the four hazard types that packages encounter in distribution, shock, vibration, com-
pression, and atmospheric conditions. Equipment for small- and large-sized packages
is selected to accommodate the packaging mix required.
10.3.8.1 Shock
Small and large packages are tested for shock, drop, and impact. Horizontal impact
testers are capable of simulating specific shocks including rail car impacts during
Figure 10.8 Incline impact tester.
switching operations. Horizontal and incline impact testers are used to simulate the
bumps and collisions of unit load and large package handling (Figure 10.8).
Small, manually handled packages are tested in drop testing. Drop testers must
release packages for dropping in a controlled manner to avoid rotation and maintain
orientation. Drop testers have variable drop heights to meet test standard requirements
(Figure 10.9).
Figure 10.9 Free-fall drop tester for small packages.

Figure 10.10 Fixed frequency vibration tester (bounce test).
10.3.8.2 Vibration
Some nonsimulation test standards call for a fixed-frequency bounce test. The tes-
ter motion may be vertical or rotational. The tester frequency is increased until the
package bounces and then is allowed to continue for a specified time (Figure 10.10).
Simulation of the complex vibrations seen in distribution requires a more sophis-
ticated test system. Vibration test systems are capable of performing simple sine tests,
including bounce, as well as random vibration test profiles. Computer-based controls
monitor and maintain the test parameter. Small and large packages are tested in this
manner according to standardized protocols (Figure 10.11).
10.3.8.3 Compression
Compressive loads in warehouse and vehicle stacking are simulated with com-
pression test systems. An entire unit load may be tested at one time in systems capable
of forces up to 50,000 pounds of force (Figure 10.12).
Smaller individual packages are tested in appropriately sized testers. For all sizes,
computer-based controls manage the load applied and document the test results
(Figure 10.13).
10.3.8.4 Atmospheric Conditions
Test chambers from bench top to room size are used to provide per-test condition-
ing as well as to test for product and package performance under extreme conditions.
Due to the susceptibility of common package materials to temperature and humidity,
these parameters are specified and controlled. Chambers may be used to soak samples
(conditions maintained over time) or may apply cyclic testing (conditions changing
over time) (Figure 10.14).
Figure 10.11 Vibration test system.
Figure 10.12 Compression test system for large packages.

Figure 10.13 Compression test system for small packages.
Figure 10.14 Atmospheric conditioning chamber.

REFERENCES
ASTM Standard D4169, 2009e1, Standard Practice for Performance Testing of Shipping
Containers and Systems, ASTM International, West Conshohocken, PA, 2003, DOI:
10.1520/C0033-03E01, www.astm.org (accessed 30 January 2013).
Goodwin, D. and Young, D., Protective Packaging for Distribution, DEStech Publications,
Lancaster, PA, 2011.
International Safe Transit Association, Guidelines for Selecting and Using ISTA® Procedures
and Projects, ISTA, East Lansing, MI, latest edition, 2015.
International safe Transit Association, ISTA Procedure 1A, Packaged-Products weighing 150 lbs
(68 kg) or less, ISTA, East Lansing, MI, latest edition, 2015.
ISO 4180:2009, Packaging—Complete, Filled Transport Packages—General Rules for the
Compilation of Performance Test Schedules, ANSI, Washington, D.C.
Meisner, R., Lecture Notes for Distribution Packaging Course, University of Wisconsin Stout.
Meisner, R., Drop Heights in the small parcel distribution system, Dimensions04 Conference
Proceedings, International Safe Transit Association, Orlando, FL, 2004.
Young, D., Lecture Notes for Packaging Courses, Michigan State University School of Packaging.
Young, D., ISTA Temperature Project Data Summary, ISTA, East Lansing, MI, 2001.
CHAPTER 11
Testing Migration from Food

Packaging Materials
Annika Ebert, Roland Franz, Carina Gehring, Diana Kemmer,

and Frank Welle
CONTENTS
11.1 Introduction...................................................................................................252
11.2 Definitions.....................................................................................................253
11.2.1 Migration ........................................................................................253
11.2.2 Extraction........................................................................................253
11.2.3 Migration Limit...............................................................................254
11.2.4 Overall Migration/Overall Migration Limit....................................254
11.2.5 Specific Migration/Specific Migration Limit ..................................254
11.2.6 Maximum Residual Content (Maximum Quantity [QM])..............255
11.2.7 Standard Tests/Conventional Tests.................................................255
11.2.8 Food Simulants ...............................................................................255
11.2.9 Alternative Tests/Screening Tests...................................................255
11.2.10 Migration Modeling........................................................................256
11.2.11 Diffusion Coefficient ......................................................................256
11.2.12 Partition Coefficient ........................................................................256
11.2.13 Exposure .........................................................................................256
11.2.14 Migration Test Cell.........................................................................256
11.2.15 Total Immersion..............................................................................256
11.2.16 One-Sided Contact ..........................................................................256
11.3 Standard Migration Tests..............................................................................257
11.3.1 Elements of a Migration Test .........................................................257
11.3.2 General Migration Testing Scheme ................................................258
11.3.3 List of Food Simulants ...................................................................258
11.3.4 Specific Assignment of Food Simulants to Foods..........................259
11.3.5 Test Conditions for Migration Testing ...........................................260
251
11.3.6 Overall Migration Testing...............................................................261

11.3.7 Specific Migration Testing..............................................................263
11.3.8 Testing for the Residual Content in the Polymer ...........................264
11.4 Alternative Migration Tests ..........................................................................266
11.4.1 Semidirect Migration Test Using Substitute and
Alternative Fat Simulants ...............................................................266
11.4.2 Extraction and Total Mass Transfer Assumption ...........................269
11.4.3 Solubility as a Migration Limiting Factor ......................................270
11.4.4 Diffusion Characteristics Similar to but More
Severe Than Standard Migration Testing .......................................271
11.4.5 Nonrequirement of Migration Tests................................................272
11.4.6 Functional Barriers..........................................................................272
11.5 Migration Modeling ...................................................................................... 274
11.5.1 State of the Art of Migration Modeling..........................................275
11.5.2 Recent Developments in Diffusion Modeling ................................277
11.6 Screening Analysis to Ensure Quality and Safety-In-Use of FCM ..............279
11.6.1 Screening Methods .........................................................................280
11.6.2 Examples for NIAS.........................................................................281
11.6.3 Potential and Limitations of Screening Analyses ...........................282
11.7 Recycling of FCMS into New FCMS ............................................................283
11.7.1 Metals and Glass.............................................................................283
11.7.2 Plastics ............................................................................................283
11.7.3 U.S. Food and Drug Administration Criteria for
Evaluation of Recycled Plastics in Food Contact...........................284
11.7.4 EFSA Criteria for Evaluation of Recycled Plastics
in Food Contact ..............................................................................286
11.7.5 Paper and Board..............................................................................288
11.8 Active and Intelligent FCMs ........................................................................289
11.8.1 Passive Parts of the Packaging .......................................................290
11.8.2 Active Packaging ............................................................................290
11.8.3 Intelligent Packaging ......................................................................290
11.8.4 Scavenging Systems .......................................................................291
11.9 Nano Applications in Plastic FCMs .............................................................291
11.9.1 Definition of Nano and Legal Nano Applications in Europe .........292
11.9.2 Analytical Approaches to the Determination of Nanoparticles ......294
11.9.3 Migration of Nanoparticles from Food Contact Plastics ................295
References ..............................................................................................................297
11.1 INTRODUCTION
The first purpose of food packaging is to protect the food against deterioration and
to maintain it at the highest possible quality level until eaten by the consumer. In this
way, food packaging contributes essentially to saving food. In order to pack the huge
TESTING MIGRATION FROM FOOD PACKAGING MATERIALS 253
diversity of foodstuffs that can be found on the market today and to meet all their spe-
cific sensitivities, a variety of food packaging materials and combinations of them are
used. Structurally, this ranges from rigid containments made from mono-materials
such as glass, polymers, metals, and cardboard to multimaterial, multilayer flexible
film constructions and from the conventional passive protection packaging to complex
active packaging systems with integrated oxygen absorbers. Caps, closures, lids, and
other sealing or closing devices put a further complication on top of the basic package.
Set-off mass transport from printing ink on the outside layer of packaging material into
food emerged as a new risk in 2005 due to the so-called “ITX crisis” that involved
2-iso-propyl thioxanthone (ITX), a photoinitiator used in ultraviolet (UV) printing
inks (EFSA 2005). This resulted in an increased awareness that food contact materials
(FCMs) can contain additives in nanoform that are further contributors to the complex
world of food packaging, particularly when it comes to lawful compliance testing of
FCMs and articles, and ensuring their safe use.
The objective of this chapter is to provide the needed technical and scientific back-
ground in the area of migration testing and, more importantly, to give guidance and
assistance to better understand and better perform migration testing as well as to cri-
tically evaluate migration test results. In this context, migration testing is understood
not only to be experimental standard migration testing but also alternative and quick
test procedures including migration modeling. In addition, cases will be presented and
discussed where migration testing may no longer be necessary based on scientific
grounds. This chapter will also focus on the question of safe recycling of food contact
plastics, such as polyethylene terephthalate (PET) for direct food contact, as well as on
active and intelligent food packaging applications. Finally, nano-applications in food
contact plastics, which is a newly emerging area of concern, will be discussed speci-
fically with regard to ensuring compliance with food packaging legislation.
11.2 DEFINITIONS
11.2.1 Migration
Migration means the mass transfer from a packaging material into the filling
good and is caused by a concentration gradient in the packaging system—for exam-
ple, between adjacent packaging layers or between the packaging and the filling
good (Figure 11.1). Migration takes place until an equilibrium is reached in the
whole system, and it depends on various factors related to the properties of the
packaging material, the filling goods, and the migrating substance itself as well as
the storage conditions (time and temperature).
11.2.2 Extraction
Whereas during the migration process, the packaging material maintains its phy-
sical characteristics, extraction is a more intensive interaction between a solvent and
a packaging material. The solvent causes physical changes in the material such as
Polymer Product
Ct
Ct = 0
Figure 11.1 Migration as a process caused by a concentration gradient between polymer

and filling.
swelling and thus leads to a complete release of a migratable component from the
material (Franz and Störmer 2008).
11.2.3 Migration Limit
In order to ensure the safety of a final material or article as demanded in Article 3

of the European Framework Regulation 1935/2004 (EU 2004) and to protect the con-
sumer, quantitative restrictions or migration limits are necessary. Such restrictions are
laid down in the European Plastics Regulation 10/2011 (EU 2011a) and include over-
all and SMLs as well as maximum residual contents.
11.2.4 Overall Migration/Overall Migration Limit
The overall migration (OM) is a generic term for the inertness of a plastic material
and is determined by gravimetric methods. It is the implementation of the Article 3
requirement of the European Framework Regulation 1935/2004 (EU 2004) not to
bring about an unacceptable change in the composition of the food. Overall migration
limit (OML) means the maximum permitted amount of nonvolatile substances
released from a material or article into food simulants (IVLV 2011).
11.2.5 Specific Migration/Specific Migration Limit
The European Plastics Regulation 10/2011 (EU 2011a) contains a list of nearly
900 authorized monomers and additives. Several of these are restricted with specific
limitations. The specific migration limit (SML) means the maximum permitted
amount of a given substance released from a material or article into food or food simu-
lants. The SML values have been derived from the toxicological parameters accepta-
ble daily intake (ADI) or tolerable daily intake (TDI), which are given in mg per kg
body weight per day in connection with several conservative conventional assump-
tions. It is assumed that an average European person with a body weight of 60 kg con-
sumes an average amount of 1 kg food per day that is packed by 6 dm2 packaging
material (EU-cube) and contains the respective substance in the SML concentration.
Thus, the SML value generally results from the ADI/TDI value and a factor of 60.
11.2.6 Maximum Residual Content (Maximum Quantity [QM])
In cases where determination of the specific migration of a substance is difficult or

impossible due to chemical instability or high volatility of the migrant, maximum per-
mitted residual contents in the material (QM) apply. Examples of such substances are
butadiene or vinyl chloride. QM values are based on a conventional historic assump-
tion of a QM/SM ratio of 100. For some substances, an area related residual limit
(QMA) is given in European Union (EU) Regulation 10/2011. This especially
plays a role for thin layers such as lacquers and coatings (IVLV 2011).
11.2.7 Standard Tests/Conventional Tests
In order to achieve comparable results in the verification of compliance with the

overall and SMLs, testing is performed under standardized test conditions including
testing time, temperature, and test medium (food simulant) that represent the worst fore-
seeable conditions of use of the plastic material or article. These standard or conven-
tional tests are carried out in accordance with the rules set out in EU Regulation 10/2011.
11.2.8 Food Simulants
Food simulants are test media imitating foods. In their behavior concerning inter-
action with the packaging material and solubility for migrants, they should mimic food
as closely as possible. Simulants are used instead of real foods due to a simpler matrix
that prevents analytical problems. The EU Regulation 10/2011 gives a list of official
food simulants and an assignment of these simulants to food categories. The list includes
simulants for aqueous, acidic, fatty, and dry food.
11.2.9 Alternative Tests/Screening Tests
Alternative tests, or so-called screening tests, are simplified or accelerated tests that
can be used to show compliance of a material or article with the migration limits pro-
vided that they are more severe than the conventional methods. Due to their overestimat-
ing character, alternative tests do not allow demonstration of noncompliance. The
following alternative tests may be applied according to EU Regulation No. 10/2011:
• Replacing specific migration by overall migration (only possible for nonvolatile

substances)
• Determination of the residual content in the material and calculation of the
total transfer
• Migration modeling
• Food simulant substitutes (alternative migration test with 95% ethanol or
isooctane or rapid extraction)
11.2.10 Migration Modeling
Migration modeling is a tool for the prediction of the migration of substances from
packaging materials based on the knowledge that the migration obeys Fick's laws of
diffusion. Migration can be calculated using suitable software and appropriate, scien-
tifically based modeling parameters.
11.2.11 Diffusion Coefficient
The diffusion coefficient describes the mobility of a substance in a polymer that

occurs due to a concentration gradient; it is dependent on the molecular mass of the
migrating molecule and the grade of cross-linking in the polymer.
11.2.12 Partition Coefficient
The partition coefficient is the ratio of the concentration of a certain substance in

the packaging material and the concentration in the food in a state of equilibrium.
11.2.13 Exposure
Exposure can be expressed in a simplified way as a function of the consumption

factor of a certain food, the usage factor of a packaging material for that food, and the
migration of a substance from the packaging material into that food (Franz 2007).
11.2.14 Migration Test Cell
A migration cell is a device where a test specimen can be fixed and covered with a
food simulant for a one-sided migration test (DIN 2002).
11.2.15 Total Immersion
Total immersion is a method of migration testing where the whole surface of a sam-
ple (i.e., both the food contact side and the nonfood contact side) is brought into contact
with the food simulant. For thin materials, this procedure will lead to the same migration
values as obtained by a one-sided test. Therefore, only the one-sided surface area is used
for migration calculation. For samples with a thickness of 500 µm or higher, the total
surface has to be considered.
11.2.16 One-Sided Contact
One-sided contact is a method of migration testing where only the food contact
side of the test specimen is brought into contact with the food simulant (e.g., by
using a migration cell).
11.3 STANDARD MIGRATION TESTS
Migration testing is a useful instrument for the control, monitoring, and prevention
of unwanted and legally prohibited transfers of components from packaging materials
into packed food. Therefore, migration testing serves to ensure the safety of food and
to protect the consumers. Today, a large variety of analytical methods and analytical
approaches are available for migration testing. The basic approaches comprise con-
ventional migration testing with food simulants as well as alternative extraction and
screening methods but also include the mathematical calculation of migration using
recognized diffusion models (IVLV 2011).
Conventional compliance testing focuses on the specific analysis of migrants based
on the knowledge of the composition of the FCMs. The aim of the investigation of these
migrants (e.g., monomers and additives) is to quantify their concentration in the food
packaging material or in the final food or food simulant. In contrast, the so-called
“nontarget” migration testing targets on nonintentionally added substances (NIAS)
such as oligomers, by-products, and reaction products as well as impurities. These
kinds of components may also be present in the FCM even though they were not
added intentionally and, therefore, can potentially migrate into food. Both approaches
are to be complementary, in order to ensure compliance of a food packaging material
with the safety requirements of Article 3 of the European Framework Regulation
1935/2004 (Veraart and Coulier 2007). In this section, an overview of the currently
established methods and approaches for conventional migration testing will be
presented, while nontargeting screening approaches will be introduced in Section 11.6.
11.3.1 Elements of a Migration Test
Each procedure and approach to control migration must be linked, either directly or
indirectly, to the measurement and assessment of the real or maximum concentration of
a migrant in the food. This concentration results from the transfer (migration) of com-
ponents from the packaging material at the given conditions (temperature, time, nature
of the food, or food simulant). The analysis of migration from FCMs can be performed
according to different protocols. However, the migration ratio into the food is the rele-
vant parameter obtained from each migration testing procedure. Consequently, the
concentration of a migrant determined in the food or food simulant will then be com-
pared to the legally binding or recommended migration limits—for example, accord-
ing to the European Plastics Regulation 10/2011 (EU 2011a), the “Recommendations
on Food Contact Materials” of the German Bundesinstitut für Risikobewertung (BfR),
or other relevant national legislation of EU member states (BfR 2013). The analytical
methods, which are currently publically available in order to implement the regulatory
requirements for FCMs made of plastics, are summarized in the following sections.
Generally speaking, these are widely standardized methods or (pre-) validated meth-
ods that were developed and validated within the work of subcommittees and working
groups of the European Committee for Standardization (CEN) (TC194/SC1) or within
European research programs (IVLV 2011).
11.3.2 General Migration Testing Scheme
In the EU, compliance testing of FCMs is performed by migration tests. For this
purpose, test specimens of FCMs are brought in contact with food simulants. This
initial step simulates the interaction of the FCM (e.g., packaging material) with the
food, taking into account the contact conditions of the real application (temperature
and time). The interaction of the FCM with the food simulant is generally referred
to as migration contact or migration exposure. The quantification of the migrants is
performed as a second step. Specific analytical methods are used to determine the con-
centration of specific migrants and to evaluate their compliance with SMLs (SMLs),
while a gravimetric analysis is used for the determination of the overall migration. For
some specific substances, the residual content in the FCM must be analyzed using
additional specific methods.
For plastic materials and for “multimaterial multilayer materials” (composed of
two or more layers of different types of materials with at least one of them a plastic
layer), the relevant general rules for compliance testing are laid down in Annex V
(Chapters 1–3) of the European Plastics Regulation 10/2011 (EU 2011a). These gen-
eral rules describe the aspects of sample preparation, choice of food simulant, and con-
ditions of contact when using food simulants and cover both overall and specific
migration tests.
11.3.3 List of Food Simulants
As food is a complex matrix, the analysis of migrating substances in food may

pose analytical difficulties. Therefore, test media have been assigned that simulate
the transfer of substances from plastic materials into food. These food simulants
represent the major physicochemical properties exhibited by food. According to
Annex III, Sections 1 and 2, of the EU Regulation 10/2011, the food simulants listed
in Table 11.1 have been set out for compliance testing.
Food simulants A, B, and C have been assigned to foods that have a hydrophilic
character and are able to extract hydrophilic substances. Food simulant B is used
Table 11.1 List of Food Simulants According to EU

Regulation 10/2011
Food Simulant Abbreviation
Ethanol 10% (v/v) Food simulant A

Acetic acid 3% (w/v) Food simulant B
Ethanol 20% (v/v) Food simulant C
Ethanol 50% (v/v) Food simulant D1
Vegetable oil Food simulant D2
poly(2,6-diphenyl-para-phenylene Food simulant E
oxide), MPPO, Tenax® particle size
60–80 mesh, pore size 200 nm
for those foods that have a pH below 4.5. Food simulant C is used for alcoholic foods
with an alcohol content of up to 20% and those foods that contain a relevant amount of
organic ingredients that render the food more lipophilic.
Food simulants D1 and D2 are assigned for foods that have a lipophilic character
and are able to extract lipophilic substances. Food simulant D1 is used for alcoholic
foods with an alcohol content above 20% and for oil in water emulsions. Food simu-
lant D2 is used for foods that contain free fats at the surface. Food simulant E is
assigned for testing specific migration into dry foods.
11.3.4 Specific Assignment of Food Simulants to Foods
Based on the general assignments mentioned in the previous section, food simu-
lants are specifically assigned to certain categories of food as laid down in Table 11.2
of Annex III (Section 2) of the European Plastics Regulation 10/2011 (EU 2011a).
Table 11.2 presents some examples for the assignment of food simulants to food
categories.
With the European Plastics Regulation 10/2011 coming into force, the rules on
food simulants and migration testing as laid down before in Directive 78/42/EEC
and in the Annex to Directive 82/711/EEC were substantially revised due to recent
scientific findings comparing migration into food with migration into food simulants.
It was shown that, in many cases, the aqueous simulants according to Directive
82/711/EEC (water, 10% ethanol) showed a significantly lower solubility for the
migrating substances than the foods themselves. Therefore, the food simulants were
changed to higher ethanol contents and thus to a better solubility for lipophilic sub-
stances. Furthermore, the use of the food simulant D1 (50% ethanol), which was already
established for milk and milk products by Directive 2007/19/EC, was expanded to
include additional categories of food. Because the specific migration onto dry foods
is not negligible, simulant E (MPPO, Tenax®) was introduced as an additional offi-
cial food simulant. Even though the use of food simulants may be required due to
Table 11.2 Examples for the Specific Assignment of Food

Simulants to Various Categories of Food
Description of Food Food Simulants
Yogurt (B) and (D1)

Chocolate (D2)
Clear drinks (e.g., water, clear fruit juices, (B) and (C)
coffee, tea, beers, soft drinks)
Cereals, unprocessed, puffed, in flakes (E)
(including popcorn, corn flakes, and the like)
Meat of all zoological species (including poultry (A) and (D2)
and game): (a) Fresh, chilled, salted, smoked
(b) Processed meat products (such as ham,
salami, bacon, sausages, and other) or in the
form of paste, creams
analytical needs, it is clearly indicated that the results of specific migration testing
obtained in food should prevail over the results obtained in food simulants (Article
19 of EU Regulation 10/2011).
11.3.5 Test Conditions for Migration Testing
When migration tests are performed using food simulants, the testing conditions
(time and temperature) should reproduce, as far as possible, the migration that may
occur from the article into the food. The test conditions introduced by the EU
Regulation 10/2011 distinguish between overall migration testing and specific migra-
tion testing. For the overall migration testing, seven standardized test conditions
(OM1 to OM7) and two substitute tests for OM7 (high temperature applications for
fatty foods) are laid down according to Annex V (see Table 3.3) of EU Regulation
10/2011. For the specific migration analyses, the conditions of contact are given in
Table 2.1 (contact time) and Table 2.2 (contact temperature) of Annex V, Chapter 2.
As a general requirement, the sample should be placed in contact with the food simulant
in a manner representing the worst of the foreseeable conditions of use with regard to the
contact time and contact temperature.
In addition, specific migration testing for contact times exceeding 30 days requires
specific test conditions, according to the EU Regulation 10/2011. Migration testing
using the previously utilized conditions (10 days at 40°C) may underestimate the
real migration for barrier materials (e.g., PET, polystyrene, and multilayer laminates
with barrier layers) as well as for thick polyolefin materials during long-term storage
at room temperature. Therefore, specific test requirements, such as accelerated tests,
were introduced by the EU Regulation 10/2011 for packaging materials that are
intended to be stored for more than 30 days.
For the investigation of the migration at long-term storage (> 30 days), the follow-
ing aspects must be considered:
• 10 days/60°C: The strictest condition—for long-term storage for more than six
months at room temperature and below, including heating up to 70°C for up to
2 hours or heating up to 100°C for up to 15 minutes.
• 10 days/50°C: Long-term storage up to 6 months at room temperature; all sto-
rage time at refrigerated and frozen conditions including heating up to 70°C for
up to 2 hours or heating up to 100°C for up to 15 minutes.
• 10 days/40°C: All storage times at refrigerated and frozen conditions including
heating up to 70°C for up to 2 hours or heating up to 100°C for up to 15 minutes.
• 10 days/40°C: For storage at room temperature, testing time can be reduced to
10 days at 40°C if there is scientific evidence that migration of the respective
substance in the polymer has reached equilibration under this test condition.
• Calculation of the test conditions considering the real application condition
using the Arrhenius equation (worst-case activation energy of 80 kJ/mol).
• The maximum testing temperature is governed by the phase transition tempera-
ture of the polymer. At the test temperature, the test specimen should not
undergo any physical changes.
The conditions for the substitute tests using isooctane and 95% ethanol, according
to Table 4 of the repealed Directive 97/48/EC, were not included in the EU Regulation
10/2011. Therefore, these standardized conventional conditions for substitute tests
are no longer applicable. However, alternative food simulants may still be used for
migration testing according to the EU Regulation 10/2011. They are referred to as
“screening approaches” and are discussed in more detail in Section 11.4.
As migration testing is a very complex issue, these basic rules set out in the EU
Regulation 10/2011 cannot cover all foreseeable cases and details necessary for
performing the testing. A guideline document in support of proper interpretation and
use of the EU regulation and dealing with more detailed aspects of the migration testing
rules is currently in preparation within a task force of the EU Commission and will be
made publicly available after finalization. Currently, “Guidelines on Testing Conditions
for Articles in Contact with Foodstuffs,” published in 2009 by the European Joint
Research Centre (JRC) gives practical information on the overall and specific migration
testing of food contact articles with a focus on kitchenware (Simoneau 2009). Although
the current version of the guide is not up to date with regard to the previously described
changes in test conditions and simulants, it may be consulted for general information
purposes and for the testing of materials other than plastics.
It should be noted that, for nonplastic FCMs, different rules for migration testing
may apply according to the legislation of EU member states or according to harmonized
EU law. For example, migration testing of ceramics should be performed with 4%
acetic acid for 24 hours at 22°C regardless of the real-life application of the test
article, according to Directive 84/500 EEC and Directive 2005/31/EC (Veraart and
Coulier 2007).
11.3.6 Overall Migration Testing
According to Article 3 (1) (b) of the European Framework Regulation 1935/2004,

the release of substances from FCMs and articles should not bring about unacceptable
changes in the composition of the food. This requirement is implemented by the over-
all migration (value), which is a generic measure for the inertness of a plastic material.
The OML is defined as the maximum permitted amount of nonvolatile substances
released from a material or article into food simulants. In contrast with the SML,
the OML has no toxicological relevance but is a conventional parameter. The method
for the determination of the overall migration is a gravimetric analysis (i.e., the migra-
tion residue is determined by weighing). Consequently, volatile substances are not
covered by this analytical approach.
According to Article 12 of the EU Regulation 10/2011, plastic materials and
articles shall not transfer their constituents to food simulants in quantities exceeding
10 mg of total constituents released per square decimeter (dm2) of food contact surface
(mg/dm2). The overall migration value must be expressed as an area-related value
regardless of the size or volume of the investigated food contact article. By derogation,
the OML is 60 mg/kg for plastic FCMs and articles that are intended for infants and
young children. In order to achieve comparable results in the verification of compli-
ance with the OML, testing must be performed under standardized test conditions
Table 11.3 CEN Standards of the EN 1186 Series for the Determination of Overall Migration
EN 1186:2002 Materials and Articles in Contact with Foodstuffs: Plastics
Part 1 Guide to the selection of conditions and test methods for overall migration
Part 2 Test methods for overall migration into olive oil by total immersion
Part 3 Test methods for overall migration into aqueous food simulants by
total immersion
Part 4 Test methods for overall migration into olive oil by cell
Part 5 Test methods for overall migration into aqueous food simulants by cell
Part 6 Test methods for overall migration into olive oil using a pouch
Part 7 Test methods for overall migration into aqueous food simulants using a pouch
Part 8 Test methods for overall migration into olive oil by article filling
Part 9 Test methods for overall migration into aqueous simulants by article filling
Part 10 Test methods for overall migration into olive oil (modified method for use in
cases where incomplete extraction of olive oil occurs)
Part 11 Test methods for overall migration into mixtures of 14C-labeled synthetic
triglyceride
Part 12 Test methods for overall migration at low temperatures
Part 13 Test method for overall migration at high temperatures
Part 14 Test methods for “substitute tests” for overall migration from plastics intended
to come into contact with fatty foodstuffs using test media isooctane and
95% ethanol
Part 15 Alternative test methods to migration into fatty food simulants by rapid
extraction into isooctane and/or 95% ethanol
(testing time and temperature) representing worst foreseeable conditions of use of the
plastic material or article. Overall migration testing may only be performed with food
simulants.
For the conventional testing of the overall migration from plastics, the comprehen-
sive series of standards DIN EN 1186, Parts 1 to 12, is available (DIN 2002) as pre-
pared by the European Committee for Standardization (CEN). These standards cover
how to perform overall migration testing using different contact procedures (such as
article filling or total immersion) as well as the different conventional food simulants.
In addition, testing at higher temperatures (>100°C) may follow the European stan-
dard EN 1186-13. Alternative testing procedures can be found in EN 1186, Parts
13B, 14, and 15. An overview of the available standards is given in Table 11.3.
Additional (pre-) standards are available for food contact articles made of cellulose
fibers and of metal:
• CEN/TS 14234 (2003-01): Materials and articles in contact with foodstuffs.

