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Plastic Packaging

Edited by
Otto G. Piringer and Albert L. Baner
Further Reading

Elias, H.-G.

Macromolecules
Volume 1: Chemical Structures and Syntheses

2005
ISBN: 978-3-527-31172-9

Elias, H.-G.

Macromolecules
Volume 2: Industrial Polymers and Syntheses

2007
ISBN: 978-3-527-31173-6

Elias, H.-G.

Macromolecules
Volume 3: Physical Structures and Properties
2008
ISBN: 978-3-527-31174-3

Elias, H.-G.

Macromolecules
Volume 4: Applications of Polymers

2009

ISBN: 978-3-527-31175-0

Brennan, J. G.

Food Processing Handbook

2006
ISBN: 978-3-527-30719-7
Plastic Packaging

Interactions with Food and Pharmaceuticals

Edited by
Otto G. Piringer and Albert L. Baner

Second, Completely Revised Edition

The Editors All books published by Wiley-VCH are carefully
produced. Nevertheless, authors, editors, and
Dr. Otto G. Piringer publisher do not warrant the information contained
FABES ForschungsGmbH in these books, including this book, to be free of
Schragenhofstr. 35 errors. Readers are advised to keep in mind that
80992 München statements, data, illustrations, procedural details or
Germany other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

Dr. Albert L. Baner
Nestle Purina Petcare British Library Cataloguing-in-Publication Data
Checkerboard Square A catalogue record for this book is available from the
St. Louis, MO 63164 British Library.
USA
Bibliographic information published by
the Deutsche Nationalbibliothek
Die Deutsche Nationalbibliothek lists this
publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available in the
Internet at <http://dnb.d-nb.de>

# 2008 WILEY-VCH Verlag GmbH & Co. KGaA,

Weinheim

All rights reserved (including those of translation into

other languages). No part of this book may be
reproduced in any form – by photoprinting,
microfilm, or any other means – nor transmitted or
translated into a machine language without written
permission from the publishers. Registered names,
trademarks, etc. used in this book, even when not
specifically marked as such, are not to be considered
unprotected by law.

Typesetting Thomson Digital, Noida, India

Printing betz-druck GmbH, Darmstadt
Book Binding Litges & Dopf GmbH, Heppenheim
Cover Design Anne Christine Keßler, Karlsruhe

Printed in the Federal Republic of Germany

Printed on acid-free paper

ISBN: 978-3-527-31455-3
 V

Contents

Preface XV
List of Contributors XVII

1 Preservation of Quality Through Packaging 1

Albert Baner and Otto Piringer
1.1 Quality and Shelf-Life 1
1.2 Physical and Chemical Interactions Between Plastics and Food
or Pharmaceuticals 4
1.3 The Organization of this Book 5
Further Reading 12

2 Characteristics of Plastic Materials 15

Johannes Brandsch and Otto Piringer
2.1 Classification, Manufacture, and Processing Aids 15
2.1.1 Classification and Manufacture of Plastics 16
2.1.1.1 Raw Materials and Polymerization Processes 17
2.1.1.2 Addition Polymerization 18
2.1.1.3 Condensation Polymerization 19
2.1.1.4 Synthesis of Copolymers, Block, and Graft Copolymers 19
2.1.1.5 Polymer Reactions 20
2.1.1.6 Plastic Processing 22
2.1.2 Processing Aids 23
2.1.2.1 Initiators and Crosslinkers 24
2.1.2.2 Catalysts 25
2.2 Structure and States of Aggregation in Polymers 26
2.2.1 Structure 26
2.2.2 States of Aggregation 29
2.3 The Most Important Plastics 32
2.3.1 Thermoplastics 32
2.3.1.1 Polyethylene 32

Plastic Packaging. Second Edition. Edited by O.G. Piringer and A.L. Baner
Copyright Ó 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31455-3
VI Contents