Polymeric coatings on paper and board. Guide to the selection of conditions
and test methods for overall migration.
• DIN CEN/TS 14235 (2003-01): Materials and articles in contact with food-
stuffs. Polymeric coatings on metal substrates. Guide to the selection of condi-
tions and test methods for overall migration.
11.3.7 Specific Migration Testing
The EU Regulation 10/2011 on plastic materials and articles intended to come into
contact with food established a “Union list” of monomers, other starting substances,
and additives that may be used in the manufacture of plastic materials and articles.
Only the substances included in the Union list of authorized substances (as set out
in Annex I of the regulation) may intentionally be used in the manufacture of plastic
layers in plastic materials and articles. Currently, approximately 440 substances that
are included in this “Union list” are regulated by SMLs. The SML is the maximum
permitted amount of a substance released from a material or article into food or
food simulants. Specific migration limits ensure that the FCM does not pose a risk
to the health of the consumer. Therefore, the SMLs set by the Plastic Regulation
EU 10/2011 are based on a risk assessment considering the toxicological properties
of the substances and the possible exposure of the consumer. The basis for setting
an SML is the ADI or TDI value (given in mg per kg body weight), which describes
the acceptable or tolerable daily uptake of a substance from a toxicological point of
view. Additionally, the exposure to substances migrating from FCMs is based on
the conventional assumption that a person of 60 kg body weight daily ingests up to
1 kg of foodstuffs in contact with a plastic article always containing the considered
substance at a concentration corresponding to the SML.
In contrast to the OML, which is a generic measure for the inertness of a FCM, the
SMLs are directly related to the exposure of the consumers and the risk of an unaccep-
table contamination of a food. Depending on the toxicological significance and the
available data, SMLs are set in the range of the analytical detection limit (approximately
10 µg substance per kg food or food simulant) up to the lower ppm range (1–30 mg/kg).
If no specific value is given in the Union list, the SML is 60 mg/kg food.
The specific migration from a substance may be determined analytically in order to
verify compliance with the respective SML. For this purpose, the amount of a certain
substance listed in the EU Regulation 10/2011 is measured in a food that already was
in contact with a packaging material or in food simulants after exposure (migration
contact). Migration testing has to be performed under the worst foreseeable contact
conditions for the intended application (see Section 11.3.4). Depending on their phy-
sicochemical properties (e.g., volatility and polarity), the concentration of the analytes
in the migration solutions can be determined using a variety of analytical techniques,
ranging from gas chromatography (GC) to high performance liquid chromatography
(HPLC), with various detection systems (Table 11.4). An overview of analytical sam-
ple preparation techniques is given in the literature (Nerin et al. 2012).
Several specific analytical methods have been validated or approved by interla-
boratory comparison tests and are publically available, such as the CEN standards
and technical specifications of the series CEN/TS 13130. This series of standards
includes methods for specific migration analyses as well as methods for the determi-
nation of residual contents in polymer materials. An overview of the available stan-
dards of the series CEN/TS 13130 is given in Table 11.5. Additional standards
from CEN and the International Standards Organization are available for the analysis
of substances from materials other than plastics (e.g., for paper and board, lacquers,
Table 11.4 Examples of Analytical Approaches to Determine Specific Migration
Type of Substance Examples Predominant Analytical Method
Volatiles (boiling point Monomers, residual solvents Headspace, SPME, purge, and
<150°C) trap with GC with FID or MS
detection
Semivolatiles (boiling Plasticizers, glycols, additives Liquid injection (split, splitless,
point <300°C) MW < 400–500 Da PTV, on-column, etc.) with GC
with FID or MS detection
Nonvolatiles Antioxidants, additives MW > Liquid chromatography with diode
400–500 Da array, fluorescence, or MS
detection
Source: Simoneau, C. (editor), Guidelines on Testing Conditions for Articles in Contact with
Foodstuffs (with a Focus on Kitchenware), EUR 23814 EN, Office for Official Publica-
tions of the European Communities, Luxembourg, 2009.
Note: PTV, programmed temperature vaporizing; SPME, solid phase microextraction.
and ceramics). In addition, the JRC collects methods from petitions submitted to the
European Food Safety Authority (EFSA) for safety evaluation of new substances to be
included in the “Union list.” Upon request, the summary descriptions—as well as
standard operating protocols developed in the context of interlaboratory comparison
or method validation—can be made available for research purposes. Numerous addi-
tional analytical methods can be found in the scientific literature. The JRC also pro-
vides spectroscopic data of migrants and a database for reference substances.
11.3.8 Testing for the Residual Content in the Polymer
For some substances authorized by the EU Regulation 10/2011 (EU 2011a), the
determination of specific migration is very difficult or even impossible due to the che-
mical instability or high volatility of the substance. In these cases, residual content of
the substance in the polymer material is restricted instead of setting an SML.
For the analytical determination of the residual content, the target analyte must be
released from the polymer matrix by exhaustive extraction. This can be achieved using
several methods:
• Direct measurement of the analyte using headspace–GC analysis for volatile sub-
stances, where applicable, after dissolving the polymer in an appropriate solvent.
• Extraction of nonvolatile substances using a Soxhlet extractor or reflux by
organic solvents and subsequent analysis of the organic extracts.
• Dissolving the polymer in a suitably effective solvent and subsequent repreci-
pitation of the polymer with another solvent that would not result in the incor-
poration of the analyte in the precipitate. After removal of the precipitated
polymer, the target analyte can be measured in the solvent.
The solvents used for the dissolving and extraction processes should exhibit good
solubility for the target analyte but should also be suitably aggressive toward the poly-
mer matrix, leading to a swelling or (partially) dissolution of the polymer matrix.
Table 11.5 CEN Standards and Technical Specifications of the EN 13130 Series for the
Determination of Specific Migration
Materials and Articles in Contact with Foodstuffs:

EN 13130: 2004 Plastics Substances Subject to Limitation
Part 1 Guide to test methods for the specific migration of substances from plastics to
foods and food simulants and the determination of substances in plastics
and the selection of conditions of exposure to food simulants
Part 2 Determination of terephthalic acid in food simulants
Part 3 Determination of acrylonitrile in food and food simulants
Part 4 Determination of 1,3-butadiene in plastics
Part 5 Determination of vinylidene chloride in food simulants
Part 6 Determination of vinylidene chloride in plastics
Part 7 Determination of monoethylene glycol and diethylene glycol in food simulants
Part 8 Determination of iso-cyanates in plastics
Materials and Articles in Contact with Foodstuffs:

TS 13130: 2005 Plastics Substances Subject to Limitation
Part 9 Determination of acetic acid, vinyl ester in food simulants

Part 10 Determination of acrylamide in food simulants
Part 11 Determination of 11-aminoundecanoic acid in food simulants
Part 12 Determination of 1,3-benzenedimethanamine in food simulants
Part 13 Determination of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) in food
simulants
Part 14 Determination of 3,3-bis(3-methyl-4-hydroxyphenyl)-2-indoline in food
simulants
Part 15 Determination of 1,3-butadiene in food simulants
Part 16 Determination of caprolactame salt in food simulants
Part 17 Determination of carbonyl chloride in plastics
Part 18 Determination of 1,2-dihydroxybenzene, 1,3-dihydroxybenzene,
1,4-dihydroxy-benzene, 4,4′-dihydroxybenzophenone and
4,4′-dihydroxybiphenyl in food simulants
Part 19 Determination of dimethylaminoethanol in food simulants
Part 20 Determination of epichlorohydrin in plastics
Part 21 Determination of ethylenediamine and hexamethylenediamine in food
simulants
Part 22 Determination of ethylene oxide and propylene oxide in plastics
Part 23 Determination of formaldehyde and hexamethylenetetramine in food
simulants
Part 24 Determination of maleic acid and maleic anhydride in food simulants
Part 25 Determination of 4-methyl-pentene in food simulants
Part 26 Determination of 1-octene and tetrahydrofuran in food simulants
Part 27 Determination of 2,4,6-triamino-1,3,5-triazine in food simulants
Part 28 Determination of 1,1,1-trimethylolpropane in food simulants
Sample preparation for the extraction processes usually involves the cutting or grind-
ing of the test specimen. Some methods for the analysis of the residual content of
migrants are included in the EN 13130 series of standards as presented in Table 11.5.
Alternatively, practical measurement of the residual content of an analyte may be
omitted in cases where the residual limit cannot be exceeded (e.g., by considering the
amount of substance added to the FCM). However, this kind of “worst-case calculation”
can only be used for additives and processing aids but not for monomers.
It should be noted that the determination of the content of a migrant in a FCM or
article may also be involved for the verification of compliance with SMLs. Following
exhaustive extractions, the maximum possible migration of the analyte can be calculated
assuming its total transfer into the contacting foodstuff. This calculated migration poten-
tial can be compared to the SML. In case the SML is not exceeded, no additional migra-
tion testing will be necessary (see Table 11.3). Furthermore, the information on the
residual content of an analyte in the polymer may also be used for mathematical migra-
tion modeling (see Section 11.5). However, this approach may only be used for the ver-
ification of compliance with SMLs. When stating noncompliance with SMLs, migration
testing into food or food simulants is required.
11.4 ALTERNATIVE MIGRATION TESTS
The assessment of migration can be attained either directly using the standard migra-
tion tests as described previously in Section 11.3 or by semidirect and indirect alterna-
tive migration tests, which are described in this section. Because migration testing is
complex, costly, and time consuming, compliance can also be demonstrated by calcula-
tions, including modeling, other analysis, and scientific evidence or reasoning, if these
obtained results are at least as severe as the results obtained with standard migration tests
(EU 2011a). Indeed, in most cases, these tests strongly overestimate. Therefore, indirect
migration testing can be used to show compliance. In cases of noncompliance, the con-
ventional migration tests must be consulted. In general, it is advisable to consider the
alternative migration test first to avoid unnecessary costs and to save time. Several con-
ventional alternative tests for testing OM and SM are laid down in Regulation 10/2011,
Annex V, Chapters 2 and 3, as so-called “screening approaches” (EU 2011a).
The approach as to how to use alternative tests is not universal but rather is depen-
dent on each specific case and considering the characteristics of the materials. Alterna-
tive testing can be seen as a tiered approach, starting with the most convenient and
simplest consideration followed by more elaborate investigation when no positive result
is obtained. A flow chart for an appropriate procedure is given in Figure 11.2. The single
steps are described more precisely in the following subsections.
11.4.1 Semidirect Migration Test Using Substitute and

Alternative Fat Simulants
Fat usually provides good solubility for many typically used monomers and
additives; therefore, fat is a primary influencing factor for migration (Franz 2005;
TESTING MIGRATION FROM FOOD PACKAGING MATERIALS
Analytical approach Theoretical approach
Analytical Nominal
Gravimetric determined value
determination Migrant concentration
possible? in the material (QM)
OM < SML ? QM < SML ?
No No
No Migrant insoluble Polymer
in food? thickness
Specific migration No
tests QMA < SML ?
Are modeling
No parameters
Contact Material Solubility available?
conditions information of migrant
Direct Semidirect Yes Migration

migration test No migration tests modeling
Yes No
No Yes
Yes Migration modeling < SML ?
Contact
conditions
Noncompliance Compliance Yes
Yes Yes
267
Figure 11.2 Scheme for the determination and evaluation of polymers.
Franz and Simoneau 2008). The fat simulant prescribed for the migration tests for fatty
foods is vegetable oil (simulant D2), according to Regulation 10/2011. Edible oil pre-
valently causes considerable analytical problems due to its rather complex matrix. To
avoid these problems, semidirect migration tests with alternative and substitute fat
simulants can be conducted (Baner et al. 1995). For these tests, simulants are chosen
with respect to the interaction properties between polymer and solvent. The procedures
are described in EN 1186-14 and 1186-15 (see Table 11.3). In EN 1186-14, simulant
D2 is replaced by 95% ethanol and/or isooctane, depending on the polymer. Nonpolar
polymers are used in conjunction with polar solvents (e.g., 95% ethanol/polyolefins)
and vice versa. The standardized conditions described earlier (in Section 11.3) are
used as test conditions. However, when using the substitute food simulants, it must
be ensured that migration results are overestimated compared to the regulated food
simulants (DIN EN 1186-14).
Method EN 1186-15 is based on the determination of the extraction of migratable
substances from plastics. Isooctane is used as the extraction solvent for nonpolar
materials, such as polyolefins, and 95% ethanol for polar materials, such as polyamide.
In this combination, the solvent penetrates the polymer (e.g., causing swelling) due
to strong interaction according to the principle that “like dissolves like” (DIN EN
1186-15). As an example, the difference in the extraction efficiency for laurolactam
from a polar polyamide 12 film into isooctane and 95% ethanol is depicted in
Figure 11.3. Due to the interaction between polyamide and 95% ethanol, laurolactam
is rapidly extracted within several hours, while isooctane does not swell the material.
Therefore, laurolactam migrates slowly (Piringer and Baner 2008:363).
For some materials, the polarity of the polymer is not clear. In those cases, both
tests are required, although the higher value has to be consulted for the assessment.
1.6
Isooctane
1.4 95% ethanol
1.2
Migration (mg/dm2)
1.0
0.8
0.6
0.4
0.2
0 200 400 600 800 1000

Square root time (s)
Figure 11.3 Migration of laurolactam from polyamide 12 into isooctane (rapid extraction)
and into isooctane (migration). (From Piringer, O.G. and Baner, A.L., Plastic
Packaging—Interactions with Food and Pharmaceuticals, Wiley-VCH, Weinheim,
Germany, pp. 363, 2008. With permission.)
Table 11.6 Material/Solvent Combinations Together with the Test Conditions

Applied for OM Testing According to EN 1186-15
Polymer Type of the Food Extraction Solvent Extraction Conditions

Contact Layer to Be Applied to Be Applied
Polyolefins and copolymers Isooctane 24 h/40°C

Polyamides 95% ethanol 24 h/40°C
Polystyrene Isooctane and 95% ethanol 24 h/40°C
Polyethylene terephthalate 95% ethanol 24 h/50°C
Polyvinyl chloride (plasticized) Isooctane and 95% ethanol 24 h/40°C
Polyvinyl chloride (rigid) 95% ethanol 24 h/50°C
Cases in doubt or unknown Isooctane and 95% ethanol 24 h/50°C
An overview on the material/solvent combinations together with the test conditions

applied for OM testing according to EN 1186-15 is given in Table 11.6.
11.4.2 Extraction and Total Mass Transfer Assumption
The simplest way to state compliance can be done by a worst-case calculation

assuming total mass transfer from a packaging constitute into food. For this
approach, the concentration of the substances in the material and the thickness of
the polymer need to be known. The nominal concentration of substances such as
additives and polymerization production aids in the material is directly available
by knowing the composition of the material. If the concentration is unknown, the
actual residual content has to be determined analytically. For the analytical approach,
the substance has to be extracted completely using suitable solvents depending on the
physicochemical properties of substance and polymer. Thin films can be extracted
directly, while thicker materials should be crushed before extraction. If the residual
content of a substance in a polymer (in mg/kg material) is lower than the SML
(in mg/kg food), the migration limit can logically never be exceeded (QM < SM).
This situation appears only rarely. Usually the QMA, which takes the layer thickness
into account, is compared with the SML by applying the conventional surface-
to-volume ratio of 6 dm2/kg. In both cases, QM < SM and QMA < SML tests are
superfluous (Franz 2000).
It is obvious that the QMA value and, consequently, the SM value are dependent
on the polymer thickness. In very thin layers, the area related concentration is lower
compared to thicker layers. Legally based, the ratio for QM/SML is set at 100 (QM
[mg/kg plastic]/SML [mg/kg food]) by convention. Butadiene can be considered as
an example. For this substance, the residual content is set at 1 mg/kg in the final pro-
duct, and the SML is set as not detectable with a detection limit of 0.01 mg/kg, accord-
ing to EU Regulation 10/2011. Assuming a polymer density of 1 g/cm3 and applying a
surface-to-volume ratio of 6 dm2/kg food (EU cube model), the QM restriction coin-
cides with the SML when applying a layer thickness of 166 µm. Taking the previously
described assumption but changing the layer thickness, the concentration of butadiene
18
16
14
Conc. in polymer (mg/kg)
12
10
2 QM = SML
0 100 200 300 400 500 600

Layer thickness (μm)
Figure 11.4 Maximum butadiene concentration in the material for different layer thicknesses
that correspond to an SML of 0.01 mg/kg.
in the material that corresponds to an SML of 0.01 mg/kg becomes <1 for thicker
layers and >1 for thinner layers. In Figure 11.4, the relation of QM/SM versus the
layer thickness that corresponds to an SML of 0.01 mg/kg is given. From this curve,
it is apparent that for thin layers the QM is too severe, while for thick layers it is too
relaxed (Franz 2000; Piringer and Baner 2008:356). This total transfer approach is
only applicable for a single substance or for the total of all potentially migratable
substances in the material. One main advantage of the indirect migration evaluation
for analysis of the material is a higher substance concentration and a simpler analytical
matrix. However, this is a worst-case approach that does not consider any partition and
kinetic effects.
11.4.3 Solubility as a Migration Limiting Factor
If compliance with the limit cannot be shown assuming total mass transfer, less
severe approaches can be used that consider the mass balance with respect to partition-
ing of a substance between food and plastic material. Knowing the initial concentra-
tion of a respective substance in the material cP0, the geometry of the packaging
system (polymer thickness dP, volume of packaging VP, and food VF, and the contact
area between packaging and food A) as well as the partition coefficient between poly-
mer and food KP/F, migration into food at equilibrium cF,∞, can be calculated accord-
ing to Equation 11.1 (Franz 2002)
cPo
cF1 = (11.1)
1 + K A dP V1L
whereas the partition coefficient is defined as given in Equation 11.2 (Simoneau

2010)
cP1 ρP
KP=F = (11.2)
cF1 ρF
Other than the partition coefficient, all other input parameters for the calculation of
migration are easily accessible. However, in most cases, KP/F is not known and the
determination of this parameter is quite complex. To use this approach nevertheless,
some general considerations can be made.
In commercially available packaging systems, the volume ratio between packaging
and food, VP/VF, is <1. In this case, the entire amount of substances is transferred into
the food, which results in a KP/F at equilibrium of 1 (= total mass transfer). Assuming
that a substance is more soluble in the polymer than in the food, the substance stays
in the polymer instead, which leads to a KP/F > 1. This scenario typically occurs for
nonpolar substances in contact with aqueous simulants. For example, octadecyl
3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate is used as a widespread plastic
additive with an SML of 6 mg/kg food (simulant). From the water solubility and the
log PO/W of this substance (water solubility: 6.09 10−9 mg/l; log PO/W = 13), it is obvious
that octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate is largely insoluble in
aqueous simulants such as 3% acetic acid and 10% and 20% ethanol. This leads to a
KP/F > 1000 and, therefore, to very low migration. It has been shown that migration
is strongly dependent on the type of food and food simulant (Franz 2000; Piringer
and Baner 2008:362). Migration tests for nonpolar substances (log PO/W > 8) embedded
in nonpolar polymers (e.g., polyolefins) into aqueous simulants are therefore superfluous.
11.4.4 Diffusion Characteristics Similar to but More

Severe Than Standard Migration Testing
In addition, the diffusivity of a given polymer also can be considered. For poly-
mers with low diffusivity, the mobility of substances in the polymer is low. PET
can be used as an excellent case example. PET is a very inert material that is usually
manufactured with low amounts of additives and contains only low migratable con-
stitute content (e.g., monomers). Consequently, migration from PET is expected to
be low. Extensive research on PET bottles has been performed within the last few
years. The overall migration on representative PET bottles as well as the specific
migration of the PET typical monomers monoethylene glycol (MEG), diethylene
glycol (DEG), and terephthalic acid was tested into the food simulants 3% acetic acid,
10% ethanol (10 days at 40°C), and 95% ethanol (10 days at 40°C and 24 hours at
50°C). The overall migration was found to be below 0.5 mg/dm2 in all cases. These
values are far below the OML of 10 mg/dm2 and within the analytical uncertainty of
the standard method EN 1186 of ± 2 mg/dm2 (Störmer et al. 2004). No migration of
the typical PET monomers MEG, DEG, and terephthalic acid was observed at a detection
limit of approximately 0.5 mg/dm2 for MEG and DEG and of approximately 1 mg/dm2
for terephthalic acid. All obtained values were far below the SML of 30 mg/kg and
5 mg/dm2 for the sum of MEG and DEG (including stearic acid glycol ester) and
7.5 mg/kg and 1.25 mg/dm2 for terephthalic acid, respectively. It can be concluded
that migration is only influenced by surface effects and that migration is largely indepen-
dent on the type of contact medium (i.e., independent of KP/F). Furthermore, it can be
concluded that the overall migration as well as the SMLs for MEG, DEG, and terephtha-
lic acid from PET can never be exceeded even using the alternative fat simulant 95%
ethanol that swells the polymer. In this case, conventional migration tests are not neces-
sary. On the other hand, due to the low diffusivity of PET, extremely high concentra-
tions in the material would be necessary to obtain concentrations in the food as high
as the SML. Such high concentrations in the material would change the material proper-
ties significantly (Welle 2013a).
Similar conclusions can be made for acetaldehyde where the SML of 6 mg/kg can
never be exceeded. However, regarding migration of acetaldehyde, there is a risk of
deterioration of the food because the organoleptic threshold of this substance is
already in the range of 0.01 to 0.02 mg/kg. However, this fact is only relevant for car-
bonated water. In noncarbonated water, acetaldehyde is not stable; and in fruit juices,
soft drinks, and beer, migration of acetaldehyde is negligible because acetaldehyde is
present in food itself in much higher concentrations. Again, it is superfluous to deter-
mine the specific migration but strongly recommended sensory tests be performed,
especially for carbonated water (Welle 2013a).
11.4.5 Nonrequirement of Migration Tests
Migration tests are not required in the following cases (IVLV 2011):
1. Overall migration tests for materials that are intended to come into contact with
dry food (without fat on the surface).
2. Specific migration tests are not required in cases:
a. Where the SML cannot be exceeded assuming total mass transfer
b. When calculated migration values applying migration models are below the
SML
c. When the OML (including analytical tolerance of the overall migration
method) is below the SML provided that the substances is not volatile
and is determined with this gravimetric method. In which case, the overall
migration test conditions must be adapted to the specific test conditions.
11.4.6 Functional Barriers
EU Regulation 10/2011 on plastic materials and articles that are intended to come
into contact with food covers multilayer materials consisting exclusively of plastics
that are bound together by adhesives or by any other means as well as in combination
with other materials such as board or aluminum (multimaterial multilayer materials)
(EU 2011a). The aim of packaging is to act as a barrier to protect food from external
influences. To obtain packaging materials with good barrier properties for food
and reduction of packaging waste, packaging materials usually are combinations
consisting of different layers (as many as 15). In very few cases, the packaging material
is an absolute barrier where the migration is nearly zero (e.g., glass). On the contrary, in
the majority of cases, the materials may be barriers with respect to specific substances
(e.g., oxygen), while migration of other substances from layers behind the barrier is
unavoidable.
According to the definition in Article 3 of Regulation 10/2011, “A functional barrier
means a barrier consisting of one or more layers of any type of material which ensures
that the final material or article complies with Article 3 of Regulation 1935/2004 (EU
2004) and with the provisions of this Regulation.” In other words, the term functional
barrier describes the ability of a multilayer packaging system to prevent or delay the
migration of compounds from a nonfood contact layer into the food. The functional
barrier can be divided into kinetically controlled and thermodynamically controlled
functional barriers. The functional barrier is related to a “functional” quantity in
terms of migration that is dependent on the application (storage conditions = diffusion
and kinetic controlled) and on technological factors (= diffusion controlled) (Piringer
and Baner 2008:350).
According to Article 13 of Regulation 10/2011, nonauthorized substances may be
used behind a functional barrier provided that those substances are not classified as
carcinogenic, mutagenic, reprotoxic (CMR) substances, they are not nanoscaled,
and that their migration is below a limit of 0.01 mg/kg (EU 2011a).
After production of a material, substances from the outside may migrate into adja-
cent layers right up to the food contact layer. This step is strongly time dependent. At
very short storage times after production of the material (e.g., some days), no significant
migration of substances from the adjacent layers has taken place—possibly the food
contact layer has not been reached yet, and consequently, migration of these substances
into food is low. This phenomenon can be described as the lag-time effect (Franz 2003).
As another important influencing factor, the manufacturing method should be con-
sidered. Multilayer structures are usually manufactured by coextrusion at temperatures
above the melting point of polymers. During this manufacturing step, substances from
outer layers can penetrate the functional barrier within some seconds or even millise-
conds, which consequently leads to an impurity of the “virgin” barrier layer. Conse-
quently, at the time when the food is inserted in the packaging, the food has already
had direct contact with outer layer constitutes and no migration time lag appears (see
Figure 11.5). In structures where the food contact layers consist of highly diffusive poly-
mers such as polyolefin, the lag-time effect can be assumed to be very low after the
applied manufacturing conditions. On the other hand, for polymers such as PET, the
functional barrier efficiency remains as is due to the inherent low diffusivity.
Migration from multilayer materials can be investigated in analogy to conventional
migration tests as laid down for monolayer materials. However, for those materials, the
lag-time effect must be considered. Thus, the lifetime of multilayer packaging (from the
time of the production of the packaging until the shelf life of the packed food) must
be taken into account. In cases where the lifetime of the product is shorter than the lag
time, the packaging material can be considered as safe. On the other hand, when the
lag time is shorter than the lifetime or when both periods are about the same, migration
tests are necessary (Franz 2003). Taking the lag time into account, the specific migration
Adjacent FB Filling good

layers
“Virgin” FB
(a)
Adjacent FB Filling good
Migration
layers
(a) (b)
(c)
Partially loaded FB
(b)
Lag time (a) Time
Adjacent layers FB Filling good
Lag time (b)
Completly loaded FB
(c)
Figure 11.5 Migration from multilayers at the time of filling.
test conditions have been changed from 40°C to 60°C since EU Regulation 10/2011 came
into force. With this elevation in temperature, the respective substance in the polymer
should have reached equilibration, considering the lag time. Examples of materials
that can be defined as “recognized” functional barrier systems where no migration
tests are required include glass, aluminum layers (≥7 µm), metal, PET and polycarbonate
(PC) bottles (≥100 µm), and polystyrene (≥300 µm)—but also thick polyolefins such as
polypropylene (≥500 µm) beakers and thick high-density polyethylene (HDPE) bottles
(≥ 500 µm) (Franz 2003).
11.5 MIGRATION MODELING
Experimental specific migration testing is a labor-intensive, time-consuming, and,

therefore, expensive procedure. Migration modeling, on the other hand, is a tool for
the fast and economic specific migration prediction and compliance evaluation of a
known polymer type. Within the last few decades, diffusion of organic molecules
in (packaging) polymers has been studied intensively. Nowadays, the migration
phenomenon for organic compounds into food is well understood and can be simu-
lated by the use of mathematical diffusion models. As a consequence, migration
modeling has been included in European legislation. EU Regulation 10/2011 mentions,
“To screen for specific migration, the migration potential can be calculated based on the
residual content of the substance in the material or article applying generally recognized
Are modeling parameters

available for the polymer?
Yes No
Perform migration Experimental

modeling migration test
Predicted migration Predicted migration Migration is Migration

is below SML exceeds SML below SML exceeds SML
Product compliant Product not compliant
Figure 11.6 Decision tree for compliance evaluation using of migration models.
diffusion models based on scientific evidence that are constructed such as to overesti-
mate real migration.” Based on this legislative background, migration modeling can
be applied for the compliance evaluation of FCMs. For that purpose, in principle, migra-
tion modeling should be overestimative, which means that in every case the predicted
migration should be at least as severe as experimental migration testing. As a conse-
quence, migration modeling can be used to show compliance of a FCM but not to
show noncompliance. The decision tree for compliance evaluation based on migration
modeling is given in Figure 11.6.
11.5.1 State of the Art of Migration Modeling
In general, the migration from a polymer can be calculated at a certain temperature

according to Equation 11.3 (Crank 1975). The parameter m/A is the area related mass
transfer from the polymer into the foodstuff (typically expressed in µg/cm2). The
concentration of the migrant in the polymer before the migration experiment is cP,0
(in mg/kg). The diffusion coefficient of the migrant in the polymer is DP (in cm2/s)
and t (in s) is the storage time. ρp (g/cm3) is the density of the polymer, and the thickness
of the packaging material is dP (in cm). The dimensionless factor α (Equation 11.4) con-
tains the partition coefficients KP,F and the volumes of the packaging and foodstuff (VP
and VF).
2 3
m α X1
2αð1 + αÞ
q2
− DP t 2n
= cP,0 ρP dP 41 − e d
P 5 (11.3)
A 1+α n=1
1 + α + α 2 q2
n
1 VF
α= (11.4)
KP,F VP
For a given polymer or packaging material, the parameters such as polymer

density, film or bottle wall thickness, volume of the foodstuff, and so on are easily
available due to the given material properties and due to the packaging geometry.
Therefore, most of the parameters in Equation 11.3 are well known. In addition, the
concentration of the migrant in the packaging material (cP,0) can be determined experi-
mentally by the extraction of the packaging material. In conclusion, only the diffusion
coefficient DP and the partition coefficient KP,F are typically not directly available.
Both parameters, however, play an important role in the prediction of the migration.
Therefore, intensive work has been done in order to predict the diffusion coefficients
and the partition coefficients between the food contact article and food (simulant) for a
potential migrant.
Partition coefficients can be predicted from experimental migration tests
using ethanolic solutions of different concentrations in water. On the other
hand, as mentioned earlier, migration modeling for compliance evaluation should
be overestimative. Therefore, worst-case partition coefficients can be assumed for
the prediction of the specific migration of organic molecules into foodstuffs. A
worst-case situation can be assumed if the organic molecule is well soluble in
food (simulant). Good solubility of an organic molecule is established for K = 1.
Therefore, K = 1 can be used in any case for the specific migration prediction
from FCMs into food (simulants). It should be noted here that the partition coeffi-
cient plays a role when the predicted migration nearly reaches the equilibrium. On
the other hand, in cases where the predicted migration is far away from the equili-
brium state, only the diffusion coefficient determines the mass transfer into the
foodstuff.
Several equations for the prediction of diffusion coefficients have been developed.
An overview of the published prediction models for diffusion coefficients in polymers
is given in the literature (Pocas et al. 2008). The currently accepted model for the pre-
diction of diffusion coefficients was developed by Piringer (Piringer 2007; Simoneau
2010). According to this model, an equation has been established for the prediction
of diffusion coefficients in common food contact polymers from their molecular
weight M. In this equation, D is the diffusion coefficient (in cm2/s) and T is the
temperature (in K). AP represents a dimensionless polymer specific factor that
could be understood as some kind of conductance of the polymer toward diffusion.
In general, soft polymers such as low density polyethylene (LDPE) with higher
diffusion constants are characterized by higher AP values, whereas stiff chain polymers
such as polyesters with lower diffusion constants have lower AP values. Where AP
varies with temperature, AP′ is introduced as a temperature independent term according
to Equation 11.6. Table 11.7 summarizes the currently accepted AP′ parameters
for packaging polymers (Simoneau 2010). The parameter τ represents the activation
energy EA of diffusion of a migrant in the FCM (Equation 11.7). R is the gas constant
(8.31446 J/K mol).
Table 11.7 Currently Accepted AP′ and τ Values for Different

Packaging Polymers (Simoneau 2010)
Polymer AP′ τ (K) EA (kJ/mol)
LDPE and LLDPE 11.5 0 87

HDPE 14.5 1577 100
PP (homo and random) 13.1 1577 100
PP (rubber) 11.5 0 87
PS –1.0 0 87
HIPS 1.0 0 87
SBS 10.5 0 87
PET (<Tg) 3.1 1577 100
PET (>Tg) 6.4 1577 100
PEN 5.0 1577 100
PA6 0 0 87
PA6,6 2.0 0 87
PA12 2.6 0 87
PVC (rigid) −1.0 0 87
Note: HDPE, high density polyethylene; HIPS, high impact poly-

styrene; LDPE, low density polyethylene; LLDPE, linear
low density polyethylenene; PA, polyamide; PEN, polyethy-
lene naphthalate; PET, polyethylene terephthalate; PP,
polypropylene; PS, polystyrene; PVC, polyvinyl chloride;
SBS, styrene butadiene styrene copolymere.
D = 104 eAP − 0:1351M + 0:003M − 10454

2=3
T (11.5)
τ
AP = A0P − (11.6)
T
EA = ð10454 + τÞR (11.7)
11.5.2 Recent Developments in Diffusion Modeling
It is obvious from Table 11.7 that the parameter τ is set either to 0 K or to 1577 K,
which represents activation energies of diffusion EA of 86.9 kJ/mol or 100.0 kJ/mol,
respectively. Therefore, the activation energy is set as a conservative default parameter
for compliance evaluation purposes and applied for all kinds of migrants. This fixed
activation energy leads to an overestimation of the diffusion coefficients, especially
for high molecular weight molecules. This effect becomes particularly evident for low
diffusive polymers such as PET (Ewender and Welle 2013). Consequently, in recent
years, new equations have been developed for the more realistic prediction of diffusion
coefficients for PET. Realistic migration modeling is important for exposure estimations.
The first, more realistic equation for PET is given by Piringer (Piringer and Baner
2008:192). Equation 11.8 is valid for PET below the glass transition temperature Tg.
A similar equation is available for PET for temperatures above the glass transition
temperature Tg, where Mr,I is the molecular weight of a migrant (in g/mol), Mr,p is
the molecular weight of a polymer (in g/mol), and T and Tg are the storage temperature
and the glass transition temperature of the polymer (both in K), respectively. The indi-
vidual terms of Equation 11.8 are given in Equations 11.9 through 11.15.
2=3 2=3 2=3 Tg R

DP,i = Du e wi,e − wp,e 0:14wl ð14j + 2Þ − wwi,e RT (11.8)

2π i=e
wi,e = 1 + (11.9)
i

2π p=e
wp,e = 1 + (11.10)
p
w = 22π=e (11.11)
pffiffiffiffiffiffiffiffiffiffiffiffi
w1 = 1 + 2π (11.12)
Mr,i − 2
i= (11.13)
14

Mr,i − 2 1=3
j= (11.14)
14
1=3
Mr,p
p= (11.15)
14
Another more convenient equation for the prediction of diffusion coefficients

in PET (Equation 11.16) has been published more recently (Welle 2013b). This
equation is based on the molecular volume V of the migrant instead of the molecular
weight. The parameters a through d are PET specific parameters, which were
determined experimentally to a = 1.93 10−3 1/K, b = 2.37 10−6 cm2/s, c = 11.1 Å3,
and d = 1.50 10−4 1/K (Welle 2013b); T is the temperature (in K). This equation is
valid below as well as above the glass transition temperature because activation
energies of diffusion measured below and above Tg were used to determine the
PET specific parameters a through d (Ewender and Welle 2013; Welle 2013b).
a −d T1
V
DP = b (11.16)
c
1,E-09 Welle
Piringer
Diffusion coefficient (cm2/s)
1,E-11 AP΄ = 3.1
Experimental data
1,E-13
1,E-15
1,E-17
1,E-19
1,E-21
0 100 200 300 400
Molecular weight (g/mol)
Figure 11.7 Correlation between the molecular weight and the diffusion coefficients of the
current model with AP′ = 3.1 (Simoneau 2010), Piringer (Piringer and Baner 2008: 192) and
Welle (Welle 2013b) for PET at 40°C (experimental data from Table 3 in Welle and Franz 2012).
Figure 11.7 shows the comparison of the currently accepted migration model
(AP′ = 3.1, τ = 1577 K) for the prediction of diffusion coefficients, with recent devel-
opments by Piringer (Piringer and Baner 2008:192) and Welle (Welle 2013b), at 40°C. It
becomes obvious that the current model (AP′ = 3.1, τ = 1577 K) significantly overesti-
mates the diffusion coefficient for molecular weights of >80 g/mol. On the other hand,
small molecules such as permanent gases (carbon dioxide, oxygen, and so on) are signif-
icantly underestimated by the current model. Both the new equations (Equation 11.8 and
Equation 11.16) fit the experimental data much better. Therefore, Equation 11.8 and
Equation 11.16 also can be applied for the prediction of the permeation of permanent
gases through PET bottles or for the loss of carbon dioxide during storage. On the
other hand, both equations are not overestimative in some cases because some of the
experimental points are slightly above the predicted values. Therefore, on the first glance,
both equations cannot be used for compliance evaluation. However, in the case of Equa-
tion 11.16, an uncertainty of ± 20% of the molecular volume V for the prediction of the
diffusion coefficients was suggested. By using this variance, all experimental data are
within the corridor for the predicted diffusion coefficients (Welle 2013b). The upper bor-
der of the 20% uncertainty can be considered as worst case and can be used for compli-
ance evaluation.
11.6 SCREENING ANALYSIS TO ENSURE QUALITY

AND SAFETY-IN-USE OF FCM
By conducting the aforementioned migration tests, compliance with the overall SMLs
of known monomers and additives can be tested (see Section 11.3). However, these
tests do not cover NIAS that are not listed as authorized monomers or additives in EU
Regulation 10/2011 but that might still be present in packaging materials. Those
substances are included in the general safety requirements of Article 3 of the European
Framework Regulation 1935/2004 and must not endanger human health (EU 2004).
Typically, the limit of 10 µg/kg for nonevaluated substances, according to EU Regulation
10/2011, is applied for NIAS.
Unlisted substances that can be found in FCMs may include:
• Impurities in starting substances

• Reaction intermediates
• Decomposition products
• Reaction products
• Oligomers
• Substances originating from use or misuse by the consumer of repeated use
packaging/recycling materials
• Substances that are applied on the nonfood contact side that might be trans-
ferred to the food contact side (e.g., by set-off)
In such cases, nontarget screening assays are required that ideally are able to detect,
identify, and quantify a wide range of chemical components differing in structure, polar-
ity, and molecular weight (Veraart and Coulier 2007).
11.6.1 Screening Methods
Screening methods aimed at the detection and identification of unknown, migratable

substances include headspace and liquid injection gas chromatography-flame ioniza-
tion detector/mass spectrometry (GC–FID/MS) and LC–MS techniques for organic
compounds, and atomic absorption spectrometry (AAS) and inductively coupled
plasma (ICP) techniques for inorganic compounds, and element analysis (Veraart
and Coulier 2007). Volatile substances can be analyzed by headspace-GC. Identifi-
cation can be achieved by coupling with MS and comparison of the obtained mass
spectra with databases such as the National Institute of Standards and Technology
(NIST) database. The principle of headspace-GC is the partitioning of compounds
between the gas phase and the liquid phase, which in turn is strongly dependent
on the chemical properties of a molecule (Veraart and Coulier 2007). Quantification
can be achieved by multiple headspace extraction, using the respective substance or
a structurally related substance with similar polarity for calibration.
The retention time of a substance correlates with the molecular mass and can there-
fore be used for estimation in the case of unknown substances. Experiments have also
shown that there is a correlation between the retention time and the detector response
of the headspace screening. The detector response decreases with increasing molecu-
lar weight. With the help of this correlation, the concentration of unknown substances
can be estimated from the retention time of the unknown substance (Franz et al. 2004).
Substances of lower volatility are analyzed directly in migration solutions or extracts
of FCMs by GC–FID/MS. Typically, extracts of a material are used for the identification
Table 11.8 Examples of NIAS Clearly Identified in PET Bottles and Closures
Compounds Possible Source or Introduction Pathway
Acetaldehyde, 2-methyl-1,3-dioxolane, Degradation products of PET

ethylene glycol, PET cyclic trimer
Linear and branched hydrocarbons Side products from the polymerization of
HDPE and PP
Saturated and unsaturated aldehydes Degradation products from the HDPE and PP
as well as from polymer masterbatches
Propanoic acid, butyric acid Degradation products from masterbatches
found in closures
Isophthaldialdehyde, caprolactam, Polymerization side-products and impurities
cyclopentanone, ortho-, meta-, para-xylene, from (active and passive) PA barriers in PET
tetrahydropyranone bottles
Dichlorobenzene Impurity of color masterbatches
Anthranilamide reaction products Acetaldehyde scavenger in PET bottles
with aldehydes
Nonylphenol (several isomers) Degradation product from additive
masterbatches
Note: HDPE, high density polyethylene; PP, polypropylene.
of unknown substances because the concentration is higher than in migrates. With this
method, the compounds detected can be semiquantified using a universal standard as
the signal if the FID correlates in theory with the mass of carbon atoms per time unit
in the column output (Franz and Störmer 2008).
For nonvolatile compounds that can only be measured by HPLC, such a generally
applicable method for a semiquantitative determination based on a universal calibration
is not yet available (Franz and Störmer 2008). Moreover, identification of unknown
peaks in the chromatogram is often very difficult due to the fact that no large databases
exist for LC–MS. Very nonpolar components (e.g., aromatics, alkanes) might not be
ionized at all with LC–MS and will therefore not be visible in LC–MS chromatograms.
11.6.2 Examples for NIAS
Some examples of NIAS are given in Table 11.8. These substances have been
identified in PET bottles and polyolefin closures by headspace–gas chromatography.
Headspace screening for NIAS is a crucial parameter for compliance testing of
PET materials. Because PET is a very inert packaging polymer, the limit for the overall
migration as well as the SMLs for monomers and catalysts given in EU Regulation
10/2011 cannot be exceeded even if worst-case storage conditions and swelling food
simulants are applied (see Section 11.4). Therefore, mainly volatile NIAS are of
concern for compliance testing. Due to their low molecular weight, such NIAS have
high diffusion coefficients, and concentrations of 10 μg/kg in food might be exceeded
very fast. The organoleptic threshold of volatile components also might be exceeded
(Welle 2013a). Figure 11.8 shows the headspace-GCs of a typical PET bottle and a
PET bottle containing NIAS.
Critical molecular Anthranilamide

weight range
Detector response (counts)
Acetaldehyde
Ethylene glycol
2-Methyl-1,3-dioxolane
Retention time (min)
Figure 11.8 Headspace-GC of PET bottles. Bottom: Typical PET bottles; top: PET bottle
with NIAS. (From Welle, F., Approach for compliance testing of PET packaging
materials, 26th IAPRI Symposium on Packaging, Espoo, 2013, pp. 381–385.)
11.6.3 Potential and Limitations of Screening Analyses
Screening analyses are a way for manufacturers to control raw materials during the
production process in order to ensure constant material composition and quality.
Screening analyses can also be applied in order to investigate a possible set-off of print-
ing ink components or lacquers that are applied on the outer side of an FCM but that
might be transferred to the food contact side during storage in a stack or in rolls thereby
ensuring that materials or articles are manufactured in accordance with good manufac-
turing practices as demanded by EU Regulation 2023/2006 (EU 2006) as well as with
the general safety requirements of Article 3 of the European Framework Regulation
1935/2004 (EU 2004). When extracts of FCMs are used for GC–FID/MS screening
analysis, the residual content of unknown substances can be semiquantified using a
universal standard. The molecular mass of the molecule can be estimated by its retention
time. Knowing the concentration in the material and the molecular mass of a substance,
migration can be estimated by migration modeling (see Section 11.5). Using this strategy,
compliance with the migration limit of 10 µg/kg for nonevaluated substances, according
to EU Regulation 10/2011, can be evaluated even if the substance cannot be identified
by screening analyses.
Semiquantitative screening analyses can also replace specific migration tests for
known monomers or additives provided that the concentration measured by screening
is well below the SML. Typical substances that are covered by the GC screening method
are the antioxidants Irganox® 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)

propionate) or di-tert-butyl-hydroxytoluene. On the other hand, if the semiquantified
concentration of a substance found in the screening analysis is close to the migration
limit, a specific determination should be carried out to confirm compliance. It must be
noted that none of the screening methods described or even a combination of all these
methods will be able or sensitive enough to detect all possible migratable substances.
However, screening tests give at least a good indication of the presence of potentially
migrating substances in FCMs or in food simulants.
11.7 RECYCLING OF FCMS INTO NEW FCMS
11.7.1 Metals and Glass
Metals and glass are traditionally recycled into new FCMs. Due to the very high
temperatures during remelting, all postconsumer substances are removed during
recycling and production of the new FCMs. Recycled metal and glass FCMs have
to comply with the existing applicable EU and national legislations.
11.7.2 Plastics
In contrast to metals and glass, postconsumer substances might be absorbed into a

polymer during the first use of a plastic packaging material. The amount of absorbed
substances and their concentrations in postconsumer materials foreseen for recycling
depends on the first use, the storage conditions, the diffusivity of the polymer, the
recollection systems, the recycling processes, and so on. Due to this complex situa-
tion, the evaluation of the suitability of postconsumer plastics for reuse in food packa-
ging applications means they cannot be treated like virgin polymers because, in post-
consumer polymers, the nature and concentrations of potential migrants are only
roughly known. The concentrations can be determined with screening methods similar
to NIAS for virgin polymers; however, the results depend on the subsample that was
analyzed. Compared to virgin polymers, postconsumer polymers are more inhomoge-
neous. As a consequence, the control of the input materials (feedstock control) as well
as the cleaning efficiencies of the recycling processes play an important role.
The feedstock materials for recycling can be divided into pre-consumer and post-
consumer waste. Pre-consumer scrap is material from production by the manufactur-
ing or converting industry. Typically, the history and contamination levels are well
known and the material is under the control of the processor. Provided that good man-
ufacturing practices are followed and contamination can be excluded, this material is
suitable for direct food contact similar to virgin polymers. On the other hand, the eva-
luation of postconsumer plastics for recycling into FCMs has to consider special leg-
islation or recommendations (FDA 2006; EU 2008). Postconsumer plastics can be
either chemically recycled into new feedstock materials (monomers, oligomers) for
the production of new FCMs, or they can be mechanically recycled. In addition,
the recyclates can be applied in direct contact with food or behind a functional barrier
(e.g., a virgin layer of the same polymer).
From a legislative point of view, chemically recycled FCMs are treated similarly
to virgin polymers (FDA 2006; EU 2008). During chemical recycling, several purifi-
cation steps are applied for the monomers/oligomers so that they are similar in purity
to other monomers used for polymerization of food contact plastics. Chemically
recycled FCMs are typically indistinguishable from the same materials/polymers
manufactured from conventional resources (e.g., crude oil). Recycled postconsumer
polymers behind functional barriers are not covered by the EU Recycling Regulation
282/2008 (EU 2008). Therefore, these FCMs should be evaluated similarly to sub-
stances in multilayer packages (see Section 11.4.6). In contrast, mechanically recycled
packaging materials that come into direct contact with food are within the scope of the
European Recycling Regulation 282/2008. FCMs that are mechanically recycled may
contain traces of substances from the first use of the FCM. These postconsumer com-
pounds can be considered as NIAS. Therefore, nontargeting screening approaches
(see Section 11.6) should be applied in order to determine postconsumer substances
or degradation products in the recyclate containing FCMs.
Overall or specific migration testing is not applicable for compliance tests of recy-
clate containing FCMs because the concentration and type of postconsumer sub-
stances depends on the recycling process and the input materials for the recycling
processes. In principle, it is impossible to individually evaluate all possible substances
that could come into contact with packaging materials during their first usage or if
there is improper use (e.g., filling PET bottles with household cleaners or garden che-
micals). This is why the evaluation can only be undertaken by considering worst-case
scenarios. Recycling processes are typically evaluated based on their cleaning effi-
ciency toward postconsumer substances. The cleaning efficiency is determined in a
so-called “challenge test.” A challenge test is carried out on FCMs that have been
deliberately contaminated with (model) contaminants. The artificially contaminated
FCMs are then subjected to the recycling process. The difference between the initial
contamination and the residual contamination in the end product is a measure of the
cleaning efficiency of the recycling process. The challenge test procedure and the
model compounds (“surrogates”) typically used in challenge tests are described in
detail elsewhere (Franz et al. 2004; Welle and Franz 2007). Due to the fact that the
evaluation strongly depends on the applied recycling process, an individual authoriza-
tion process has been established in Europe and in the United States for postconsumer
plastics (FDA 2006; EU 2008).
11.7.3 U.S. Food and Drug Administration Criteria for