2.3.1.2 Polypropylene 34
2.3.1.3 Polybutene-1 36
2.3.1.4 Polyisobutylene 36
2.3.1.5 Poly-4-methylpentene-1 (P4MP1) 36
2.3.1.6 Ionomers 36
2.3.1.7 Cyclic Olefin Copolymers (COC) 37
2.3.1.8 Polystyrene 38
2.3.1.9 Polyvinyl Chloride 39
2.3.1.10 Polyvinylidene Chloride 41
2.3.1.11 Thermoplastic Polyesters 41
2.3.1.12 Polycarbonate 42
2.3.1.13 Polyamide 43
2.3.1.14 Polymethylmethacrylate 44
2.3.1.15 Polyoxymethylene or Acetal Resin 45
2.3.1.16 Polyphenylene Ether (PPE) 45
2.3.1.17 Polysulfone 45
2.3.1.18 Fluoride Containing Polymers 46
2.3.1.19 Polyvinylether 46
2.3.2 Thermosets 46
2.3.2.1 Amino Resins (UF, MF) 47
2.3.2.2 Unsaturated Polyester (UP) 47
2.3.3 Polyurethanes 48
2.3.4 Natural and Synthetic Rubber 49
2.3.5 Silicones 51
2.3.6 Plastics Based on Natural Polymers Regenerated Cellulose 54
2.3.6.1 Biodegradable Polymers 54
2.3.7 Coatings and Adhesives 55
2.3.7.1 Lacquers 56
2.3.7.2 Plastic Dispersions 57
2.3.7.3 Microcrystalline Waxes 57
2.3.7.4 Temperature-Resistant Coatings 58
2.3.7.5 Printing Inks and Varnishes 59
References 60

3 Polymer Additives 63
Jan Pospíšil and Stanislav Nešpu°rek
3.1 Introduction 63
3.2 Antifogging Agents 64
3.3 Antistatic Agents 65
3.4 Blowing Agents 65
3.5 Colorants 66
3.6 Fillers and Reinforcing Agents 66
3.7 Lubricants 67
3.8 Nucleating Agents 67
3.9 Optical Brighteners 68
 Contents VII

3.10 Plasticizers 68
3.11 Stabilizers 70
3.11.1 Antiacids 71
3.11.2 Antimicrobials 72
3.11.3 Antioxidants 72
3.11.3.1 Chain-Breaking Antioxidants 73
3.11.3.2 Hydroperoxide Deactivating Antioxidants 74
3.11.4 Dehydrating Agent 75
3.11.5 Heat Stabilizers 75
3.11.6 Light Stabilizers 76
3.11.6.1 Light Screening Pigments and UV Absorbers 76
3.11.6.2 Photoantioxidants 77
3.12 Transformation Products of Plastic Stabilizers 78
3.12.1 Transformation Products from Phenolic Antioxidants and UV
Absorbers 79
3.12.2 Transformation Products from Hydroperoxide Deactivating
Antioxidants 83
3.12.3 Transformation Products from Hindered Amine
Stabilizers 84
3.12.4 Transformation Products from Heat Stabilizers for PVC 85
3.13 Conclusions 86
References 86

4 Partition Coefficients 89
Albert Baner and Otto Piringer
4.1 Experimental Determination of Polymer/Liquid Partition
Coefficients 89
4.2 Thermodynamics of Partition Coefficients 90
4.2.1 Equilibrium Between Different Phases in Ideal Solutions 91
4.2.1.1 Partitioning in Ideal Solutions: Nernst’s Law 92
4.2.2 Equilibrium Between Different Phases in Nonideal Solutions 93
4.2.2.1 Partition Coefficients for Nonideal Solutions 94
4.2.3 Partition Coefficients for Systems with Polymers 96
4.2.4 Relationship Between Partition Coefficients and Solubility
Coefficients 98
4.3 Estimation of Partition Coefficients Between Polymers and
Liquids 99
4.3.1 Additive Molecular Properties 99
4.3.2 Estimation of Partition Coefficients Using QSAR and QSPR 102
4.3.3 Group-Contribution Thermodynamic Polymer Partition Coefficient
Estimation Methods 102
4.3.3.1 Estimation of Partition Coefficients Using RST 104
4.3.3.2 Estimation of Partition Coefficients Using UNIFAC 104
4.3.3.3 Estimation of Partition Coefficients Using Group-Contribution
Flory Equation-of-State 108
VIII Contents