Evaluation of Recycled Plastics in Food Contact
The U.S. Food and Drug Administration (FDA) has published guidelines for the recy-
cling of postconsumer plastics into direct FCMs (FDA 2006). The FDA suggests that
dietary exposures to contaminants from recycled FCMs at a concentration of 0.5 µg/kg
or less generally are of negligible risk. With the help of so-called consumption factors
(CFs), these dietary exposures can be converted into migration limits (FDA 2007).
Currently, the FDA applies a CF = 0.05 as the valid consumption factor for postconsu-
mer plastics. Therefore, the migration limit of PET recyclate-containing packages is
10 µg/kg for each individual substance. This concentration should be understood as
the maximum migration of surrogates (after a challenge test with worst-case contamina-
tion levels) in a FCM with a certain amount of postconsumer recycled plastics. Using
migration models, this 10 µg/kg migration value can be transformed into maximum
bottle wall concentrations. The latter can be easily controlled by the use of GC screening
methods. Figure 11.9 shows the maximum bottle wall concentration for HDPE and PET
that corresponds with the FDA 10 µg/kg migration limit after storage for 10 days at 40°C
(surface 6 dm2, volume 1 L, K = 1) for the packaging polymers PET and HDPE.
100
90
Bottle wall concentration (mg/kg)
80
70
60
50
40
30
20
10
0
0 100 200 300 400
(a)
5
Bottle wall concentration (mg/kg)
0
0 200 400 600 800 1000
(b)
Figure 11.9 Bottle wall concentration corresponding to the 10 µg/kg migration after storage
for 10 days at 40°C calculated using the currently accepted AP′ values: (a) PET,
AP′ = 3.1, t = 1577 K; and (b) HDPE, AP′ = 14.5, t = 1577 K (see Table 11.7).
It becomes obvious that the residual concentrations of postconsumer substances in

PET are significantly higher than for HDPE. This reflects the much lower diffusivity
of PET in comparison to HDPE (see Section 11.5). Regarding recycled PET behind
a functional barrier, the FDA considers a thickness >25 μm at room temperature
and below and a thickness >50 μm at higher temperatures, including use as a dual-
ovenable container for cooking food at 150°C for 30 minutes, as sufficient functional
barrier thicknesses. It should be noted here that the approval of the recycling process
by the FDA is not mandatory.
11.7.4 EFSA Criteria for Evaluation of Recycled Plastics

in Food Contact
Postconsumer recyclates in direct contact with food are regulated by EU 282/2008

(EU 2008). According to this regulation, each recycling process that intends to produce
postconsumer recycles for direct contact with food must undergo a safety assessment
by the EFSA. In 2011, the EFSA published criteria for such an evaluation for post-
consumer recycled PET (EFSA 2011). Other polymers are not included in the
evaluation criteria of this report.
The EFSA’s evaluation principle for postconsumer PET in direct food contact is
essentially based on the cleaning efficiency of the recycling process. The EFSA
assumes a concentration of 3 mg per kg substance in the (washed) input materials
for PET recycling processes is a worst-case scenario. Using the cleaning efficiency
of the recycling process for each individual compound, the residual concentration
(cres) in the recyclate is specified. Subsequently, the residual concentration cres is com-
pared to a (calculated) concentration (cmod). The concentration cmod represents the
expected migration of a (model) substance into the food by the end of the shelf life
of the packaged food. In the case of PET bottle-to-bottle recycling, it is mainly recycl-
able bottles for mineral water and soft drinks that are manufactured. Consequently,
the EFSA has set a storage time of 365 days at 25°C as the boundary usage condition.
For calculating cmod, the currently used migration model is based on AP′ = 3.1 and
τ = 1577 K (Simoneau 2010); see also Table 11.7. The calculation of cmod also
assumes that a 1-l drink is packaged having a surface area of 6 dm2. It is also assumed
that the PET bottle is made of 100% recyclate and that the migrating substance has
good solubility in the beverage (partition coefficient K = 1). The EFSA adopts an
exposure scenario for toxicological evaluation of postconsumer PET recyclates
based on the assumption that exposure to 0.0025 µg of a substance per kg body weight
per day is not harmful to human health. This threshold is low enough to cover all
toxicological effects. This also ensures that even unknown contaminants are dealt
with conservatively. For the exposure scenario, the EFSA considers an infant having
a body weight of 5 kg. It is assumed that this infant drinks 0.75 L water from a PET
bottle (made of 100% recyclate). This means that the migration into the food by the
end of the shelf life may not exceed 0.017 µg/L. From this concentration, one can cal-
culate a concentration in the PET bottle wall under the aforementioned usage condi-
tions. This then corresponds to the (calculated) concentration cmod. Due to the fact that
the underlying migration model for calculating the corresponding maximum
3
Infants
Toddlers
2.5 Adults
Maximum bottle wall concentration
2
(mg/kg)
1.5
0.5
0
0 100 200 300 400 500 600
Figure 11.10 Calculated concentrations of substances in recyclate-containing PET bottles after

improper usage, corresponding to migration of 0.1 µg/l (infants), 0.15 µg/l (toddlers),
and 0.75 µg/l (adults). Contact conditions: 365 days at 25°C, 1-l fill volume, contact
surface area 6 dm2, current migration model with AP′ = 3.1, τ = 1577 K.
concentration in the PET bottle wall (cmod) overestimates the migration by at least a
factor of five, the EFSA rounds the value of 0.017 to 0.1 µg/L. In concrete, this
means that the migration of a substance from a PET bottle containing recyclate by
the end of its shelf life may amount to a maximum of 0.1 µg/l. If, therefore, at the
end of the shelf life, the concentration cres of each (model) substance is smaller than
cmod, then the recycling process is deemed to be safe. Due to the different amounts of
food people eat relative to their body weight, older children (toddlers) and adults
have higher migration values of 0.15 µg/l and 0.75 µg/l, respectively, compared to
infants. These higher values naturally also mean proportionally lower required mini-
mum cleaning efficiencies. Because mineral water producers clearly cannot ensure
that only adults consume water from recyclate-containing PET bottles, only the lowest
limit value (for infants) actually applies. Due to the fact that the migration is dependent
on the molecular weight of the migrating substance, the maximum bottle wall concen-
tration can be calculated assuming migration of 0.1 µg/l after storage for 365 days at 25°
C. The calculated maximum bottle wall concentrations (cmod) are shown in Figure 11.10
as a function of the molecular weight. Experimental migration tests are not foreseen
in the EFSA evaluation approach and, in contrast to the FDA, the EFSA defined
the migration modeling parameters. Therefore, new migration modeling parameters
need to reevaluated by the EFSA. A discussion of the influence on new prediction
methods for diffusion coefficients in PET (see Section 11.5.2) is given in the literature
(Welle 2013c).
A further criterion stipulated by the EFSA is that the fraction of PET bottles from
nonfood applications may only be a maximum of 5% of the input stream to the recy-
cling plant. The reason given by the EFSA for this is that nonfood PET containers may
also contain additives not listed under EU Regulation 10/2011 (EU 2011a). Further-
more, chemicals may have migrated in higher concentrations into the PET bottle
wall than would be the case for food packaging. In order to therefore rule out the possi-
bility of higher concentrations of contaminants in the recyclate, the fraction of PET from
nonfood applications that can be input into recycling processes was limited by the EFSA.
Ultimately, recycling companies must put measures in place to ensure that this 5% of PET
from nonfood applications is not exceeded. The EFSA is of the opinion that monitoring of
the input material specifications and the specifications stipulated for “good manufacturing
practice” are necessary in order to guarantee the compliance of the recyclate.
11.7.5 Paper and Board
Other FCMs with high amounts of recyclates are paper and board. In comparison
to PET, the recycling processes for paper and board have significantly lower cleaning
efficiencies. In addition, the input materials for recycling (e.g., newspapers or printed
board) have higher amounts of contaminants from the first use. Therefore, serious
migration issues have been reported within the last decade (Castle et al. 1997; Gruner
and Piringer 1999; Biedermann et al. 2011; Dima et al. 2011; Vollmer et al. 2011). The
migratable compounds are related to substances that typically are used for the paper
production or recycling process as well as for printing processes—for example,
inks, solvents (mineral oil), UV-cured ink photoinitiators, defoamers, biocides, slimi-
cides, pesticides, optical brighteners, coating materials, or adhesives. In conclusion, the
contamination profile of cardboard is very complex, which makes the safety evaluation
of recycled paper and board difficult (Honkalampi-Hamalainen et al. 2010). The
migration of compounds from recycled fibers into food is not specifically regulated
in Europe. Therefore, only Article 3 of the Framework Regulation 1935/2004 is
applicable. However, regarding mineral oil components, a draft regulation of the
German Federal Ministry of Food, Agriculture and Consumer Protection is under dis-
cussion (as of March 2017). According to this draft, the maximum concentration
mineral oil saturated hydrocarbons will be 0.6 mg/kg and mineral oil aromatic hydro-
carbon (MOAH) should be nondetectable. A concentration of 0.15 mg/kg is assumed
as the detection limit for MOAH. It is interesting to note that the 0.15 mg/kg for
MOAH is a factor 1500 higher than the 0.1 µg/kg criteria that the EFSA applied
for the evaluation of recycled PET in FCMs (see Section 11.7.4).
There are several options for reducing the concentrations of contaminants from
recycled fibers (e.g., mineral oil components) (Ewender et al. 2013):
• Substitution of recycled fibers with fresh fibers

• Elimination of mineral oil components or photoinitiators from printing inks
• Better decontamination of recycled fibers during paper and cardboard recycling
• Sorting of the input streams of paper and board recycling
• Barrier materials for mineral oil components
From the aforementioned five options, barrier materials seem to be the fastest
solution for minimizing migration into packaged foodstuffs. Such layers will act as
a functional barrier toward typical cardboard recycling contaminants (e.g., mineral
oil, di-iso-propylnaphthaline [DIPN], Michler's ketone, phthalates, and so on). A
method for the determination of barrier properties of inner layers or cardboard coat-
ings is published and can be found in the literature (Ewender et al. 2013).
11.8 ACTIVE AND INTELLIGENT FCMs
Active and intelligent materials may be used for food packaging in various forms
depending on the intended application. The substances responsible for the active and/
or intelligent function can be contained in a separate container (e.g., inclusion in a
small paper sachet) or the substances can be directly incorporated into the packaging
material (e.g., incorporation in the plastic of a bottle using mono- and multilayer struc-
tures) (EU 2009). Systems that are on the market today are predominantly moisture
absorbers and oxygen scavengers present in active systems, while intelligent packa-
ging systems, such as time/temperature indicators, currently only play a minor role
in the food packaging sector.
Generally, migration testing of such materials follows the conventional approaches
as described previously in Section 11.3. However, active and intelligent packaging dif-
fers from traditional packaging materials; therefore, migration testing of active and intel-
ligent packaging needs a rather individual approach in some cases. Migration studies
can be used to show compliance with the general safety requirements set out in Article
3 of the Framework Regulation 1935/2004 (EU 2004) because these also apply to active
and intelligent packaging materials. Additionally, migration testing for specific compo-
nents of active/intelligent packaging systems must be used to verify compliance with
specific restrictions to be set in the forthcoming community list of authorized substances
that may be used in active and intelligent components (“community list”).
According to Regulation 450/2009 (EU 2009) on active and intelligent materials
and articles for food contact applications, the substance (or combination of substances)
responsible for the active/intelligent function must undergo a safety assessment by the
EFSA prior to their authorization. In the dossier submitted to the EFSA, migration
data of active and/or intelligent substances (including possible impurities, reaction
products, and degradation products) must be provided using (where appropriate) conven-
tional migration tests or dedicated migration/evaluation tests in foods or simulants with
demonstrated adequacy for the intended/recommended conditions of use. Alternatively,
calculations based on worst-case transfer scenarios or recognized mathematical migra-
tion models also may be used (EFSA 2009).
For the migration testing as well as for the safety evaluation of active and intelli-
gent packaging materials, an essential differentiation is made between “active” and
“passive” parts of the packaging. Additional aspects must be taken into account for
the migration testing of intelligent packaging materials and scavenging systems.
11.8.1 Passive Parts of the Packaging
Substances that do not contribute to the active function of the packaging (e.g., carrier
substances) or the polymeric matrix into which the active substance is incorporated
(e.g., sachet, multilayer films) are considered as passive parts of the packaging. These
passive parts of the active packaging must comply with the existing EU and national
legislation applicable to those FCMs. For example, if the layer in which the active sub-
stance is incorporated is a plastic layer, the plastic layer must comply with the require-
ments according to the Plastics Regulation 10/2011 (EU 2011a). For materials such as
paper and board that are not yet regulated at the EU level, national legislation of the EU
member states applies (EFSA 2009; EU 2009). Migration testing of such passive parts
follows the conventional testing procedures applicable to the specific materials used in
the passive parts.
11.8.2 Active Packaging
Active FCMs and articles are designed to deliberately incorporate “active” com-
ponents intended to be released into the food or to absorb substances from the food.
Therefore, such releasing systems are not inert by their design and are dissimilar from
traditional materials and articles intended to come into contact with food. If the
released active substance has a technological function on the food (e.g., an antioxi-
dant), the released active substance is considered as a food additive and therefore
must comply with EU food law. Additionally, it must be considered that there may
be a risk of exceeding the OMLs described in EU or national legislation due to the
release of the active substance. The OML is a measure for the inertness of a material
(the material of the passive part). Consequently, because the active function is not an
inherent feature of the passive material, the amount of released active substance
should not be included in the calculation of the OML (EFSA 2009; EU 2009).
11.8.3 Intelligent Packaging
In contrast to active systems, intelligent systems are not intended to release their
constituents into the food (e.g., time-temperature indicators). These intelligent sys-
tems may either be positioned on the outer (nonfood) surface of the packaging or
be incorporated into the food contact surface of the packaging. According to Article
3 of the EU Regulation 450/2009 (EU 2009), the functional barrier concept may also
apply to these structures. Thus, nonauthorized substances may be used if it can be
demonstrated that the packaging material acts as a functional barrier preventing the
migration of substances from behind that barrier into the food and provided that
these nonauthorized substances are not classified as “mutagenic,” “carcinogenic,”
or “toxic to reproduction” and are not used in the form of engineered nanoparticles
(ENPs). The migration of nonauthorized substances from the intelligent components
should not be detectable, setting the maximum tolerable migration at 0.01 mg sub-
stance per kg food (EFSA 2009; EU 2009).
11.8.4 Scavenging Systems
Oxygen scavenging systems are designed to scavenge or capture residual oxygen

from inside the packaging (from the environment surrounding the foodstuff or from
the foodstuff itself) to reduce exposure to oxygen. Because they exert an intended
reaction of the scavenging components with oxygen, special attention should be paid
to the resulting reaction and degradation products and their migration potential for
such scavenging systems. Most appropriate are nontargeting screening approaches
(see Section 11.6) and, in case of their presence in the material identification, the (specific)
migration analysis of such reaction and degradation products should be applied.
11.9 NANO APPLICATIONS IN PLASTIC FCMs
Nanotechnology is a relatively novel field in science and engineering. It makes

use of ENPs in many technical areas but also in consumer products, including
FCMs. The use of nanomaterials in food packaging materials has received increasing
worldwide attention in the public, scientific, and legislative domains as a logic conse-
quence of the still ongoing social dialogue on the pros and cons of nanotechnology in
general and of the risk-benefit discussion on the use of nanoparticles in food contact
applications, in particular. Several review articles, reports, and official statements/
opinions have been published recently in which the type and nature of already existing
or potential nano-applications in the food packaging sector as well as their consumer
safety and regulatory implications have been described (Chaudhry et al. 2008; FSA
2008; Miller and Senjen 2008; Arora and Padua 2010; Duncan 2011; Hatzigrigoriou
and Papaspyrides 2011). A useful summarizing description that highlights the complexity
of the nanotechnology issue has been given by Hatzigrigoriou and Papaspyrides: “The
term nanotechnology refers to a multidisciplinary field of applied science and technology
that aims to control matter in the nanometer-scale range. One nanometer (nm) is one
billionth (10−9th) of a meter. On a nanometer scale, that is, from 100 nm down to the
size of atoms, the properties of materials can be very different from those on a larger
scale. The interest in nanoscale materials stems from the fact that new properties are
acquired at this length scale and, equally important, that these properties change with
their size or shape. The broadness in the scope of nanotechnology makes it hard to be
defined, as it may mean different things when approached from a scientific, legal,
environmental, regulatory, or even ethical point of view. A practical definition
implies that nanotechnology is the design, characterization, production, and applica-
tion of structures, devices, and systems by controlled manipulation of size and shape
at the nanometer scale (atomic, molecular, and macromolecular scale) that produces
structures, devices, and systems with at least one novel/superior characteristic or
property” (Hatzigrigoriou and Papaspyrides 2011).
Application of nanotechnology in the polymer food packaging sector, for instance,
in terms of polymer nanocomposite materials, is reported to improve mechanical,
thermal, and light protection material properties as well as enhancing gas and
aroma barrier performance. In addition, further novel and beneficial characteristics
for plastic packaging materials are expected such as induction of antimicrobial proper-
ties, oxygen scavenging, enzyme immobilization, and sensing or even triggering food
conditions (Duncan 2011). Particular bio-based nanocomposites as so-called green
materials with enhanced performance for food packaging applications have been
recently reported (Rhim et al. 2013).
From a food safety and consumer health impact point of view, the focus needs to
be directed on the question whether, and if yes, to which extent migration of nanosized
particles into packaged foodstuff can occur under the conditions of use. Standard test
procedures are not available in this area. Therefore, key points to be addressed here are
which analytical-methodological approaches are suitable and could be taken to give
satisfying answers to this extremely challenging question.
11.9.1 Definition of Nano and Legal Nano Applications in Europe
Primary nanoparticles (pNP) can occur in three principal geometries: they can be
nanosized in one (platelets), two (rods, bars, or other lengthy structures), or three
(spheres or similar structures) dimensions (Figure 11.11). Furthermore, a typical
behavior of pNP is that they form aggregates (Figure 11.12) and agglomerates that
are larger ensembles of pNP and that may still be partly nanosized or larger and
fully exceed the nano-dimension scale. As a consequence of an EU wide-open scien-
tific discussion, the EU Commission has published the definition of nanomaterial that
gives, in its Article 2, an important size criterion for the definition of the nano-range
(EU 2011b): “Nanomaterial means a natural, incidental, or manufactured material
containing particles, in an unbound state or as an aggregate or as an agglomerate
and where, for 50% or more of the particles in the number size distribution, one or
more external dimensions is in the size range of 1–100 nm.”
z
2D y 1D
z
2D
2D
z
y
3D x
Figure 11.11 Nanoparticles can be nanoscaled in one, two, or three dimensions.

100 nm
Figure 11.12 TEM image of TiN nanoparticles in PET polymer. Size of primary nanoparticle is
approximately 20 nm in diameter.
Some important considerations on the implications of this EU definition in the

European regulatory-political environment have been published (Bleeker et al. 2013)
where further guidance as to the interpretation of this definition can be found. This
definition represents the reference point when it comes to evaluation of the compliance
of nanoparticles present as potential migrants in food contact plastics. The European
Plastics Regulation 10/2011 explicitly establishes rules for nanomaterial food contact
plastics in its Article 9(2), where it is stated that substances in nanoform shall only be
used if explicitly authorized (which means on the basis of an evaluation by the
EFSA) and mentioned as such in the specifications of the Positive List for Monomers
and Additives as set out in Annex I of the regulation (EU 2011a). Currently, there
are only three entries in this list that are attributed to approved nanosized additives
with certain structural specifications:
• Carbon black—FCM Substance no. 411

• Silicon dioxide—FCM Substance no. 504
• Titanium nitride (TiN), nanoparticles—FCM Substance no. 807
TiN is used (as nanoparticles with pNP diameter of 20 nm) as a so-called reheat
additive into PET to improve thermal conductivity during blow-molding PET pre-
forms into drink bottles, which allows higher bottle production rates. Figure 11.12
shows a transmission electron microscopic (TEM) image of TiN nanoparticles
in PET.
11.9.2 Analytical Approaches to the Determination of Nanoparticles
Metrology of ENPs comprises numerous physical-chemical measurements and ana-

lytical methods. The sort of measurement depends on the type and nature as well as the
environment of the target nanomaterial. Comprehensive guidance for nanoparticle
measurements and suitable analytical methods can be found in the published literature.
A sizable consortium of experts undertook a nano metrology action within the European
project “Co-Nanomet” (Co.Nanomet 2010) and developed definitions and strategies for
the characterization and measurement of nanoparticles in general. More specifically,
helpful information and details for analysis of nanoparticles occurring in foods or
FCMs can be found in a review (Filella 2012) on sampling and sample preparation
of ENPs and in a review article on detection and characterization of ENPs in food
and the environment (Tiede et al. 2008). The important properties of ENPs (which
include size, shape, surface properties, aggregation state, solubility, structure, and che-
mical composition) are typically analyzed by methods using microscopy, chromatogra-
phy, spectroscopy, centrifugation, filtration, and often combinations thereof.
For the analysis of ENPs as potential migrants from FCMs and the evaluation of
their compliance with food packaging law requirements, the two key analyte proper-
ties are their size, more specifically their size distribution, and their chemical nature.
Both properties are measurable separately or by hyphenated techniques. Field flow
fractionation (FFF) represents one important technique to separate macromolecules
and particles according to their molecular mass (Reschiglian et al. 2011). A fre-
quently used modification of FFF is asymmetric flow field flow fractionation
(AF4) analysis, which can be coupled with multiangle light scattering to determine
the size distribution of ENPs based on their hydrodynamic diameter (Gigault and
Hackley 2013). This method allows the quantitative detection of particles down
to approximately 2 nm to 5 nm in size (diameter). It should be noted that this analy-
tical method requires substantial operator experience in setting up the right instru-
mental conditions and in selecting suitable solvents for sample preparation and
the mobile phase. The method of choice for the elemental characterization depends
on the chemical nature of the ENP analyte. In general, however, inductively coupled
plasma-mass spectrometry (ICP-MS) is the method of choice. For instance, in the
case of silver nanoparticles, ICP-MS measures the total elemental concentration
in the normal mode, independent of whether ionic species or solid particles are enter-
ing the plasma chamber. ICP-MS can also be run in the “single-particle operation
mode” (SP-ICP-MS) that makes use of kinetic effects in the plasma chamber to dif-
ferentiate between ionic species and particles and even among different sizes of
nanoparticles. Coupling AF4 with either SP-ICP-MS or ICP-MS appears to be a
highly promising approach for quantification and size distribution determination
with direct multi-element analysis of ENPs (Bustos et al. 2013).
Finally, it should be noted that these analytical techniques are suitable for the ana-
lysis of ENPs when they are dispersed in a liquid matrix—for instance, in a food simu-
lant obtained from a migration test. To verify that ENPs are present as potential migrants
in a food contact plastic, TEM imaging is the method of choice. Figure 11.12 shows a
TEM image of TiN incorporated in a PET polymer. It can be recognized that primary
ENPs with a size of approximately 20 nm diameter are assembled to aggregates of

around 100 to 200 nm in size.
11.9.3 Migration of Nanoparticles from Food Contact Plastics
For risk assessment of ENPs from potential exposure via packed food from food
contact plastics, the key question is: Can nanoparticles, when incorporated in plastics,
migrate or be released into the packed food? And, if yes, under what conditions and to
what extend and how can this be determined? In the case of the EU-approved nano-
additive TiN, the EFSA has concluded that no migration can be expected in this par-
ticular case, where only 20 ppm of the additive is incorporated into PET, a polymer
with very low intrinsic diffusivity (EFSA 2012).
Numerous publications have dealt with this key question by attempting to measure
and model migration of ENPs from plastics. One publication (Simon et al. 2008) pre-
sented a physicochemical view on the key question and used the Stokes-Einstein rela-
tion to calculate diffusion coefficients in polymers as a function of the size (radius) of
ENPs and taking as an approximation that the polymer matrix would be a fluid char-
acterized by a recalculated dynamic viscosity at the particular food contact tempera-
ture (up to 25°C). As a result, it was concluded that ENPs with a radius in the order of
1 nm are not expected to migrate from polymers. Concerning experimental studies, in
most cases, nanosilver polyethylene composites have been selected as model systems
and ICP-MS measurement of total silver has been used in migration solutions (Huang
et al. 2011; Song et al. 2011; von Goetz et al. 2013). Another attempt was made to
study migration of inorganic nanosized platelets from a polylactide nanocomposite
(Schmidt et al. 2011).
The results of all these studies cannot be considered as conclusive concerning the
key question because of analytical and methodological confounders. The Stokes-
Einstein relation is only applicable to fluids and would lead to high diffusion coefficients
for ENPs in polyolefins from which significant migration values in the mg/l (ppm)
range could be calculated when using recognised migration models (see Section
11.5). Most experimental migration tests have been done by total immersion with
cut edges of the test samples in direct contact with the migration solutions, which
may cause mechanical release of ENPs due to the physical disintegration of the cut
edge surface. In the case of silver measurements, it has not been shown whether the
measured silver is due to ionic species or silver particles.
Our own studies (Bott et al. 2012a) on migration of silver from nanosilver contain-
ing LDPE films into isooctane and 95% ethanol have shown that, even after 10 days at
60°C, silver (ICP-MS determination) was not detectable, whereas contact with 3%
acetic acid gave significant migration in the μg/l (ppb) range. However, it could be
shown that nanosilver is not stable under these acidic test conditions and that the
migrating species is ionic silver. In a second test system using high concentration
of nano TiN incorporated into LDPE films, migration testing with all EU official
food simulants—including 3% acetic acid—did not give detectable titanium levels
even after the same severe contact conditions of 10 days at 60°C (Bott et al.
2012b). Although not dealing with migration into foods or food simulants but with
the self-diffusion of nanosilica particles in polyproylene/ethylene vinyl acetate

(PP/EVA) polymer blends, one interesting study (Elias et al. 2008) found that those
nanoparticles with a size of around 100 nm (radius) would not migrate by Brownian
motion (self-diffusion of the particles) at melt temperatures of 200°C. Under these
conditions, a diffusion coefficient D = 1.3 10−14 cm2/s was derived. From this value,
using a purely qualitative approach, it can be assumed that the nanoparticle mobility in
the solid state of the polymer (e.g., at room temperature) would be extremely low.
Migration modeling appears to provide a useful tool for approaching the key ques-
tion concerning migration potential of nanoparticles and how to estimate diffusion
coefficients of nanoparticles in polymers. For PET polymers, the calculation of diffu-
sion coefficients has been shown to be a function of the size (molecular volume) of the
migrant. From Equation 11.16 in Section 11.5, diffusion coefficients of nanoparticles
in PET can be calculated as a function of their size and the temperature. For a diameter
range from 1 nm to 10 nm, diffusion coefficients at a test temperature of 40°C would
range from D = 2 10−20 cm2/s to 1 10−45 cm2/s. These values are extremely low and
demonstrate that nanoparticles are immobilized in the PET polymer matrix. In case
of polyolefins, an analogous equation as for PET does not exist. However, Piringer
has established an equation (Piringer and Baner 2008, equation [6.28] in p. 188) for
the prediction of diffusion coefficients for n-alkanes in polyolefins that can be used
to estimate (as an approximation) diffusion coefficients for nanoparticles. Taking carbon
black particles (instead of n-alkanes) as migrants of different sizes in diameter and at a
density of 1 g/cm3, the particle mass can be calculated for each particle and used as mole-
cular weight in the Piringer and Baner equation. As result, for a diameter range from 1 nm
to 10 nm, diffusion coefficients at a test temperature of 40°C would range from D = 3
10−9 cm2/s to 4 10−31 cm2/s. From these D values, it can be concluded (for polyole-
fins) that only nanoparticles in a size range up 3 or 4 nm (in diameter) could cause
measurable migration if present in high amounts in the polymer. Particles larger than
10 nm in diameter would be immobilized in polyolefins and would not migrate
according to the Fickian law of diffusion. To ensure food law compliance and
safety-in-use of food contact nanocomposite plastics, two major considerations
should be addressed:
1. Are the ENPs incorporated in the food contact plastic present there in a nano-
form and size that could mobilize them in the polymer matrix and lead to migra-
tion out of the polymer? This is generally not the case because ENPs added to
food contact plastics are present there in much larger sizes than 1 to 5 nm. This
can be qualified by visualization using TEM imaging of the nanocomposite, for
instance. Additional information on the size distribution of the neat ENP mate-
rial will assist in the conclusion on their migratability.
2. Is there a possibility other than Fickian diffusion–controlled migration from the
food contact plastic? To find a conclusive answer to this question, a suitable
migration test may be carried out under exaggerated material stress test condi-
tions, for instance, using a solvent with an expected somewhat more severe
aggressiveness than the foreseen foodstuff itself. Depending on the type of poly-
mer, this could be isooctane and 95% ethanol for polyolefins or 50% and 95%
ethanol for more polar polymers such as PET, for instance. These tests always
should be carried out in the single side test mode (and not by total immersion of
cut samples) under more severe time-temperature test conditions—for instance,
10 days at 60°C. Electron microscopic analysis of the surface of the plastic in
combination with AF4 analysis of the migration solution and careful evaluation
of any positive test results versus the real application conditions will allow us to
answer this question.
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CHAPTER 12
Food Package Testing Authorities

and Regulations
Angela Störmer and Keun Taik Lee
CONTENTS
12.1 Introduction...................................................................................................304
12.2 European Food Contact Material Regulations..............................................304
12.2.1 Food Contact Legislation and Authorities in the EU,
the Member States, Switzerland, and Norway................................304
12.2.2 General Requirements.....................................................................307
12.2.3 Plastic Materials..............................................................................307
12.2.4 Regenerated Cellulose ....................................................................309
12.2.5 Paper and Board..............................................................................310
12.2.6 Printing Inks....................................................................................310
12.2.7 Other Materials ...............................................................................311
12.2.8 Multilayer Materials and Functional Barrier Principle ...................312
12.2.9 Recycling ........................................................................................312
12.2.10 “Active and Intelligent” Materials ..................................................314
12.2.11 Nanomaterials .................................................................................314
12.2.12 Good Manufacturing Practices .......................................................315
12.2.13 Labeling, Declaration of Compliance, and Traceability .................315
12.2.14 Authorization of New Substances...................................................316
12.3 United States Food Contact Materials Regulations ......................................317
12.3.1 General Rules and Structure of Regulations...................................317
12.3.2 Materials and Additives Regulation in 21 CFR..............................318
12.3.3 GRAS Substances ...........................................................................318
12.3.4 Prior Sanctioned Substances ...........................................................319
12.3.5 Threshold of Regulation .................................................................319
12.3.6 No Migration Exemption, Functional Barrier Principle,
and Possibilities of Self-Determinations.........................................320
303
12.3.7 Food Contact Notifications—Applications to New Substances .....320

12.3.8 Nanomaterials .................................................................................322
12.3.9 Recycling Materials ........................................................................322
12.4 Asian Food Contact Material Regulations....................................................323
12.4.1 Overview of Regulatory Frameworks for Food Contact
Materials in Asian Countries ..........................................................323
12.4.2 China...............................................................................................324
12.4.3 Japan ...............................................................................................325
12.4.4 Korea...............................................................................................326
Acknowledgments..................................................................................................328
References ..............................................................................................................328
12.1 INTRODUCTION
Packaging materials or other food contact materials (FCMs) are not completely
inert but may release constituents into the food. If this happens, consumers will
be exposed to substances from the packaging. In the last decades, the awareness of
consumers, media, and also industry about packaging-related substances has been
increasing. All countries have at least general rules for the safety of FCMs in their leg-
islation. In Europe and the United States, plastic materials and some other packaging
components are regulated in detail. Both systems are different. Whereas the European
Union (EU) has their Positive List, which usually does not assign monomers or addi-
tives to specific polymers, the US system has regulations for specific material types
and, since 2000, premarket notifications for specific products. The EU system controls
the materials using migration limits. However, in the United States, migration from
materials is evaluated in depth during the premarket approval process, and the
compliance of the actual material is indicated primarily by specifications and end
tests. The Asian countries do not have a uniform system. Some have negative lists
and others have positive lists. In this chapter, the regulations for FCMs in Europe,
the United States, and Asia are introduced. Common to all systems is requirement
that producers and suppliers are responsible for providing the market with safe and
compliant materials and articles.
12.2 EUROPEAN FOOD CONTACT MATERIAL REGULATIONS
12.2.1 Food Contact Legislation and Authorities in the EU,

the Member States, Switzerland, and Norway
Harmonization of legislation within the EU is an ongoing process. The main moti-

vation is to facilitate trade within the member states. In the past, legislation for FCMs
was mainly based on European Directives. These are not directly binding laws but
must be implemented by each member state in its national legislation. This process
usually took at least a year. For quite some time, new European legislative measures
FOOD PACKAGING TESTING AUTHORITIES AND REGULATIONS 305
in the area of FCMs have been published as EU Regulations. These regulations are
directly binding in all member states. The competency for FCMs is located at the
Directorate-General for Health and Consumers of the EU Commission (DG SANTE).
The general requirements for all FCMs are common law. In 1976, Framework
Directive 76/893/EEC was published harmonizing the existing legal requirements
in the member states. This directive was replaced in 1989 by Directive 89/109/
EWG and, in 2004, by the actual Framework Regulation (EC) No. 1935/2004
(EU 2004). Furthermore, specific rules on plastics, regenerated cellulose, certain cera-
mics, and nitrosamines (from rubber teats and soothers) as well as on the use of some
epoxy derivatives, are coordinated throughout the EU. Switzerland and Norway are
not members of the EU but usually adopt EU rules in their legislation. For other mate-
rials, as well as for components that do not fall under the European legislation (e.g.,
catalysts for plastics), some member states have their own legally binding rules,
recommendations, or standards. A summary is given in Table 12.1 and can be
found in more detail in a European Commission’s Joint Research Centre (JRC)
study (Simoneau et al. 2016).
In Europe, risk assessments are performed at the European Food Safety Authority
(EFSA), which is located in Parma, Italy. These assessments are made by expert
scientific panels and their working groups. The Panel on FCMs, Enzymes, Flavorings
and Processing Aids (CEF) deals with questions related to safe usage of materials that
come in contact with food, enzymes, flavorings, and processing aids as well as to the
safety of processes. The assessment results are published as opinions in the EFSA
Journal and are freely accessible (EFSA). In some member states, expert scientific
committees or bodies of authority perform assessments for substances that are
intended for or used in materials that are not yet specifically regulated on the
European level (e.g., in Germany: Bundesinstitut für Risikobewertung (BfR) and its
Bedarfsgegenstände-Kommission; in France: Agency for Food, Environment and
Occupational Health and Safety; in the Netherlands: Commission G4; and in Italy:
Istituto Superiore di Sanità). In the EU, the principle of free flow of goods and of
mutual recognition was established in 1957 in Articles 30 and 36 of the Treaty of
Rome at the founding of the European Economic Community (Montfort 1996,
2004). These rules have since been transferred to the Treaty on the Functioning of
the EU (Articles 34 and 36). In principle, goods that are lawfully manufactured and
brought into the market in one member state also should be allowed to be placed
into the market in other member states. The protection of human health and life
may allow single member states to be exempt from this rule. Non harmonized
goods such as paper and board, printing inks, coatings, rubber, colorants, wood,
cork, and other materials are on the market based on different rules or legislations
and thus on different risk assessment approaches. In 2010, the EFSA set up the
Scientific Cooperation (ESCO), Working Group on Emerging Risks that collected
information at the member state level and made proposals to anticipate emergency
situations dealing with substances for which no harmonized risk assessments are
available when they are released into foods by nonplastic FCMs (EFSA 2012).
This working group’s report is a useful source for substances evaluated in the member
states, Norway, and Switzerland as well as for a compilation of the actual risk
306
Table 12.1 Overview of National Specific Regulations, Recommendations, or Standards in EU Member States and Norway (EC 2012)
Member Mandatory Metals Paper Varnish Printing Ionexchange

States Registration Adhesives Ceramics Glass Enamel Alloys Cork Wood Textile Board RCF Plastics Coating Inks Silicone Wax Rubber Resin Other
Austria − − + − + − − − − − − − − − − − − −
Belgium − − − + − + − − − + − − + − − − − −
Bulgaria − − + + + − − − − − + + − − − − + − Resolutions
Cyprus − − − − − − − − − − − − − − − − − −

Czech − − + + + + + + − + − − + + + − + −
Republic
Denmark + − + + − − − − − − − − − − − − − −
Estonia + − − − − − − − − − − − − − − − − −
Finland + − − − − + − − − − − − − − − − − −
France − − + + + + − + − + − + + − − − + −
Germany − + + + + − − − − + − + − − + + + −
Greece − − − − − + − − − + − + + − − − − −
Hungary − − + − + + − − − − − + − − + − + −
Ireland − − − − − − − − − − − − − − − − − −
Italy − − + + + + − − − + + + + − + − + −
Latvia − − − − − − − − − − − − − − − − − −
Lithuania − − − − − + − − − + − − − − − − − −
Luxembourg − − − − − − − − − − − − − − − − − −
Malta − − − − − − − − − − − − − − − − − −
Netherlands − − + + + + + + + + + + + + + + + −
Poland + − + + − − − − − + − − − − − − − −
Portugal − − − + + − − − − − − − − − − − − − Steel, tin
Romania − − − − − − − − − − − − − + − − + − colors
Slovakia − − − + − + + + + + − − + − − − + −
Slovenia + − − − − − − − − − − − − − − − − −
Spain − + − − − − − − − − − − + − + − + + Nat. standards
Sweden − − − − − + − − − − − − − − − − − −
UK − − − − − +9 − − − − − − − − − − − −
Norway + − + + + + − − − − − − − − − − − −
assessment approaches. The Council of Europe (CoE) also tackles such materials
that are not yet harmonized in the EU in the form of resolutions and policy statements.
The CoE does not perform risk assessments for substances but collects and evaluates
information from its members and from the EU. The policy statements and resolutions
are not legally binding and have the status of recommendations.
12.2.2 General Requirements
The general rules for all materials and articles in contact with food are harmonically
laid down for all member states in the Framework Regulation (EC) No. 1935/2004
(EU 2004). Article 3 of this regulation gives the general requirements for safety:
1. Materials and articles, including active and intelligent materials and articles, shall be
manufactured in compliance with good manufacturing practice so that, under normal or
foreseeable conditions of use, they do not transfer their constituents to food in quantities
which could:
a. endanger human health; or
b. bring about an unacceptable change in the composition of the food; or
c. bring about a deterioration in the organoleptic characteristics thereof.
2. The labelling, advertising and presentation of a material or article shall not mislead
the consumers.
These rules have to be applied to all materials independently from their composi-
tion. In their generality, these requirements are difficult to evaluate—both for industry
and for enforcement authorities. Therefore, specific rules are needed for the individual
materials. For some materials, there are EU-wide harmonized directives or regula-
tions; for other materials, there are national decrees or recommendations; and for
others, specific regulations are lacking. The requisites for various materials will be
described in the following subchapters. Furthermore, labeling of material articles
that have not been in contact with food, traceability, conformity declarations, and
authorization of new substances are addressed in the EU’s Framework Regulation
No. 1935/2004 and will be explained later in this chapter.
12.2.3 Plastic Materials
Materials and articles made of plastics are almost completely and harmonically
ruled in the EU by the Regulation No. 10/2011 on plastic materials and by its amend-
ments (EU 2011c). This so-called “plastic implementation measure” substituted and
actualized the former Plastics Directive 2002/72/EC and the directives on migration
testing.
Plastics means all polymers that are the main structural element of final materials
and are obtained by polymerization processes such as polycondensation or polyaddi-
tion, by chemical modification of synthetic or natural macromolecules, or by bacterial
fermentation. Excluded from the scope of the plastics regulation are ion exchange
resins, rubber, and silicones. The regulation applies not only to plastic monomaterials
and plastic multilayers but also to plastic layers in multimaterial multilayers (e.g., with
paper, board, or aluminum layers). Furthermore, plastic layers as gaskets of closures
(e.g., metal closures) are included in the scope.
All monomers, other starting substances, additives, and polymer production aids,
as well as macromolecules obtained by bacterial fermentation, need to be approved
and listed in the so-called “Union list” in Annex I of the Plastics Regulation. When pre-
polymers are used for polymerization, it is sufficient that the monomers or other starting
substances for the synthesis are listed. Natural or synthetic macromolecules are included
in the list as base polymers for modification but only if their monomers are not already
on the list. The chemicals used for modification fall under monomers and starting sub-
stances. Polymer production aids are defined as substances that are used in the production
of polymers to provide a suitable medium (e.g., dispersants and emulsifiers) but that do
not have a technical effect on the final material. Yet, these are only partially included on
the list. Additional substances may be used according to national law. Solvents and color-
ants are explicitly not included in the regulation. Furthermore, aids to polymerization that
are substances that initiate polymerization (e.g., catalysts) or that control the formation of
the macromolecular structure (e.g., chain stopper) are excluded from the substances that
are subject to this regulation. However, these aids to polymerization are nationally regu-
lated in some member states (e.g., by decree in the Netherlands or by recommendation in
Germany).
The approval of substances is mainly without restriction to the use in certain poly-
mers. This means an approved additive may be used principally in all polymers and
also that new combinations of approved monomers are possible without new approval.
Only some substances are restricted in their specification for single applications.
Depending on their toxicological properties or the knowledge about these toxicolo-
gical properties, the substances are restricted by specific migration limits. These are
derived from the acceptable daily intake (ADI) or tolerable daily intake values (TDI).
These represent the doses that do not lead to adverse health effects at lifelong daily intake
according to actual knowledge. For calculation of the limit, the following—usually very
conservative—exposure assumption is used: a person with an average 60-kg body
weight eats 1 kg food daily containing the respective substance in the concentration
of the migration limit. Generally, this exposure assumption is related to all groups of age
or population. But, since 2005, deviating limits have been set for some substances in
materials or articles intended for infant nutrition. In addition, some substances of similar
toxicological properties, or that are metabolized to a common substance, have group
restrictions. These are referenced in the Union list in a separate table in Annex I of
the regulation. Salts (including double salts and acid salts) of aluminum, ammonium,
barium, calcium, cobalt, copper, iron, lithium, magnesium, manganese, potassium,
sodium, and zinc are not included in the list but are only allowed if the respective
acids, phenols, or alcohols are authorized. The migration limits of the respective metals
appear on an additional list in Annex II. Furthermore, in this annex, a general require-
ment is given that primary aromatic amines may not migrate in detectable amounts
(this detection limit is 10 μg/kg for the sum of amines). Those amines may derive, for
example, from isocyanates in polyurethanes or from pigments.
Substances without specific migration limits on the Union list are restricted by the
general maximum migration limit of 60 mg/kg food or food simulant. Some sub-
stances with a very low odor or taste threshold (e.g., styrene) do not have specific
migration limits either. These would lead to an off-odor or off-taste at levels below
toxicological limits and are restricted by the requirement not to deteriorate the sensory
properties of the food. Highly volatile or reactive compounds are either difficult to
determine or cannot be determined at all in migration solutions. In addition to their
migration limits, these substances also have limits related to residual concentration
in the finished material or in the surface area. Examples of very volatiles are butadiene,
vinyl chloride, or vinylidene chloride; examples of reactive substances are isocya-
nates, epichlorohydrin, or ethyleneimine. Notes on how to verify compliance are
referenced in the last column of the Union list.
Specific migration limits are given in mg/kg of food or food simulant. Usually, the
real surface to volume ratio of the existing or intended application is considered except
for some important exemptions. For small packages below 500 g or 500 ml, large
packages above 10 l, films and sheets for which the real surface to volume ratio is
not known, and articles for which the estimation of the surface to volume ratio
is impracticable or not possible, a conventional surface to volume ratio of 6 dm²/kg
is used for evaluation of the migration limits. This surface to volume ratio corresponds
to a cube of 1-dm edge length. For small packages, it is assumed that smaller amounts
of food will be consumed compared to larger packages. Therefore, the exposure will
be smaller. This is compensated by using the cube model instead of the often clearly
larger real surface to volume ratio. If the material or article is intended for packing
infant’s food or that of young children, the real surface to volume ratio needs to be
considered for evaluation in any case.
Purity restrictions or other specifications are set for some substances. These are
included in the Union list or in a separate list (Annex II, Table 4) with a reference
in the Union list. The list of specifications is incomplete. National specifications for
other substances than those on the list are also valid.
Besides the requirements for composition and specific limits, there is a general
limit on overall migration. Overall migration is a measure of the sum of migrating sub-
stances and is a gravimetrical value. Therefore, only nonvolatile compounds are cov-
ered by the overall migration limit, which is the implementation of the requirement
“not to bring about an unacceptable change in the composition of the food.” The para-
meter has no toxicological relevance. Since May 2011, the overall migration value is
only related to the surface, except for packages for infant food. Although the overall
migration limit is 10 mg/dm² of surface area, in case of infant’s and small children’s
food packages, the limit is 60 mg/kg.
Rules for migration testing are included in the Plastics Regulation and are
described in detail in Chapter 11.
12.2.4 Regenerated Cellulose
Regenerated cellulose is regulated in EU Directive 2007/42/EC (EU 2007) and

implemented in the national decrees of the respective member states. The directive
contains positive lists for coated and uncoated regenerated cellulose films and restric-
tions or specifications for those components. Contrary to the Plastics Regulation, most
restrictions are related to amounts in the film or in the surface of the film. Coatings
made of plastics and lacquers from polymers regulated in the Plastics Regulation
(EC) No. 10/2011 need to comply with regard to composition and to observe the
specific and overall migration limits given there. Synthetic casings (sausage casings)
made of regenerated cellulose are excluded from the directive because their composi-
tion may deviate from the directive’s requirements. Casings may need moisturizers
(e.g., glycerin) in higher amounts. In Germany, BfR Recommendation XLIV (BfR)
sets requirements for such synthetic casings.
12.2.5 Paper and Board
Specific requirements for paper and board are not yet harmonized in the EU.
National rules for paper and board exist in Belgium, the Czech Republic, France,
Germany, Greece, Italy, Lithuania, the Netherlands, Poland, and Slovakia. For eval-
uating conformity with Article 3 of the Framework Regulation 1935/2004, BfR Recom-
mendations XXXVI (paper and board in food contact), XXXVI/1 (cooking papers, hot
filter papers, and filter layers), XXXVI/2 (paper and board for baking purposes), and
XXXVI/3 (absorber pads based on cellulosic fibers) are used in Germany (BfR).
Furthermore, the Council of Europe has a resolution (ResAP (2001) 1) and a policy
statement containing inventory lists of substances used for manufacture and refining
that has been regularly updated (CoE). The lists in the BfR recommendations contain
those substances that have been evaluated specifically by the BfR Consumer Goods
Commission (formerly the Plastics Commission). Technical Document No. 1 of the
Council of Europe Policy Statement, on the other hand, has two lists. List 1 contains
substances that already have been evaluated on the European level, nationally, or by
U.S. Food and Drug Administration (FDA). List 2 contains substances that have been
not yet evaluated by any national authority and also those for which no sufficient
toxicological data are available for an evaluation.
12.2.6 Printing Inks
Printing inks are not yet regulated in the EU or in any of the member states.
Switzerland, which is not member of the EU, has a positive list for printing ink sub-
stances within the Swiss Bedarfsgegenständeverordnung that has been in place since
2011 (EDI 2013). Germany finalized a draft decree in 2016. But, instead of that, the
Commission is actually working on a European printing ink regulation. For a long
time, the possible invisible transfer of substances from printing inks on the outside
of packaging was only briefly considered, and possible set-off issues were often
neglected. Set-off occurs when the printed side of a packaging material is in direct con-
tact with the food side during storage of the packaging material on a roll or in
a stack. The turning point was the so-called “ITX crisis.” In the summer of 2005,
the photoinitiator isothioxanthone (ITX) was found in infant milk that was packed
in a multilayer with aluminum as an absolute barrier for transfer of substances.
Subsequently, this photoinitiator was detected in various food packed in different types
of packaging in concentrations up to several hundred μg/kg. The common link in these
packages was that all had been printed on the outside with ultraviolet curing inks. At that
time, ITX was not officially evaluated, and the available toxicological data were not suf-
ficient to show harmlessness for the amounts found in the food. The Italian authorities
mandated product callbacks and the whole European packaging and food industry
was impacted. ITX has since been almost completely replaced because it is no longer
tolerated in the market. But because the problem was far-reaching, this crisis initiated
a host of regulatory activities. In the fall of 2005, the Council of Europe published the
resolution ResAP (2005) 2 on printing inks (CoE) that requires that nonevaluated sub-
stances should not migrate at a detection limit of 10 μg/kg (ppb). In its guidelines, the
European Printing Ink Association (EUPIA 2012) outlines a method for the selection
of raw materials and recommends that substances without toxicological data should
not migrate more than 10 ppb. Three mutagenicity studies should be available that
show nonmutagenicity and nongenotoxicity when migration is up to 50 ppb. At higher
concentrations, more toxicological data are needed—similar to the EFSA’s require-
ments for the approval of new substances for plastics. In the Swiss positive list, sub-
stances without sufficient toxicological data must not be detectable at 10 ppb. All
other substances have migration limits according to their toxicological evaluations.
For new substances, only those with a sufficient data set will be approved.
12.2.7 Other Materials
For materials other than plastics, only specific aspects are harmonically regulated.
Some have national requirements in single member states; for others, there is no
authoritative ruling as to how to show conformity with Article 3 of Framework
Regulation No. 1935/2004.
For ceramic articles, migration limits for cadmium and lead are set in EU Directive
84/500/EEC (EU 1984), which was amended by rules for compliance declarations and
actualization of the analytical part of Directive 2005/31/EC. The directives are imple-
mented in the national regulations of the member states.
The release of N-nitrosamines and N-nitrosatable substances from elastomer and
rubber teats and soothers is restricted by EU Directive 93/11/EEC (EU 1993), and
basic rules for determination are set there. Further specific requirements for rubbers
do not exist yet on the European level. Some member states have national rules.
In Germany, there are several BfR recommendations for rubbers and elastomers in
various applications. Whereas in the old EU Plastics Directive 2002/72/EC, all
elastomers had been generally excluded from the scope of the directive, in the new
EU Plastics Regulation 10/2011, these are only rubbers and silicones. This means
that nonvulcanized elastomers i.e. thermoplastic elastomers (TPE) fall under the
scope of the Plastics Regulation.
Silicones are nationally regulated in several member states. In Germany, BfR
Recommendation XV applies and includes substance lists and testing requirements.
On the European level, the CoE had published a policy statement with the resolution
ResAP (2004) 5. The substance lists in its Technical Document are inventory lists
separated into evaluated substances (List 1) and nonevaluated substances (List 2) as

described for the Policy Statement in Section 12.2.5.
A further substance specific EU Regulation (No. 1985/2005) addresses epoxy
derivatives in all types of FCMs (EU 2005). It includes specific migration limits set
for bisphenol A diglycidyl ether and its derivatives. Furthermore, the use of bisphenol
F diglycidyl ether and novolac glycidyl ether is prohibited except for larger containers
or storage tanks of more than 10,000 L and their corresponding pipelines.
12.2.8 Multilayer Materials and Functional Barrier Principle
The composition of plastic materials is strictly regulated. Only substances from the
Union list in the Plastics Regulation 10/2011 may be used. But, since 2007, there
has been an exemption for multilayers. In layers behind the food contact layer,
nonauthorized substances may be intentionally used if they do not migrate in detect-
able amounts above a detection limit of 0.01 mg/kg, corresponding to 10 ppb (Article
13 Regulation (EU) No. 10/2011). Carcinogenic, mutagenic, and reproduction toxic
substances (also known as CMR substances) as well as nanomaterials are excluded
and may not be used without prior authorization. This exemption for nonauthorized
substances is called the “functional barrier principle.” The properties of a functional
barrier depend on the contact conditions (filling and storage time and temperatures),
whereas an absolute barrier (e.g., an aluminum foil) acts as a barrier in all conditions.
“Not detectable” at a detection limit of 0.01 mg/kg is the lowest migration limit in
the Union list. Carcinogenic monomers (e.g., vinylchloride) carry this migration limit.
Following this rule for plastic layers, the functional barrier principle with its
migration limit of 10 ppb may be used for evaluation of substances with unknown tox-
icology (e.g., for migration from layers that are not specifically regulated, by-products
or degradation products of additives, and so on). In practice, this means that, in cases
of migration below 10 ppb, identification and toxicological evaluation are not needed.
The recommendation for nonevaluated printing ink components in the CoE resolution
ResAP (2005) 2 is a practical application of this principle.
Multilayers assembled of additional layers other than plastic (the so-called multi-
material multilayers) were included in the Plastics Regulation 10/2011 for the first
time. The composition of the plastic layers has to comply with regulation 10/2011,
and the functional barrier principle is applicable. The migration limits fall under
national rules in this case. But, in practice, overall migration limit and specific migra-
tion limits from the EU plastics regulation are also applicable.
12.2.9 Recycling
Reduction of packaging waste and reuse or recycling of packaging materials are

general aims of the EU as laid down in Directive 94/62/EC (EU 1994) (last amended
by Commission Directive 2013/2/EU). However, reuse for food contact needs specific
measures to ensure consumer safety, especially in cases where misuse of postconsumer
materials cannot be excluded.
Several processes for super-clean recycling of PET bottle material for reuse as
food bottles were developed (Welle 2011). Such recycling was allowed in some mem-
ber states and principally forbidden in others. In 2008, the European Commission
(EC) published the EU Regulation 282/2008 (EU 2008), which sets the prerequisites
for recycling of plastic materials to reuse in FCMs throughout the EU. Each process in
each recycling plant must be evaluated by the EFSA. Excluded from the need for a
specific authorization is the use behind a suitable functional barrier and the reuse or
recycling of plastic made from unused plastic production offcuts and/or process scraps
within the sites as well as recycling back to the monomers. The Union list of approved
recycling processes does not yet exist, so national rules still apply.
The recycling process needs to be able to remove residues before future reuse (e.g.,
limonene from soft-drinks) as well as contaminants (e.g., when a bottle was filled with
chemicals or solvents by the consumer before recollection). Cleaning efficiency is
usually tested with a so-called challenge test in which the input material (usually plas-
tic flakes) is fortified with defined chemicals. These flakes are subjected to the recy-
cling process, and the depletion of the chemicals is determined analytically.
Furthermore, the selection of the input material and the quality assurance measures
of the recycler are evaluated by the EFSA. The approved processes will be published
by the EC in a Union list. Mostly, recycling processes for PET material are filed for
approval. For PET recycling, the EFSA had published their evaluation criteria in
2011 (EFSA 2011), with very low limits for possible exposure to contaminants,
which were determined by setting the exposure of infants as the measure.
In contrast to recycling plastics for food contact use, recycling of paper and board
has been ongoing for quite a long time. But specific legislation was not established
until recently. In its annex, BfR Recommendation XXXVI gives some migration
limits of typical substances that are brought into the recycling loop (e.g., from printing
inks or adhesives). The collection of paper and board does not distinguish between
materials from food contact uses and other papers and boards. In this way, substances
that are not approved for food contact are introduced into the recycled paper. Some
years ago, iso-butylphthalate was in the headlines because it was found in relatively
high amounts in foods. It had originated from adhesives in waste paper and board.
Industry use of this plasticizer was reduced in adhesives for technical applications
and, at the same time, the concentration of iso-butylphthalate decreased in recovered
paper. Recently, the focus has been on mineral oils. The main sources are printing inks
for newspapers but, until some years ago, mineral oil-containing printing inks were
used also for food contact paper and board. Although the mineral oil content has
now been reduced, it cannot be eliminated completely. An in-depth investigation of
unwanted substances in packaging materials from reused paper and board, financed
by the German Ministry of Nutrition, Agriculture and Consumer Safety, has studied
mineral oils in materials and foods (Harling et al. 2012). Many papers were published
on mineral oils in connection with this project, especially by the working group
Koni Grob (Kantonales Labor Zürich). A migration limit of 0.6 mg/kg for mineral oil
saturated hydrocarbons (MOSH) was discussed. The value was derived from a tempor-
ary ADI established by the Joint Expert Committee for Food Additives (JECFA 2002)
for low to medium viscous mineral oils. Mineral oil aromatic hydrocarbons (MOAH)
are suspected of being mutagenic. Polyaromatic hydrocarbons are known carcinogens.

In mineral oils, the aromatic hydrocarbons are mainly alkylated, which changes the tox-
icological properties. But exact toxicological data for these MOAH are lacking (BfR
2010). The actual draft of a German mineral oil decree requires nondetectability of
MOAH transfer onto food at a detection limit of 0.5 mg/kg food. For most applications,
the solution for preventing migration of unwanted substances from recovered papers
will actually only be to use barrier layers or barriers inside pouches—or something
similar. A limit for migration of MOSH is not included in the actual draft (dated
07.03.2017).
12.2.10 “Active and Intelligent” Materials
Active food contact materials and articles are intended to extend the shelf life or
to maintain or improve the condition of packaged goods by intentionally transferring
components onto the foods or absorbing substances from the food and/or the inside
of the packaging. A definition is given in Article 2 of the Framework Regulation
(EC) No. 1935/2004 as well as in Regulation (EU) No. 450/2009 for active and intel-
ligent materials and articles (EU 2009). Examples are materials that release preserva-
tives and absorber materials for oxygen or humidity. The EC established a guideline
for whether or not a system falls under this regulation (EC 2011). Intelligent materials
are those that monitor the status of a food or its environment. Examples are temperature
or oxygen sensors that change their color when exceeding a certain temperature or
oxygen concentration. Active and intelligent systems need to be evaluated for their
safety by the EFSA. The approved components of the active or intelligent systems
should then be published on a Union list. But this list does not exist yet. Food additives
or flavoring substances approved for food that are released into the food do not need to
be separately approved as active systems. They have to comply with the regulations for
food. The overall migration limit is not applicable to the active components; their
amount shall not be included in the overall migration value. Active and intelligent
systems need to be labeled. Masking spoilage or faking a better quality of food that
could mislead the consumer is forbidden.
12.2.11 Nanomaterials
Nanomaterials are defined in EU Recommendation 2011/696/EU (EU 2011).

Therein, “nanomaterial” means a natural, incidental, or manufactured material con-
taining particles in an unbound state, as an aggregate, or as an agglomerate, where,
for 50% or more of the particles in the number size distribution, one or more external
dimensions is in the size range of 1–100 nm. Fullerenes, graphene flakes, and single-
wall carbon nanotubes fall under the definition at even smaller dimensions. The
definition is only related to size and does not distinguish if a nanomaterial exhibits
other properties (e.g., higher chemical reactivity or significantly changed physical
properties) compared to the material without nanoscale features. But this is exactly
the justification for the highly restrictive regulation of nanomaterials in the Plastics
Regulation 10/2011. Because these different properties may lead to different
toxicological properties, these substances should be assessed on a case-by-case basis

by authorities (Recital (23) of EU Plastics Regulation 10/2011). All nanomaterials
need to be separately approved and included in the Union list with their nano
dimensions specified. Furthermore, nanomaterials are not allowed to be used behind
a functional barrier even if it completely will prevent migration. The reason for this
cautious handling of nanomaterials is insufficient knowledge about their toxicological
properties.
12.2.12 Good Manufacturing Practices
Food contact materials need to be produced according to good manufacturing prac-

tices (GMP). This is required by Article 3 of Framework Regulation No. 1935/2004 and
had already been in its predecessor, Directive 89/109/EEC. But for a long time, GMP
were not specifically defined. Industry associations worked out guidelines for their
members. As a reaction to the ITX crisis, in 2006, the EC published a regulation on
good manufacturing practices (Regulation (EC) 2023/2006) (EU 2006). General
requirements for quality assurance, quality control, and documentation are included
there. The regulation applies to all sectors and to all stages of the manufacturing, pro-
cessing, and distribution of materials and articles—except for the production of starting
substances. Documentation needs to be made available to the respective competent
authority upon request.
The annex of this regulation gives detailed rules for materials with printing on
the outer side and underpins that transfer of substances from the printed layer through
the material or via set-off has to comply with Article 3 of Framework Regulation
No. 1935/2004. An additional annex is related to recycling processes and is published
in the EU Recycling Regulation No. 282/2008.
12.2.13 Labeling, Declaration of Compliance, and Traceability
Materials and articles that are intended for food contact but that are not yet in
contact with food have to be labeled with the words “for food contact” or a specific
indication as to their use—such as coffee machine, wine bottle, soup spoon-, or the
glass-fork symbol (see Figure 12.1). If it is obvious from the characteristics of the arti-
cle that it is a food contact material, such a label can be omitted. If specific instructions
have to be observed for safe and appropriate use, these need to be put on the label.
Examples are “wash before use” or “not for fatty foods.” The name or the trade
name of the manufacturer, processor, or responsible seller—and, in all cases, the
address or the registered office—need to be declared. The labeling requirements are
laid down in Article 15 of Framework Regulation No. 1935/2004.
With the exception of direct sale to consumers, at all stages of the supply chain, food
contact materials or their pre-products have to be accompanied by declarations of
compliance in which the suppliers state that the materials are in conformity with the
respective rules. The general requirement is laid down in Article 16 of Framework
Regulation 1935/2004. The details are given in the respective specific regulations or
directives. For plastic materials, the information to be filled in on such a declaration
Figure 12.1 Article 15 of framework regulation (EC) No. 1935/2004 on materials and articles
intended to come into contact with food specifies the labeling requirements, noting
that food contact materials are to be accompanied by the words “for food contact” or
this symbol, unless it is obvious that the article is for food contact.
is given in Annex IV of Plastics Regulation 10/2011. The supporting documents

on which such a declaration of compliance is based (e.g., migration test reports
or supplier certificates) need to be stored and, on request, disclosed to the respective
authorities.
A further general requirement is traceability at all stages of the supply chain. This
will “facilitate control, the recall of defective products, consumer information and the
attribution of responsibility” (Article 17, Regulation (EC) 1935/2004). The suppliers
need to install an appropriate system of labeling and documentation. Industry asso-
ciations have worked out guidelines for their members as to how to implement
traceability at their sites. An identification code (e.g., a lot number for traceability)
is part of the labeling elements required on the finished products.
12.2.14 Authorization of New Substances
For authorization of new substances, the general procedure and competencies are
laid down in the Framework Regulation (EC) 1935/2004. Petitions with petitioner
summary data sheets and technical dossiers have to be filed with the EFSA via the
national contact points in the member states. A petition consists of data about physical
and chemical properties of the substance, impurities, intended applications, existing
approvals elsewhere in the world, migration, residual content, and toxicology. The
toxicology data needed depend on the amount of migration. If migration is below
0.05 mg/kg, only a core set of three in vitro mutagenicity tests will be needed: bacteria
reverse mutation assay (Ames test), induction of gene mutations in mammalian cells
(preferably the mouse lymphoma assay), and induction of chromosomal aberrations in
mammalian cells. At migration higher than 0.05 mg/kg but below 5 mg/kg, an addi-
tional 90-day oral toxicity study as well as data to demonstrate the absence of potential
for accumulation in humans will have to be provided. If migration exceeds 5 mg/kg,
a complete toxicological data set is needed that comprise the mutagenicity studies
noted previously; 90-day oral toxicity studies (normally in two species); studies on
absorption, distribution, metabolism, and excretion; studies on reproduction in one
species and developmental toxicity, normally in two species; as well as studies on
long-term toxicity/carcinogenicity, normally in two species. These toxicological
data are required for the substance to be approved, but data for impurities might
also be needed showing that their amount of migration is safe. Details as to how a peti-
tioner data sheet is to be structured and which information is needed are given in a note
for guidance (EFSA 2008a). A separate note for guidance is established for active and
intelligent materials (EFSA 2009). A third note for guidance describes the procedure
for a petition for a recycling process (EFSA 2008b).
12.3 UNITED STATES FOOD CONTACT MATERIALS REGULATIONS
12.3.1 General Rules and Structure of Regulations
General safety requirements are outlined in the Federal Food, Drug, and Cosmetic
Act (FDCA or the Act) (USA 1938/1958) by the prohibition to adulterate food in
Sec 301 [21 U.S.C. 331]. Food is defined as adulterated in Sec 402 [21 U.S.C. 342]
of the Act as follows: “If it bears or contains any poisonous or deleterious substance
which may render it injurious to health” including substances from packaging materi-
als. Food contact materials fall under the definition of food additives as indirect addi-
tives. In Section 402, the use of an uncleared food additive is constituted as an act
of food adulteration. Food additives are defined in Sec 201 [21 U.S.C. 321] as, “Any
substance the intended use of which results or may reasonably be expected to result,
directly or indirectly, in its becoming a component or otherwise affecting the
characteristics of any food.” This includes any substance intended for use in packing,
packaging, or holding food. Substances that are generally recognized as safe (GRAS),
“prior sanctioned,” or not reasonably expected to become components of food (no
migration exemption) are excluded from needing FDA clearance. Between 1958
(when the Food Additives Amendment to the FDCA came into force) and 1997,
requests for approvals of indirect food additives needed to be filed as petitions
that were then promulgated into general regulations for the respective polymer or
polymer additive. These approvals were laid down in the Code of Federal Regulations
21 (21 CFR) (FDA). With the FDA Modernization Act of 1997 (USA 1997), the
petition-regulation system changed mainly to food contact notifications (FCNs).
These are proprietary to the notifier and the manufacturer/supplier listed in the
FCN. The FCN is related only to the notified product but not to similar products
from others. J. Heckman describes the history of the U.S. food contact materials reg-
ulations, including explanations of developments and rules (Heckman 2005). In gen-
eral, the concept of good manufacturing practices is an important requirement for all
food contact materials as well as direct food additives. According to 21 CFR § 174.5,
additives may be used only in amounts that are necessary to achieve the intended
effect and must be of suitable purity for their use in food contact (i.e., it is the manu-
facturer’s responsibility that impurities do not lead to adulteration of the food).
12.3.2 Materials and Additives Regulation in 21 CFR
The specific rules for food contact materials are laid down in 21 CFR in Parts 170 to
189 (FDA). The basic definitions are given in Section 170.3, and the general provisions
applicable to indirect food additives in Part 174 (e.g., the requirement of good manufac-
turing practices). The following parts contain the specific rules for adhesives and coat-
ings (175), paper and paperboard (176), polymers (177), and adjuvants, production aids,
and sanitizers (178). Part 180 contains rules for food additives permitted on an interim
basis, which are acrylonitrile copolymers in case of food contact materials, and Part 189
deals with substances that are prohibited from being used. Other sections refer to direct
food additives only. The principle of US food contact materials regulation is premarket
approval. When a petition is filed, a material is investigated in depth on migration into
simulants, impurities, and so on and is evaluated for safety. Results are generalized for
the respective type of materials regardless of differences in polymerization processes,
leading to an entry in the respective part of 21 CFR. In contrast to the EU, where
compliance with the regulation has to be shown by periodical migration testing, in
the United States, the conformity with the material that was evaluated in depth is usually
checked by specifications and so-called end tests that are mainly simple extraction tests.
Evaluation of polymers is related to the base polymer as a whole and includes catalysts,
cross-linking agents, reaction control agents, and other essential components at the
polymerization stage. These substances, which are essential for the polymerization
process, are considered part of the basic polymer and are implicitly cleared along
with that polymer. This view is called the “basic polymer doctrine” (Heckman 2005).
A few catalysts are included in 21 CFR but only on the specific request of the petitioner.
Additives, such antioxidants, stabilizers, and pigments that are added after polymeriza-
tion, need specific clearance as indirect food additives. In an FCN, the manufacturing
process, including the catalysts and so forth, is part of the evaluation and substantial
changes in the process will require a new FCN or at least a pre-notification consultation
with the FDA (Twaroski et al. 2007).
If physically blended or otherwise physically combined (e.g., in a multilayer),
mixtures of polymers are regarded as conforming to the rules if all single components
comply. If one of the polymers is limited to a certain use (e.g., only for dry foods or not
for alcoholic foods), then the whole mixture is limited to that use. When the polymers
are not only physically blended but react with each other or are cross-linked with each
other, then a new polymer is formed that needs a specific clearance. This view is called
the “mixture doctrine” (Heckman 2005).
12.3.3 GRAS Substances
Substances that are deemed to be GRAS are excluded from the need to be regu-
lated by the FDA. GRAS substances do not fall under the definition of food additives.
These GRAS substances need to be adequately shown to be safe under the conditions
of their intended use through procedures undertaken by experts qualified by their

scientific training and experience to evaluate safety. Under 21 CFR 170.30 (b), general
recognition of safety through scientific procedures requires the same quantity and
quality of scientific evidence as is required to obtain approval of the substance as a
food additive and ordinarily is based upon published studies, which may be corrobo-
rated by unpublished studies and other data and information. The data and information
relied on to establish the safety for use of a GRAS substance must be generally avail-
able (e.g., through publication in the scientific literature), and there must be a basis to
conclude that there is consensus among qualified experts about the safety of the sub-
stance for its intended use. Thus, the difference between use of a food additive and use
of a GRAS substance relates to the widespread awareness of the data and information
about the substance, that is, who has access to the data and information and who has
reviewed those data and information (FDA 2004). GRAS substances do not need pre-
market approval by the FDA but a GRAS determination may be voluntarily evaluated
by the FDA via a GRAS notification.
12.3.4 Prior Sanctioned Substances
Substances that were sanctioned or approved before September 6, 1958, for use by
the FDA or the U.S. Department of Agriculture (e.g., by an opinion letter) are
excluded from the definition of food additives in Sec. 402, Title 21 § 321 (s), of the
Act. That is the date when the Food Additives Amendment to the Act came into
force. This means those substances may be used without further clearance of the
FDA and listing in 21 CFR. A list of prior sanctioned substances from food contact
materials is given in 21 CFR, Part 181. But there are more prior sanctioned substances
than those listed there (Heckman 2005). Although the FDA is not entitled to regulate
prior sanctioned substances due to this definition, in cases where actual scientific data
or information show that their use may be injurious to health, the FDA will establish or
amend an applicable prior sanction regulation and set limitations or other conditions
for safe use or prohibition (21 CFR 181.1 (b)).
12.3.5 Threshold of Regulation
In 1995, the FDA introduced a threshold of regulation (TOR) exemption process.

This means that the likelihood or extent of migration to food of a substance used in a
food contact article (FCA) is so negligibly small that it does not require regulation
(21 CFR 170.3) (FDA 1995). Information about those substances undergoes an abbre-
viated review by the FDA. The conditions for applying the TOR and the procedure are
defined in 21 CFR 170.39. The TOR is set at a dietary concentration of 0.5 μg/kg,
which corresponds to a dietary exposure level of 1.5 μg/person/day. The exposure
is based on a consumption of 3 kg per day composed of 1.5 kg solid and 1.5 kg liquid
food. Excluded from the TOR are known carcinogens in humans or animals or
substances that are suspected to be carcinogens based on their chemical structure.
Furthermore, the substance must not contain a highly carcinogenic impurity (i.e.,
an impurity with a TD50 value of less than 6.25 mg/kg bodyweight). The TD50 is
the dose in a feeding study on carcinogenicity that causes cancer in 50% of the test
animals. Furthermore, the substance must not have a technical effect on or in the
food to which it migrates, and it must not have a significant impact on the environ-
ment. Also included in the TOR is the use of approved direct food additives in
food contact materials when the dietary exposure resulting from the proposed use is
maximally 1% of the ADI of the substance.
For establishing the TOR, the FDA had evaluated the carcinogenic potencies of 477
chemicals as representatives of all known and unknown carcinogens. Carcinogenic toxic
effects in test animals usually occur at lower dietary concentrations than the levels
at which noncarcinogenic toxic effects occur. Information derived from these data
indicated that most known carcinogens pose less than one in a million upper-bound
lifetime risk if present in the daily diet at 0.5 ppb or less. Thus, the TOR is low enough
to ensure that a substance without toxicological data will represent not more than a
negligibly low risk even it would be identified later as a carcinogen (FDA 1995).
The information needed for a TOR exemption request is compiled in a guidance
document (FDA 2005); the TOR exemptions are listed on the FDA Web site.
12.3.6 No Migration Exemption, Functional Barrier Principle,

and Possibilities of Self-Determinations
Under certain circumstances, the US system allows self-estimations of the regula-

tory status by industry or independent experts without clearances or exemption pro-
cesses by the FDA. The first is the definition of a food additive that explicitly
excludes components of food contact materials that do not migrate or are not reason-
ably expected to migrate into food. This might be because a substance is completely
reacted or otherwise immobilized or prevented from migration under the intended
conditions of use by a sufficient functional barrier. As noted previously, substances
assessed as GRAS under the intended conditions of use also do not need a review
by the FDA. Those possibilities of self-determinations may be used for evaluation
of layers that are not yet regulated at all, such as printing inks on the external side
of packaging materials.
Furthermore housewares (i.e., food contact articles [FCAs] used exclusively in the
home or in restaurants, such dinnerware, eating utensils, or empty containers) are
exempted from regulation by the 1958 Food Additives Amendments. The FDA pro-
posed a rule to include them in 1974 but, due to opposition and limited resources, it
was never finalized (Heckman 2005). Thus, additional materials that are not regulated
may be used but requests to review safety evaluations via FCN or TOR exemption
may be sent to the FDA.
12.3.7 Food Contact Notifications—Applications to New Substances
The process of FCN is laid down in 21 CFR 170.101–106. A short description is

given by Shanklin and Sánchez (Shanklin and Sánchez 2005). Guidelines on admin-
istration, chemistry, and toxicology are provided on the FDA Web site. In contrast to
petitions and TOR exemptions, FCNs are proprietary and related only to the notifier
and the manufacturer/supplier listed in the FCN. FCNs become effective 120 days
after the acceptance date, unless the FDA objects, and the material may be legally mar-
keted at that time for the proposed use. If the cumulative daily intake of a food contact
substance (FCS) equals or exceeds 3 mg/person/day (biocides 0.5 mg/person/day) or
if a bioassay is not clearly negative for carcinogenic effects, a petition must be sub-
mitted unless the FDA agrees to accept an FCN. In these cases, a draft FCN should
be submitted to the FDA within a pre-notification consultation prior to submission
of the FCN. If the FDA has adequate time to thoroughly review the data, it will
agree to accept an FCN (Twaroski et al. 2007, Bailey et al. 2008).
An FCN (FDA Form 3480) consists of six parts: general information, chemistry
information, safety narrative, environmental information, certification, and the list
of attached documents.
Chemistry information includes data on the identity, manufacture, stability, tech-
nical effect, and proposed use of the FCS. It addresses all educts, impurities, and
degradation products. Migration is usually determined in food simulants, where
10% ethanol is used for aqueous, acidic, and low alcohol foods, 50% ethanol for
high alcohol foods, and food oil or Miglyol 812 for fatty foods; 95% ethanol, 50%
ethanol, or isooctane may also be used as fatty simulants depending on the polymer
(see chemistry recommendations, Appendix I [FDA 2007]). In addition, if food
acidity is expected to lead to significantly higher migration, 3% acetic acid is used.
Depending on the intended uses of the simulant, time temperature conditions are
given in Appendix II of the chemistry recommendations. In general, migration is
tested kinetically at a minimum of four time points so that long-term behavior can
be estimated from the migration curve. Long-term storage at room temperature usually
is evaluated with a 10-day test at 40°C; but in the case of low diffusive materials such
as polyethylene terephthalate (PET) or polystyrene, the time is extended to 30 days.
As an alternative to migration testing, 100% transfer assumption from the initial con-
centration or mathematical modeling may be used. The migration conditions are simi-
lar in the EU and the United States so that the same set of analytical data can be used
for both if some differences in details (e.g., validation requirements) are considered at
experimental planning.
The exposure is estimated from the migration data. Migration in the different
simulants is weighted by food type distribution factors (fT) that describe the fraction
of food in contact with the material that is aqueous, acidic, alcoholic, and fatty.
The fraction of the respective polymer or packaging material from the total packaged
food is considered by the consumption factor. Using these factors, the dietary concen-
tration is derived from the results of the migration tests. For estimation of the daily
intake (estimated daily intake, or EDI), a consumption of 3 kg food per person and
day is assumed. The factors and the calculations are described in the guidance docu-
ment, “Chemistry Recommendations” (FDA 2007). In case the substance is already
authorized for other uses, the cumulative estimated daily intake (CEDI) needs to be
calculated. The FDA provides a database for the CEDI on its Web site.
The extent of toxicological data needed in the safety narrative depends on the EDI or
CEDI. The narrative should be a concise summary of the scientific reasoning for the
safety assessment and should address the potential mutagenicity and carcinogenicity
of the FCS and its impurities (Sotomayor et al. 2006). For a dietary exposure at or below
1.5 μg/person/day, toxicity studies are not needed, but existing literature has to be com-
piled and evaluated. For an EDI of up 150 μg/person/day (dietary concentration 50 μg/kg),
two short-term in vitro genetic toxicity tests are recommended, the Ames test and a test for
gene mutations or chromosomal aberrations in mammalian cells. For estimated exposures
between 150 μg/person/day and 3000 μg/person/day (dietary concentration 1 ppm), an in
vivo chromosome aberration study in rodents and subchronic 90-day feeding studies in a
rodent and a nonrodent species are recommended. Depending on the results, other tests
may be needed. At higher exposures, a full set of toxicological studies will be required,
including carcinogenicity studies and reproductive/developmental studies. In addition to
the toxicity tests, structure activity relationship analysis may be used and is utilized by
FDA experts to predict the toxicological profile (Bailey et al. 2005, Sotomayor et al.
2006, Twaroski et al. 2007, Bailey et al. 2008).
An assessment of the environmental impact also must be provided if the intended
use does not qualify for a categorical exclusion claim. The legal basis for this is
provided by the National Environmental Policy Act. The environmental assessment
is defined in 21 CFR 25.40 and the categorical exclusions in 21 CFR 25.32.
A guideline can be found on the FDA Web site (FDA 2006a; Twaroski et al. 2007;
Bailey et al. 2008).
12.3.8 Nanomaterials
Actually, there are no specific rules for nanomaterials in food contact materials.
New substances with nano properties are evaluated within the FCN process. The
FDA knows that application of nanotechnology may result in product attributes that
differ from those of conventionally manufactured products and may merit examina-
tion. However, the FDA does not categorically judge all products containing nanoma-
terials as intrinsically benign or harmful. The FDA considers not only engineered
nanomaterials with at least one dimension in the nanoscale range (approximately
1 nm to 100 nm) but also larger materials up to 1 mm that exhibit properties that
are attributable to its dimensions. When manufacturing changes alter the dimensions,
properties, or effects of an FDA-regulated product or any of its components, the FDA
encourages industry to consult with the agency early on to address any questions
related to the safety, effectiveness, or other attributes of products that contain nanoma-
terials or about the regulatory status of such products (FDA 2014, 2015).
12.3.9 Recycling Materials
Safety of recycling processes (e.g., bottle to bottle recycling of PET) is evaluated

by the FDA. These evaluations are published as no objection letters on the FDA Web
site. For evaluation requests, the FDA provides a nonbinding guidance document
(FDA 2006). The safety of recycling processes is evaluated via challenge tests with
material which is fortified by addition of selected contamination surrogates. The
FDA proposes such a contamination scheme but also accepts other scientifically
justified schemes such as that proposed by Franz and Welle (2002). The first
no-objection letters for recycling processes were published in 1990; by 2013, that
number had risen to 168.
12.4 ASIAN FOOD CONTACT MATERIAL REGULATIONS
12.4.1 Overview of Regulatory Frameworks for Food Contact

Materials in Asian Countries
There are 48 currently recognized Asian countries including some in Central Asia
and Turkey but excluding Russia. Even though economic market organizations such
as the Asia-Pacific Economic Cooperation, the Association of Southeast Asian Nations,
and the Gulf Cooperative Council comprise groups of Asian countries, no Asia-wide
harmonized regulations and testing methods for FCMs exist.
Most Asian countries have included FCM regulations in their respective food
hygiene laws. Separate specifications and standards exist relating to the definition,
scope, and use conditions for FCMs or FCAs and to limit levels in materials and
migration tests for specific FCSs and methods of analyzing them. FCMs and FCAs
include packaging materials, containers, tableware, cookware, utensils, machines,
and apparatus that come into direct contact with food or food additives. FCM regula-
tions stipulate general guidelines prohibiting packaging and containers that could
yield any toxic, injurious, or hazardous substance, and they include negative lists
that limit the use of heavy metals and other hazardous substances.
In this regard, Japan is recognized as the first country in Asia to have established a
food hygiene law (1949) and specifications and standards for FCMs (1959). Japanese
FCM regulations and standards as well as their testing methods have to date been
widely accepted as references for the legislation of national rules in countries includ-
ing Korea, China, Thailand, and others. Therefore, general regulations, simulant
types, and contact conditions in migration testing methods have a lot of similarities
in most Asian countries. This is apparent, for instance, in the use of n-heptane for
fatty foodstuffs in migration tests, the simplicity of testing conditions (e.g., in the
time and temperature conditions), and in the use of concepts such as evaporation resi-
due (overall migration) without reduction factor, and the specification of heavy metal
contents in FCMs all of which show some differences from those of the EU and the
United States. Specifications and standards are in place for the following FCMs in
China, Japan, and Korea.
• China: Plastics, paper, bamboo, wood, metals, enameled ware, ceramics, glass,
rubber, rubber nipples, coatings, silicone, plant fibers, collagen casing
• Japan: Plastics, rubber, glass, ceramics, enameled ware, metal cans
• Korea: Plastics, paper, rubber, glass, ceramicss, metal, regenerated cellulose,
wood, starch
The most critical distinction in FCM regulation systems among countries may lie
in the legal stipulation and practical application of a positive list system for FCSs.
Regulatory requirements in most Asian countries are often based on a negative list
system—as opposed to the positive list system used in the EU, the United States,
and in MERCOSUR (Brazil, Argentina, Uruguay, Paraguay, and Venezuela)
countries (Kawaratani 2011). Among the Asian countries, however, China and
India have each introduced a compulsory positive list system for FCSs. Asian FCM
regulation systems are discussed in the following sections, with specific references
to China, Japan, and Korea.
12.4.2 China
The main law regulating the safety of food including FCMs in China is the
Chinese Food Safety Law. The authority responsible for the establishment of laws
for food and food-related products in China was the Ministry of Health (MOH). In
2013, the MOH was dissolved and its functions were integrated into the National
Health and Family Planning commission (NHFPC). The NHFPC is currently in
charge of licensing new FCMs and enacting the technical specifications of safety
assessment. The China National Center for Food Safety Assessment (CFSA) is
responsible for declaration and acceptance of application, safety assessment, and tech-
nical review of FCMs.
The use of FCMs in the Chinese market requires compliance with general provi-
sions contained in the Food Safety Law, food safety rules and regulations, and com-
pulsory safety standards (notified as GB). The framework of FCM standards are
composed of horizontal (basic) standards, commodity standards, test methods, and man-
ufactuing practices. A series of GBs have been published for various plastic resins,
paper, rubber, rubber nipples, silicone, aluminum, coating and lacquer, collagen
casing, diatomite, and additives since 1984.
The first compulsory regulation of additives used in FCMs, known as GB 9685-
2003, was established in 2003 and has, in all practical terms, served as a positive list
for FCMs. GB 9685-2003 regulates the general requirements of substances used
for manufacturing FCMs including the intended use, scope of the use of material,
and the maximum amount allowed in the material. The GB 9685-2003 list only
included a limited number of additives so to improve regulation, in 2008, the
MOH replaced it, implementing GB 9685-2008. This new, comprehensive positive
list required substances to be cleared by at least two of the following regulatory
bodies: the FDA, the EFSA, and the Japan Hygienic Olefin and Styrene Plastics
Association (JHOSPA) (Li and Bian 2010). GB 9685-2008 specifies the name,
chemical name, the chemical abstract service (CAS) number of each substance,
its scope of use, maximum use concentration allowed, specific migration limits
or maximum residual contents, and analysis of substances used to make FCMs
(Wang et al. 2011).
In June 2009, with GB 9685-2008 in place, the Ministry of Industry and Information
Technology ordered a “clean-up process” for additives used in FCMs in the Chinese
market, legally obliging industry to declare by June 1, 2010, the use of any additives
and resins not previously listed within the Chinese FCMs standards and henceforth
to obtain approval for their use from the authorities. On November 18, 2016, the NHFPC
released 2 general standards, 10 product standards, and 40 testing standards for FCMs,
which comes into force on October 19, 2017. General standards are composed of two
parts, i.e., general safety requirements of FCMs (GB 4806.1-2016) and Standard for
the use of additives for FCMs (GB 9685-2016). In the GB 9685-2016, the number of
listed additives is expanded from 958 to 1294. GB 31604.1-2015 specifies the migration
testing methods for FCMs. As food simulants, 10% ethanol is assigned for non-acidic
foods (pH ≥5), 4% acetic acid for acidic foods (pH <5), 20% ethanol for foods with
alcoholic content of up to 20%, 50% ethanol for foods with alcoholic content of 20%
~50%, actual ethanol concentration or 95% ethanol for foods with alcoholic content
above 50%, and vegetable oil for fatty foods, respectively.
12.4.3 Japan
FCMs are regulated by the Ministry of Health, Labor, and Welfare, which is
responsible for stipulating and enforcing regulations. Safety evaluation and risk
assessment, as well as research to establish the specifications and to develop the test-
ing methods, are conducted by the National Institute of Hygienic Sciences (NIHS).
Japanese specifications and standards for FCMs were first established in 1959 with
Notification No. 370. Notably in Japan, the specifications and standards for FCMs
used for milk and milk products are separately stipulated under the category of
Food Hygiene Law, presumably in recognition of the importance of the hygiene of
these products, particularly in relation to both young consumers and the sick. Risk
assessments and any subsequent amendments to regulations, specifications, and stan-
dards for FCMs are conducted and approved by the Food Safety Commission
affiliated with the Cabinet Office.
In Japan, however, FCM regulations have barely been amended owing to the policy
of minimum requirements (Mori 2010), resulting in limited inclusion of new FCMs and
FCSs on the regulatory plastic inventory to date. As a result, for instance, current Japa-
nese specifications and standards for FCMs include only 13 synthetic resins and some
other FCMs (e.g., glass, enameled ware, ceramic, rubber, and metal can) that might
be inadequate to cover the whole range of FCMs in a changing market (Mori 2010).
The use of synthetic resins not included in these lists must only comply with general
specifications and standards. To make up for this weakness in assuring the safety of
FCMs caused by the rigidity of governmental regulations, package makers and suppliers
and FCM producers have instituted industrial safety organizations and have established
their own specifications and standards. This process evolved through the Japan Rubber
Manufacturer Association (1950), Japan Printing Ink Makers Association (1952),
Japan Hygienic PVC Association (1967), JHOSPA (1973), Japan Adhesive Industry
Association and Japan Petrolatum Wax Industry Association (1974), and Hygienic
Association of PVDC (1977), who have created positive list systems of substances
allowed for use in the manufacture of FCMs or FCAs.
Ostensibly, the safety of FCMs in the Japanese market appears secure because
almost all packaging makers and material suppliers have joined the corresponding
hygienic industry associations. However, the key drawback of this system is that
the lists are not mandatory. Additionally, products from nonmember makers and
suppliers of both domestic and foreign origin are not obliged to comply with the
voluntary rules, even though their products can be distributed in the Japanese market.
For this reason, the Japanese government is currently collaborating with industry asso-
ciations to establish a mandatory “positive list system” of FCSs.
For overall and specific migration tests, the following food simulants are mainly
used: (1) water for nonacidic, nonalcoholic, and nonfat foods (pH > 5.0), (2) 4% acetic
acid for acidic foods (pH ≤ 5.0), (3) 20% ethanol for alcoholic foods, and (4)
n-heptane for fatty foods. The migration test conditions are applied as follows:
60°C/30 min for use below 100°C and for aqueous food simulants and 95°C/30 min
for use at 100°C or above for the water and acid simulants. As an exception, n-heptane
is used at 25°C for 1 hr.
The drawback is that current FCM testing methods in Japan as well as in Korea are
therefore limited because no specific testing conditions are provided for simulating the
migration of fatty foods used at above 100°C, where the use of n-heptane is not
available. It is also unrealistic for testing conditions using n-heptane to be fixed at
25°C/1 hr, regardless of the use temperature range, even above 100°C. Therefore, com-
prehensive studies have been conducted to resolve this by introducing reduction factors
when using fatty food simulants, diversifying the contact time and temperature condi-
tions of migration testing, and using alternative fatty food stimulants such as isooctane
and 95% ethanol, depending on the plastic types involved (Kawamura 2012).
Currently, there is no separate, specified food simulant for migration testing of dry
foods. Four different liquid food simulants can be used for dry foods: water, 4% acetic
acid, 20% ethanol, and n-heptane, each matching with its food type. Migration testing
conditions for simulating food contact are not as diverse and specific as they are in the
EU and the United States, restricting the effectiveness of simulations of actual FCMs
storage and contact conditions.
An English version of the Japanese FCM regulations, specifications, standards,
and migration testing methods is currently provided on the following Web sites,
although it is not consolidated:
http://www.mhlw.go.jp/english/topics/foodsafety/index.html
https://www.jetro.go.jp/ext_images/en/reports/regulations/pdf/foodext2010e.pdf
12.4.4 Korea
Relevant regulatory bodies for FCMs in Korea are the Food Additives Standardi-
zation Division of Ministry of Food and Drug Safety (MFDS) and the Food Additives
and Packages Division of the National Institute of Food and Drug Safety Evaluation
(NIFDS). The MFDS chiefly establishes and enforces regulations, whereas the func-
tion of the NIFDS is focused on safety evaluation and assessment and on the devel-
opment of methods for analyzing FCSs.
The Food Hygiene Law was enacted in 1962 and, initially, standards and specifica-
tions for nine kinds of FCMs were established in 1969. According to food hygiene laws
in Korea and Japan, FCMs include any utensils, containers, and packages that come into
direct contact with foodstuffs. In the main, Korea’s FCM regulations are similar to the
key elements of the Japanese system except that they have been substantially amended
with new notifications as required, and this evolution is reflected in the updated Korea
Food Code (Lee and Yoon 2011). In 2015, standards and specifications for food uten-
sils, containers, and packages (S-FCMs) were separated from the Korea Food Code.
The S-FCMs include: (1) general standards, (2) common specifications and standards,
(3) standards for end use, (4) specifications by material, and (5) testing methods for mate-
rials and migration. As of February 2017, the S-FCMs list 40 plastics to be regulated.
Furthermore, regulations for regenerated cellulose film, rubber, papers and processed
papers, metal, glass, ceramic, enameled ware, pottery, wood, and starch include specifi-
cations and standards for material and migration tests. Methods and conditions of mate-
rial and migration tests are similar to those of Japan. Exceptionally, the migration test
conditions were changed in March 2015 as follows: 70°C/30 min for use below 100°C
and for aqueous food simulants, and 100°C/30 min for use at 100°C or above for
the water and acid simulants. Besides, as of November 2012, Korea introduced the
use of a 50% ethanol simulant for foodstuffs containing more than 20% alcohol.
For FCMs or FCAs not covered by current regulations, premarket approval can be
obtained from the KFDA within 14 working days, after a review of the relevant doc-
umentation. This is called the “provisional approval of the standards and specifica-
tions system.” A provisional approval is granted to the manufacturer or supplier of
the FCMs. This can be activated and is then valid for use in the market until the mate-
rial is appended to the food code (Lee and Yoon 2011).
At present, the additives used for manufacturing FCMs or FCAs are not super-
vised by a premarket approval system like the positive list system in the EU and
the United States. That means FCMs or FCAs are assessed on the basis of their per-
formance in material and migration tests of finished products. The safety of FCMs and
FCAs is evaluated on the basis of whether or not they comply with the general pre-
scription for use condition and with material and migration tests—not by the exposure
assessments of the FCSs contained in the material.
Under the MFDS, the current Korean system for regulating FCMs is more
straightforward than the positive list system in terms of administration and market sur-
veillance. The MFDS has tended to view the personnel requirements and budget asso-
ciated with implementing a positive list system in Korea as prohibitive. The S-FCMs,
however, cannot guarantee comprehensive knowledge of every FCS in use across the
entire market even in the most ideal circumstances. Only the manufacturer of a certain
FCA knows its composition and the amounts of additives in it apart from any other
reason, and it is not practically feasible for the MFDS to identify every single sub-
stance used in the manufacture of FCAs or FCMs. Moreover, even if goods contain
FCSs unapproved by the EU or US positive lists, under the current Korean system, it
is rarely feasible to impose sanctions against them if they are unrestricted by S-FCMs
(Lee and Yoon 2011).
Currently, English information regarding the Korean FCM regulations is provided
on the Web site, http://www.mfds.go.kr/eng/eng/index.do?nMenuCode=120&page=
1&mode=view&boardSeq=70089.
ACKNOWLEDGMENTS
The authors would like to express deep gratitude to Dr. Kawamura of NIHS,
Mr. Isurugi of the Japanese Hygienic Association of PVDC, and Dr. Wang of Jinan
University for their careful reviews and kind comments on the manuscript of the
Asian subchapter.
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Index
A opacity measurements, 72–73
pallet testing, 118–120
Abbé refractometer, 212 sample conditioning, 118
Abrasion toss, 196–197 shock testing, 113–115
Absolute viscosity, 218 tear strength, 110
Acceptable daily intake (ADI), 254–255, 308 tensile properties, 108
Acceptance tests, 16 thermal shock resistance, 151
Acceptance threshold, 50 vibration testing, 115–116
Active and intelligent FCMs, 289–291, 314 viscosity, 97
Active packaging, 69 Asymmetric flow field flow fractionation
Adhesion strength, 198 (AF4), 294
Adhesion test of multilayer plastic films, 111–113 Atmospheric conditions, 241, 246
Adhesive bonds, 195–196 Atmospheric gases, 17
ADI. See Acceptable daily intake Atomic force microscopy (AFM), 85, 92
Aerosol cans, 165, 168–169, 172–173 Autoxidation, 23–24, 52
Aerosol tops and bottoms, 172–173
AFM. See Atomic force microscopy
B
Aged cheeses, 44
Air permeance, 198 Bakery products, 44–45
Alternative tests/screening tests, 255, 266–274 Barcol hardness test, 210–211
Aluminum, 4, 24, 156 Barrier properties, 7–8, 43
in can making, 173–181 Basis weight, 188–189
double seams, 176–178 Beach puncture test, 189–190
enamel rating, 180–181 Beam bending, 196
Aluminum oxide, 3 Beer, 27
Ambient oxygen ingress rate, 134 Bending stiffness, 194
American Society for Testing Materials (ASTM) “best before” date, 13, 14, 16
International, 104, 242–244 BET. See Brunauer, Emmett and Teller
Amorphous materials, 82, 83 (BET) theory
Anaerobic degradation, 225–226 Beverages, 43
Archimedes’ principle, 89 Biodegradability testing, 222–226
Ascorbic acid, 24 laboratory tests, 224
Asian food contact material regulations, 323–327 standards for compostability, 222–223
ASTM. See American Society for Testing Materials Biodegradable packaging, 69
(ASTM) International Biodegradation, methods for, 224–226
ASTM standard methods, heat distortion Bioplastics, 4, 201–229
temperature, 79 biodegradability testing, 222–226
ASTM standards compositional analysis, 220–222
adhesion test of multilayer plastic films, density, 206
112–113 environmental stress cracking, 219–220
change of dimension, 78 introduction to, 202–205
change of weight, 79 mass, 206–207
coefficient of friction, 111 material properties of, 204
compostability, 223 optical properties of, 211–215
compression testing, 117 oxygen permeability, 216–217
D3985, 132 rheological properties, 217–219
energy absorption/release, 76 testing methods, 205–220
F1307, 133–134 color, 213–215
gas transmission, 128 compression tests, 208
impact strength, 109 hardness tests, 209–211
molecular weight, 71–72 impact tests, 208
333
334 INDEX
luminous transmittance, 212–213 enamel rating on, 180–181

mechanical properties, 207–211 inspection methods, 178–179
melt index test, 218–219 Cantilever test, 196
microscopical method, 212 Capacity, of glass containers, 145–146
permeability testing, 215–217 Capilliary rheometry, 99
physical properties, 205–207 Carbon black, 293
puncture tests, 209 Carbon dioxide, 36–40, 202
refractive index, 211–212 Cardboard flavor, 36
refractometric method, 212 Carton board, 194
rheological measurements, 217–219 Catastrophic incident, 106
tensile tests, 297–298 Cellophane, 48
viscosity tests, 218 Cellulose, 186
thermal analysis techniques, 226–229 regenerated, 309–310
thickness, 206 Ceramic materials, 311
utilization of, 203 Charpy impact strength, 208
water absorption of, 221 Cheeses, aged, 44
water vapor permeability, 215–217 Chemical hazards, 15
Biopolymers, 202–205; see also Bioplastics Chemical mechanisms
Biotic mechanism, of quality decay, 37–40 of quality decay, 23–27
Blocking resistance, 197–198 autoxidation, 23–24
Board recycling, 288–289 light-induced reactions, 27
Botrytis, 39 oxidative reactions, 23, 24–26
Boxes, corrugated, 3, 192, 198–199 photooxidation, 24–25
Break point, 108 Chemical properties, of glass, 146–150
Brunauer, Emmett, and Teller (BET) theory, 32 Chinese regulations, 324–325
Bursting strength, 190 Climatic conditions, 17–18
Code of Federal Regulation (CFR), 106, 177
C Code of Federal Regulations 21 (21 CFR),
317–319
CA. See Controlled atmosphere Coefficient of friction (COF), 110–111, 192
Calorimetry, 90 Cold water baths, 150
Canada General Standards Board (CGSB), 106 Color
Can ends, 169–173 of bioplastics, 213–215
aerosol tops and bottoms, 172–173 instruments to measure, 214
easy open ends, 171–172 measurements, 72
sanitary ends, 170–171 of plastic packaging, 69–70
Can-making process, 156 Colorimeter, 213, 214
aerosol cans, 165 Communication, 3
aluminum cans, 173–181 Compact foods, 43
double seams, 176–178 Compositional analysis
draw/redraw cans, 167–168 analytical tests, 221
DWI cans, 168–169, 173 moisture analysis, 222
end making from ETP or TFS, 169–173 solubility test, 222
food cans from welded can body, 163–165 water absorption, 221
quality control in, 182–183 of bioplastics, 220–222
shallow drawn cans, 167 molecular weight, 220–221
three-piece, 159–163 Compostability standards, 222–223
tinplate, 159–169 Compost method, 225
two-piece, 159–160 Compression testing, 116–117, 208, 246
two-piece aerosol cans, 168–169 Compressive loads, 241, 246
vacuum-resistant cans, 165–167 Co-Nanomet, 294
Cans Cone and plate rheometer, 97–99
DRD, 167–168 Consumer awareness, 205, 304
DWI, 168–169 Containment, 2
INDEX 335
Contaminants, 35–36, 48–51 Dome growth, 176

Contamination, 18 Double seams
Controlled atmosphere (CA), 15–16 on cans, 176–178
Convenience, 2 destructive vs. nondestructive inspection
Convenience foods, 43 methods, 178–179
Corrugated boxes, 3, 192, 198–199 in-line monitoring to control external seam
Corrugated fiberboard, 189–190, 193–196, dimensions, 179
198–199 measurements on filled vs. empty cans, 178
Coulometric oxygen sensor, 132–133 Drawing and wall ironing (DWI), 156, 173
Council of Europe (CoE), 307 Draw/redraw (DRD) cans, 167–168
Critical water activity, 34 Dried foods, 43
Critical water content, 34 Drops, 237–239
Crystallinity, 81–84 Dry products, 31
calculation of, 87–89 DSC. See Differential scanning calorimetry
density measurements, 88–90 Durometer hardness test, 210
x-ray diffraction and, 85–87 DWI can-making process, 173
Crystallization phase transition, 75 DWI cans, 168–169
Cushioning materials, 113–114 Dynamic accumulation methods
coulometric oxygen sensor, 132–133
D of measuring GTR, 129–133
oxygen permeability, 131
Dairy products, 44 steady-state method, 132
Data storage, 183 Dynamic mechanical analyzers (DMAs), 74, 79
Date, for lifetime of food product, 13, 15, 16 Dynamic mechanical thermal analysis (DMTA),
Decay processes, 21–22; see also Quality decay 228–229
chemical mechanisms, 23–27 Dynamic viscosity, 218
classification of, 18–20
of food types, 40–45 E
Declaration of compliance, 315–316
Declaration-related shelf life, 22–23 Easy open ends, 171–172
DEG. See Diethylene glycol EC Regulation 1835/2004, 15
Density measurements, 88–90, 191, 206 Edgewise compressive strength, 192–193
Desiccants, 32 Effective size, 220
Desimetry, 89–90 EFSA. See European Food Safety Authority,
Desorption isotherms, 31 286–288
Detection threshold, 50 Elasticity, 108, 208
Dielectrics, 73 Electrical properties, of plastic packaging, 73
Diethylene glycol (DEG), 271–272 Electrolytic tinplate (ETP) coating, 156, 158, 167
Differential scanning calorimetry (DSC), 74, Electron microscopy (EM), 91–92
75–76, 226, 227 Enamel rating, on cans, 180–181
Diffusion coefficient, 256, 275–276, 277–279 Engineered nanoparticles (ENPs), 290, 294, 295
Diffusion modeling, 277–279 Environmental scanning electron microscope, 93
Diffusivity, 271–272 Environmental stress cracking, 219–220
Di-iso-propylnapjthaline (DIPN), 289 Environmental stress-cracking resistance, 219–220
Distribution environment hazards, 236–248 Environmental testing, 117–120
atmospheric conditions, 241, 246 pallet testing, 118–120
compressive loads, 241, 246 sample conditioning, 117–118
shock, 236–239, 244–245 unit load testing, 120
types of tests for, 241–242 Epoxy derivatives, 312
vibration, 239–241 Ethylene vinyl alcohol (EVAL), 216
vibrations, 246 ETP. See Electrolytic tinplate (ETP) coating
Distribution shock, 236–239 EU. See European Union
DMAs. See Dynamic mechanical analyzers EU 282/2008, 286–288
DMTA. See Dynamic mechanical thermal analysis EU Directive 2007/42/EC, 309–310
336 INDEX
EU Framework Directive 76/893/EEC, 305 requirements for, 1–2

EU Framework Regulation 1935/2004, 257, 289, shelf life and, 12–15
305, 307, 310, 314, 316–317 testing authorities and regulations, 303–328
EU Regulation No. 1169/2011, 13, 14 types of, 253
European Bioplastics, 203 Food packaging materials
European Federation of Corrugated Board active and intelligent, 289–291, 314
Manufacturers, 196 bioplastics, 201–229
European food contact material regulations, glass, 139–154
304–317 introduction to, 1–3
European Food Safety Authority (EFSA), 305 metal, 155–183
European Plastics Regulation 10/2011, 259, 264, migration testing, 251–297
272–275, 280, 293, 307–309, 312 oxygen permeability values for, 54–56
Exposure, 256 paper, 185–199
External conditions, 16–18 plastic, 67–100
Extraction, 253–254 testing methods for, 103–121
properties of, 4–7
F barrier properties, 7–8
migration aspects, 8
Fat, 266, 268 physical and mechanical properties, 8
FCMs. See Food contact materials shock and vibration testing, 233–249
FDA Modernization Act, 317 standards for, 104
FFF. See Field flow fractionation (FFF) substance transport rates and, 46–48
Field flow fractionation (FFF), 294 synthetic polymers, permeation testing,
Field testing, 235 123–136
Flat cruch (impact loading), 193–194 types of, 3–4
Flat crush (slow rate of loading), 193 water vapor permeation rate of, 54–56
Flavors Food preservation, 156
loss of, 35–36 Food products
packaging functionality and, 48–51 quality decay of, 21–27
uptake of off-flavors, 35–36 transport of, 104, 234
Flavor scalping, 36 Food quality
Flow moisture point, 32 introduction to, 12–15
Fluorescence-based oxygen measurement, 133 quality decay, 21–22
Focused simulations, 242 chemical mechanisms of, 23–27
Folding endurance, of paper, 189 physical mechanisms of, 27–37
Food, Drug, and Cosmetic Act (FDCA), 317 Food stimulants, 255
Food Additives Amendment, 317 list of, 258–259
Food contact materials (FCMs), 253, 257, 258, 263, specific assignment of, to foods, 259–260
266, 304 Food types
active and intelligent, 289–291 classification of, 40–45
Asian regulations on, 323–327 decay mechanisms, 40–45
European regulations on, 304–317 Forklift handling, 115
migration of nanoparticles from, 295–297 Fossil fuels, 202
nano applications in, 291–297 Fourier transform infrared (FTIR) spectroscopy, 78
recycling, 283–289 Fracture diagnosis, of glass, 153–154
safety-in-use of, 279–283 Fragility test, 113
U.S. regulations on, 317–323 Free-fall drop testing, 114, 245
Food contact notifications (FCNs), 317, 320–322 Freezer burn, 35
Food packaging Fresh meat/seafood, 43–44, 56
correlation of packaging functionality and shelf Fresh produce, 44, 56
life, 45–59 Frozen conditions, 18
effects of, on growth of microorganisms, 38–39 Frozen foods
functions of, 1–3, 16–17, 68–69, 252–253 decay processes, 44
nano applications in, 291–297 textural changes, 35
INDEX 337
Fruit, fresh, 44, 59 H

Functional barriers, 272–274, 312, 320
Hardness tests, 209–211
Hazardous goods packaging regulations, 106
G
Haze, 212–213
Gas chromatography (GC), 263 HDPE, 285–286
Gas permeability, 128 HDT. See Heat deformation temperature; Heat
Gas transmission rate (GTR) distortion temperature
vs. gas permeability, 128 Head space, 16–17, 18, 39
methods for measuring, 128–134 substance transport rates and, 46–48
dynamic accumulation methods, 129–133 Heat deformation temperature (HDT), 74
isostatic steady-state methods, 129 Heat distortion temperature (HDT), 79
pressure or volume increase methods, Heat resistance, 226
128–129 Henry’s law, 45, 124
Gel permeation chromotography (GPC), 70–71, High-density polyethylene (HDPE), 208
220–221 High-moisture products, 29, 30, 31, 34–35
Generally recognized as safe (GRAS), 317, High-performance liquid chromatography (HPLC),
318–319, 320 135, 263
General simulations, 242 Horizontal impact testers, 244–245
Glass, 3, 139–154 Horizontal shocks, 114–115
advantages of, 140–141 Hot water baths, 150
composition of, 141 Hysteresis, 33–34
definition of, 139–140
fracture diagnosis, 153–154 I
impact strength and testing, 149–150
internal pressure breakage, 148 IFST. See Institute of Food Science and
introduction to, 139–141 Technology
parts of glass container, 141–146 Illumination, 18
physical and chemical properties, 146–150 Impact breakage, 149
pressure resistance, 147–148 Impact loading, 193–194
recycling, 283 Impact strength
resistance to abrasion and scratching, of glass, 149–150
149–150 of plastic, 109–110
thermal shock resistance, 150–153 Impact tests, 208
vertical load strength test, 148 Induction time, 24
Glass containers Inductively coupled plasma-mass spectrometry
capacity of, 145–146 (ICP-MS), 294
defects in, 153, 154 Infrared sensing, 135–136
dimensions of, 142–143 Infrared spectroscopy, 91
ovality of, 146 In-line monitoring, 179
parts of, 141–146 Institute of Food Science and Technology
verticality of, 143–145 (IFST), 13
Glassine paper, 4, 187 Instron Universal Testing Machine, 208
Glass transition, 74, 79 Insulation property, 73
Glass transition temperature, 226 Intelligent packaging, 290, 314
Gloss, 70 Intergovernmental Maritime Consultative
Glossmeter, 214–215 Organization (IMCO), 106
Good manufacturing practices (GMP), 315, Intermediate moisture products, 29, 30, 31
317–318 Internal friction, 79
GPC. See Gel permeation chromotography Internal pressure breakage, 148
Gravimetric methods, of water vapor transmission International Air Transport Association
measurement, 134–135 (IATA), 106
Greaseproof paper, 3, 187 International Safe Transit Association (ISTA), 104,
GTR. See Gas transmission rate 106, 244
338 INDEX
International Standards Organization (ISO), 104, testing methods, 103–121

105, 206, 242–244 adhesion test of multilayer plastic films,
Intrinsic properties, 16–17, 18 111–113
ISO. See International Standards Organization of bioplastics, 207–211
Isooctane, 268 coefficient of friction, 110–111
2-iso-propyl thioxanthone (ITX), 253, compression testing, 116–117
310–311 environmental testing, 117–120
Isostatic steady-state methods, of measuring impact strength, 109–110
GTR, 129 regulation in, 104–106
ISTA. See International Safe Transit Association shock testing, 113–115
ITX crisis, 253, 310–311 tear strength, 110
tensile properties, 106–109
vibration testing, 115–116
J Mechanical shock testing, 114
Japanese regulations, 325–326 MEG. See Monoethylen glycol
Melt flow indexing (MFI), 97, 98, 218–219
Melting process, of plastic polymers, 74
K Melting temperature, 226
Metal, 4
Kinematic viscosity, 218
recycling, 283
Korean regulations, 326–327
Metal packaging, 155–183
Kraft paper, 3, 187
advantages of, 156
aluminum cans, 173–181
L history of, 156
introduction to, 156
L, a, b tristimulus system, 213 quality control, 157–173
Labeling, 3, 315–316 in can-making industry, 182–183
Laboratory tests, 235 on tinplate, 157
Laurolactam, 268 testing of coatings on steel, 158–159
Lettuce, 44 tinplate can making, 159–169
Light barrier properties, 7, 8 MFI. See Melt flow indexing
Light exposure, 18 Microbial contamination, 7
Light-induced reactions, 27 Microbiological mechanisms, of quality decay, 37–38
Light scattering, 71 Microorganisms
Light-struck flavor, 27 effects of packaging on, 38–39
Light transmittance, 52 spoilage, 37–38, 39
Logistical packaging, 113–120 Microscopical method, 212
Logistics, 234 Microscopy techniques, 85, 91–93
Low-density polyethylene (PE-LD), 48 Migration
Low-moisture products, 29–30, 31, 43 definition of, 253
Luminous transmittance, 212–213 modeling, 256
overall, 254
M specific, 254–255, 263–264, 309
Migration aspects, 7, 8
Manufacturing method, 273 Migration limit, 254, 312
MAP. See Modified atmospheric packaging Migration modeling, 274–279
Mass, of bioplastics, 206–207 diffusion modeling, 277–279
Maximum quantity (QM), 255, 269–270 recent developments in, 277–279
Maximum residual content, 255 state of the art of, 275–277
Meat Migration test cell, 256
color change in fresh, 26–27 Migration testing, 251–297
fresh, 43–44, 59 active and intelligent FCMs, 289–291
Mechanical properties, 8 alternative tests/screening tests, 255, 266–274
standards for, 104 diffusion characteristics, 271–272
INDEX 339
extraction and total mass transfer Nanotechnology, 291–297

assumption, 269–270 Naphtha, 202
semidirect migration test, 266–269 Natural gas, 202
conventional tests, 255 New substances
definitions, 253–256 application of FCNs to, 320–322
elements of, 257 authorization of, 316–317
food stimulants, 255 Newtonian fluid, 217
list of, 258–259 NIAS. See Nonintentionally added substances
specific assignment of, to foods, 259–260 Nonintentionally added substances (NIAS), 257,
functional barriers, 272–274 280–282
general scheme for, 258 Non-Newtonian fluids, 217, 218
nanotechnology, 291–297 Nonprocessed foods, biotic mechanisms relevant
nonrequirements, 272 for, 40
“nontarget,” 257 Nonsimulative tests, 241–242
one-sided contact, 256
overall, 261–262
for residual content in the polymer, 264–266 O
screening analysis, 279–283
solubility as migration limiting factor, Off-flavors, 35–36, 48–51
270–271 Off-odors, 18
specific, 263–264 One-sided contact, 256
standard tests, 255, 257–266 Opacity measurements, 72–73
test conditions for, 260–261 Optical character recognition (OCR), 176
total immersion, 256 Optical properties
Milk, 27 of bioplastics, 211–215
Mineral oil aromatic hydrocarbon (MOAH), 288 color, 213–215
Minimally processed foods, biotic haze, 212–213
mechanisms of, 40 luminous transmittance, 212–213
Modified atmospheric packaging (MAP), 36, refractive index, 211–212
specular gloss, 214–215
38–39, 44, 69
of plastic packaging, 69–70
Modulus measurements, 79
Orientation, of synthetic polymers, 84–85
Modulus of elasticity, 108
OTR. See Oxygen transmission rate
Moisture analysis, 192, 222
Ovality, of glass containers, 146
Molds, 39, 59
Overall migration (OM), 254
Molecular weight, 69
Overall migration limit (OML), 254, 261–262
determination of, 70–72
Oxidative reactions, 23, 24–26
using gel permeation chromatography,
shelf life and, 51–53
220–221
Oxygen
Monoethylen glycol (MEG), 271–272
ambient oxygen ingress rate, 134
Morphological properties
permeability, 216–217
general features of synthetic polymers, 80–85
pressure-dependent interaction of, with food
constituents, 26–27
testing methods for, 85–93
transport rate, 48
Multimaterial multilayer materials, 258,
Oxygen barrier, 7–8
273–274, 312
Oxygen partial pressure, 26–27, 52, 56
Myoglobin, 26–27
Oxygen permeability, 131
Oxygen permeation properties, 52, 54–56
Oxygen tolerance thresholds, 23, 51
N
Oxygen transmission rate (OTR), 128
Nanomaterials, 314–315, 322 dynamic accumulation methods for measuring,
Nanoparticles, 292–293 129–133
determination of, 294–295 of whole packages, 133–134
migration of, 295–297 Oxygen uptake, quantification of, 25
340 INDEX
P Permeability, 7, 43, 45–46, 56

gas, vs. gas transmission rate, 128
Packaged food oxygen, 131, 216–217
decay processes, 18–20 steady-state permeation theory, 124–125
shelf life of, 12–15 temperature dependence of, 127
Package labeling, 3, 315–316 testing, 215–217
Packaging. See Food packaging water vapor, 215–217
Packaging functionality units, 127–128
flavors, off-flavors, and contaminants, 48–51 unsteady-state diffusion, 125–126
oxidative processes and, 51–53 Permeability coefficient, 125, 128
shelf life and, 45–59 Permeation coefficient, 46
shelf life for respiring products and, 56–59 Permeation rates, 40, 45–46
substance permeation and, 45–46 Permeation testing
water uptake/losses and, 53–54 GTR measurement, 128–134
Pallet testing, 118–120 OTR measurement, 128–134
Paper, 3–4, 185–199 of synthetic polymers, 123–136
European regulations on, 310 water vapor transmission measurement,
introduction to, 186 134–136
recycling, 288–289 PET. See Polyethylene terephthalate
testing, 188–199 Photooxidation, 24–25, 52
abrasion toss, 196–197 Physical mechanisms, of quality decay, 27–37
adhesion strength, 198 Physical properties, 8
air permeance, 198 of bioplastics, 205–207
basis weight, 188–189 of glass, 146–150
bending stiffness, 194 opacity measurements, 72–73
blocking resistance, 197–198 of plastic packaging, 69–73
bursting strength, 190 testing methods for, 70–73
cantilever test, 196 Plastic packaging materials, 67–100
coefficient of friction, 192 bioplastics, 201–229
density, 191 electrical properties, 73
edgewise compressive strength, 192–193 European regulations on, 307–309
flat crush, 193–194 general features of synthetic polymers,
folding endurance, 189 80–85
moisture analysis, 192 introduction to, 68–69
peel test, 195 logistical packaging, 113–120
puncture resistance test, 189–190 morphological properties, 80–93
shear test, 194, 196 physical properties, 69–73
stiffness, 197 color, 69–70, 72
tear strength, 191 molecular weight, 69
tensile strength, 190 opacity measurements, 72–73
thickness, 189 optical properties, 69–70
vertical impact test, 198–199 testing methods for, 70–73
vibration transmissibility, 194–195 recycling, 283–286
water absorptiveness, 195 rheological properties, 93–100
water resistance tests, 195–196 testing methods, 103–121
water vapor permeability, 191–192 adhesion test of multilayer plastic films,
types of, 187–188 111–113
Paperboard, 4, 186, 191–194, 310 coefficient of friction, 110–111
Parchment paper, 4, 188 compression testing, 116–117
Partition coefficient, 256, 271, 276 environmental testing, 117–120
Pathogenic microogranisms, 37–38, 39 impact strength, 109–110
Peel test, 195 regulation in, 104–106
Percent elongation at break, 107 shock testing, 113–115
Perforation, 59 tear strength, 110
INDEX 341
tensile properties, 106–109 R

vibration testing, 115–116
Radio frequency identification (RFID)
thermal properties, 73–80
general features of, 73–75 packaging, 69
testing methods for, 75–80 Raman spectroscopy, 91
Plastics, 4, 202 Ready-to-bake foods, 44
Point of deliquescence, 32 Ready-to-cook food, 43
Poly-D-lactide (PDL), 226 Ready-to-eat food, 43
Polyethylenes, 69–70 Recycling
Polyethylene terephthalate (PET), 48, 75, 156, 271, adoption of, 202
277–279, 281, 285–286, 296, 297–298 EFSA criteria for, 286–288
European regulations on, 312–314
Polyhydroxyalkanoates (PHAs), 215
FCMs, 283–289
Polymers
density measurements, 88–90 FDA criteria for, 284–286
glass, 3
migration aspects, 8
steady-state permeation theory, 124–125 paper and board, 288–289
U.S. regulations on, 322–323
Polystyrene (PS), 48
Refractive index, 71, 211–212
Polyvinylidene chloride (PVDC), 48
Power spectral density (PSD), 240–241 Refractometric method, 212
Refrigerated conditions, 18
Preshipment testing, 234–236
Pressure resistance, of glass, 147–148 Regenerated cellulose (CE), 48, 309–310
Regulations; see also specific regulations
Primary colors, 213
Asian, 323–337
Primary nanoparticles (pNP), 292
Printing inks, 310–311 European, 304–317
U.S., 317–323
Prior sanctioned substances, 319
Product liability claims, 183 Required shelf-life period, 53–54
Protection, 1–2 Respiring products, 56–59
Retorted food, 44
Puncture resistance test, 189–190
Puncture tests, 209 Rheological properties, 93–100
capilliary rheometry, 99
Pure culture method, 224–225
Purity restrictions, 309 cone and plate rheometer, 97–99
measurements, 94–100, 217–219
melt index, 97, 98
Q
QM. See Maximum quantity stresses and strains, 95–96
QMA, 255, 269–270 viscosity, 96–97
Quality control Rheology, 93–100
in can-making industry, 182–183 Rheometers, 217–218
in metal packaging, 157–173 Riboflavin, 27
Quality decay, 21–22 Rockwell hardness test, 157, 209–210
biotic mechanisms of, 37–40
chemical mechanisms of, 23–27 S
autoxidation, 23–24
light-induced reactions, 27 “Safe life,” 13–14, 15, 39
oxidative reactions, 23, 24–26 Safety issues, with plastics, 4
photooxidation, 24–25 Sample conditioning, 117–118
color change of meat, 26–27 Sanitary ends, 170–171
flavor loss, 35–36 Scanning electron microscopy (SEM), 85, 92, 93
freezer burn, 35 Scanning TEM (STEM), 85
microbiological mechanisms of, 37–38 Scavenging systems, 291
physical mechanisms of, 27–35 Screening analysis, 279–283
textural changes, 35 Screening tests, 241–242, 255, 266–274
uptake of off-flavors, 35–36 Screw caps, 143
Quality-related shelf life, 21–22 Seafood, fresh, 43–44
342 INDEX
Seam inspection, 178–179 Steel, testing coatings on, 158–159

Semicrystalline polymers, 83, 89 Sterilized liquid dairy products, 43
Semidirect migration test, 266–269 Stiffness, of paper, 197
Senescence, 40 Storage tests, 15–16
Sensitizer molecules, 24 Strains, 95–96
Sensory attributes, 21–22 Stresses, 95–96
Sewage sludge, 225–226 Substance permeation, 45–46
Shallow drawn cans, 167 Substance transport rate, 40, 43, 46–48
Shear, 217 Sulfite paper, 3, 187
Shear rate, 217 Supply chain management, 233–234, 316
Shear stress, 95–96, 217 Synthetic polymers
Shear test, 194, 196 density measurements, 88–90
Shelf life general features of, 80–85
correlation of packaging functionality and, 45–59 crystallinity, 81–84
decay processes and, 18–20 orientation, 84–85
declaration-related, 22–23 permeation testing of, 123–136
definition of, 13 steady-state permeation theory, 124–125
effects of packaging on, 38–39 temperature dependence of permeability, 127
external conditions and, 16–18 testing methods for morphological properties,
flavors, off-flavors, and contaminants, 36, 48–51 85–93
intrinsic properties and, 16–17, 18 unsteady-state diffusion, 125–126
introduction to, 12–15
investigations, 15–16 T
oxidative processes and, 51–53
physical limitations of, 36–37 TA. See Thermal analysis (TA) techniques
quality-related, 21–22 Tear strength, 110, 191
for respiring products, 56–59 TEM. See Transmission electron microscopy
water uptake/losses and, 53–54 Temperate conditions, 17
Shock and vibration testing, 113–115, 233–249 Temperature
testing equipment, 244–248 dependence of permeability on, 127
test methods, 242–244 heat distortion, 79
types of tests for, 241–242 melting, 226
Shocks, 236–239, 244–245 Tensile properties, testing methods for, 106–109
Short-lived products, 13 Tensile strain, 95
Silicon dioxide, 293 Tensile strength, 7, 107, 190, 297–298
Silicones, 311–312 Tensile stress, 154
Simulations, 241–242 Tensile tests, 297–298
Size-exclusion chromatography (SEC), 70–71 Test chambers, 246
Smart packaging, 69 Testing authorities and regulations, 303–328
SML. See Specific migration limit Testing methods
Soil burial method, 224 for bioplastics, 205–220, 222–226
Solubility, as migration limiting factor, 270–271 for paper, 188–199
Solubility test, 222 for plastic packaging materials, 103–121
Sorption isotherms, 31–34 Textural changes, 35
Specific migration, 254–255, 263–264 TFS. See Tin free steel
Specific migration limit (SML), 254–255, 263–264, TGA. See Thermogravimetric analyzer
270, 271–272, 309 Thermal analysis (TA) techniques, 226–229
Spectrophotometers, 213, 214 differential scanning calorimetry, 226, 227
Specular gloss, 214–215 dynamic mechanical thermal analysis, 228–229
Spoilage microorganisms, 37–38, 39 thermogravimetric analysis, 226, 227–228
Starch retrogradation, 35 thermomechanical analysis, 226, 228
Stationary conditions, 46 Thermal properties
Statistical process control (SPC), 157, 182 change of dimension, 76–78
Steady-state permeation theory, 124–125 change of energy absorption or release, 75–76
INDEX 343
change of weight, 78–79 Unsteady-state diffusion, 125–126

general features of, 73–75 “Use by” date, 13, 15, 16
heat distortion temperature, 79 U.S. Food and Drug Administration (FDA),
modulus measurements, 79 284–286, 317
of plastic packaging, 73–80 U.S. food contact materials regulations, 317–323
testing methods for, 75–80 UV light, 24
Thermal shock breakage, 150–153
Thermal shock resistance, 150–153
Thermogravimetric analysis (TGA), 74, 226, V
227–228
Vacuum packaging, 39, 44
Thermomechanical analysis (TMA), 74, 76–78,
Vacuum-resistant cans, 165–167
226, 228
Vapor-grown carbon fibers (VGCFs), 73
Thermoplastics, 4
Vegetables, fresh, 44, 59
Thermosets, 4
Vertical impact test, 198–199
Thickness
Verticality, of glass containers, 143–145
of bioplastics, 206
Vertical load strength test, 148
of paper, 189
VGCFs. See Vapor-grown carbon fibers
Three-piece can making, 159–163
Vibration, 239–241
Threshold of regulation (TOR), 319–320
Vibration testing, 115–116, 246
TiN. See Titanium nitride (TiN)
Vibration transmissibility, 194–195
Tin, 158
Viscosity, 96–97
Tin free steel (TFS), 156, 158–159
absolute, 218
Tinplate, 4, 157
dynamic, 218
Tinplate can making, 159–169
kinematic, 218
Titanium nitride (TiN), 293
tests, 218
Tocopherol, 24
Volume ratio, 271
Tolerable daily intake (TDI), 254–255, 308
Tomato cans, 158
Total immersion, 256 W
Total mass transfer assumption, 269–270
Toyo Ultimate Can (TULC), 156, 159 Warehousing, 234, 241
Traceability, 315–316 Water absorption, 221
Translucency, of plastics, 211 Water absorptiveness, 195
Transmission electron microscopy (TEM), 85, Water activity, 28–31
92, 293 critical, 34
Transparency, of plastics, 211 Water content, 22
Transportation, of food products, 104, 234 changes in, 27–35
Trial shipments, 235 decrease in, 34–35
Triplet oxygen, 23 increase in, 31–34
Triplet state, 23 textural changes without overall, 35
Tropical conditions, 18 critical, 34
TULC. See Toyo Ultimate Can Water loss, 28, 53–54
21 CFR. See Code of Federal Regulations, 21 Water resistance tests, 195–196
Two-piece aerosol cans, 168–169 Water uptake, 28, 53–54
Two-piece can making, 159–160 Water vapor, 48
Type I isotherms, 31–32 barrier, 7
Type II isotherms, 32, 33 permeability, 216
Type III isotherms, 32 of paper, 191–192
permeability test, 215–217
permeation rates, 54–56
transmission measurement, 134–136
U
transmission rate, 54
Ultraviolet (UV) spectroscopy, 71 Water vapor transmission rates (WVTRs), 134–135
Unit load testing, 120 Waxed paper, 188
344 INDEX
Welded can body Y

aerosol cans from, 165
Yellowness index, 214
food cans from, 163–165
vacuum-resistant cans from, 165–167 Yield point, 108
Young’s modulus, 79, 108
Wine, 27
X Z
X-ray diffraction, 85–87 Zero-defect production, 182–183

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FOOD

© 2017 by Taylor & Francis Group, LLC

No claim to original U.S. Government works

Printed on acid-free paper

International Standard Book Number-13: 978-1-4665-5994-3 (Hardback)

Library of Congress Cataloging-in-Publication Data

Names: Singh, Preeti (Materials scientist) | Wani, Ali Abas. | Langowski,

Visit the Taylor & Francis Web site at

and the CRC Press Web site at

Horst-Christian Langowski is a professor and the chair of Food Packaging Tech-

functions, he is a member of the management board of the Bayerische

Byungjin Min Ali Abas Wani

Ali Abas Wani, Preeti Singh, and Horst-Christian Langowski

reduces chemical changes such as light- or oxygen-induced oxidation and

Figure 1.1 Major functions of food packaging.

Communication: The purpose of package labeling is to inform the consumer about

1.2 PACKAGING MATERIALS FOR FOOD APPLICATIONS

4. Glassine: This greaseproof paper has a high degree of smoothness and a

1.3 PROPERTIES OF PACKAGING MATERIALS

Packaging materials are selected on the basis of characteristics of the food to be

Mechanical, Chemical, and

Mechanical, Chemical, and

FOOD PACKAGING MATERIALS: TESTING & QUALITY ASSURANCE

1. Permeability—Should have selective permeability for gases, moisture, and

These factors will be discussed in subsequent chapters of this book. Following is a

1.3.1 Barrier Properties

The barrier properties of packaging materials have signiﬁcant inﬂuence on the

in several food products. Therefore, oxygen-sensitive food products require

1.3.2 Physical and Mechanical Properties

The physical and mechanical properties of packaging materials are important in

1.3.3 Migration Aspects of Packaging Materials

Shelf Life of Packed Food and

2.1 Introduction to Food Quality and Shelf Life ..................................................12

2.9 Biotic Mechanisms .........................................................................................37

2.1 INTRODUCTION TO FOOD QUALITY AND SHELF LIFE

Arbitrary quality parameter

“Use by” or “best before”– Time/ “Best before”–

• Declaration-related reasons where the quantiﬁable amount of an ingredient (e.g.,

2.2 DIFFERENT CASES FOR SHELF-LIFE INVESTIGATIONS

As an important prerequisite, we cannot test an isolated product without packaging—

2.3 FACTORS FROM PRODUCT, PACKAGE, AND ENVIRONMENT

• Temperate conditions, with a maximum temperature of 25°C and a maximum

• Tropical conditions, with a maximum temperature of 37°C and a maximum

2.4 GENERAL CLASSIFICATION OF DECAY PROCESSES

If we want to understand the potential effects of packaging on shelf life, we need a

Factors Inside the Package

Quality-related effects on product life → shelf life

Factors Inside the Package

Quality-related effects on product life → shelf life (continued)

FOOD PACKAGING MATERIALS: TESTING & QUALITY ASSURANCE

Declaration-related product life → shelf life

Safety-related effects on product life → safe life

Note: Factors of high effect are italicized.

2.5 FACTORS RELEVANT FOR THE ASSESSMENT OF QUALITY

• The detailed nature of the deterioration mechanisms (e.g., the development of

Cooked milk-like 0 Oily

Fatty Green, grassy

2.6 FACTORS RELEVANT FOR DECLARATION-RELATED SHELF LIFE

An indication of the contents of industrially made food packages is mandatory

2.7 CHEMICAL MECHANISMS OF QUALITY DECAY

2.7.1 Oxidative Reactions

2.7.4 Quantiﬁcation of Oxygen Uptake

Reacted amount of oxygen (a.u.) I IIa IIb

2.7.5 Pressure-Dependent Interaction of Oxygen with Food