4.3.3.4 Estimation of Partition Coefficients Using Elbro Free Volume Model 108
4.3.3.5 Comparison of Thermodynamic Group-Contribution Partition
Coefficient Estimation Methods 108
4.3.4 Vapor Pressure Index Partition Coefficient Estimation Method 109
4.3.4.1 Examples of Vapor Pressure Index Values 112
References 118

5 Models for Diffusion in Polymers 123

Peter Mercea
5.1 Diffusion in Polymers – The Classical Approach 125
5.1.1 Diffusion in Rubbery Polymers 126
5.1.1.1 Molecular Models 126
5.1.1.2 The Molecular Model of Pace and Datyner 129
5.1.1.3 Free-Volume Models 131
5.1.1.4 The Free-Volume Model of Vrentas and Duda 133
5.1.2 Diffusion in Glassy Polymers 135
5.2 Diffusion in Polymers – The Computational Approach 140
5.2.1 Molecular Dynamics 142
5.2.2 The Transition-State Approach 150
5.3 Conclusions 154
References 158

6 A Uniform Model for Prediction of Diffusion Coefficients with

Emphasis on Plastic Materials 163
Otto Piringer
6.1 Introduction 163
6.2 Interaction Model 166
6.2.1 Model Assumptions 166
6.3 Prerequisites for Diffusion Coefficients 168
6.3.1 Critical Temperatures of n-Alkanes 168
6.3.2 Melting Temperatures of n-Alkanes 170
6.3.3 Melting Temperatures of Atom Clusters 173
6.3.4 Critical Compression Factor 175
6.3.5 The Entropy of Evaporation 175
6.3.6 The Reference Temperature and the Reference Molar Volume 176
6.4 The Diffusion Coefficient 178
6.4.1 Diffusion in Gases 178
6.4.2 Diffusion in the Critical State 181
6.4.3 Diffusion in Solids 181
6.4.3.1 Self-diffusion Coefficients in Metals 181
6.4.3.2 Self-Diffusion Coefficients in Semiconductors and Salts 183
6.4.3.3 Self-Diffusion Coefficients in n-Alkanes 184
6.4.4 Diffusion in Liquids 184
6.4.4.1 Self-Diffusion Coefficients in Metals 184
6.4.4.2 Self-Diffusion Coefficients in n-Alkanes 185
 Contents IX

6.4.5 Diffusion in Plastic Materials 188

6.4.5.1 Diffusion Coefficients of n-Alkanes in Polyethylene 188
6.4.5.2 Diffusion Coefficients of Additives in Polymers 191
References 193

7 Transport Equations and Their Solutions 195

Otto Piringer and Titus Beu
7.1 The Transport Equations 195
7.1.1 The Terminology of Flow 196
7.1.2 The Differential Equations of Diffusion 197
7.1.3 The General Transport Equations 200
7.2 Solutions of the Diffusion Equation 201
7.2.1 Steady State 202
7.2.2 Nonsteady State 202
7.2.3 Diffusion in a Single-Phase Homogeneous System 203
7.2.3.1 Dimensionless Parameters and the Proportionality of Mass Transfer
to the Square Root of Time 209
7.2.3.2 Comparison of Different Solutions for the Same Special Cases 212
7.2.4 Diffusion in Multiphase Systems 213
7.2.4.1 Diffusion in Polymer=Liquid Systems 213
7.2.4.2 Influence of Diffusion in Food 224
7.2.5 Surface Evaporation 225
7.2.6 Permeation Through Homogeneous Materials 227
7.2.7 Permeation Through a Laminate 228
7.2.8 Concentration Dependence of the Diffusion Coefficient 228
7.2.9 Diffusion and Chemical Reaction 229
7.3 Numerical Solutions of the Diffusion Equation 230
7.3.1 Why Numerical Solutions? 230
7.3.2 Finite-Difference Solution by the Explicit Method 231
7.3.2.1 von Neumann Stability Analysis 236
7.3.2.2 The Crank–Nicholson Implicit Method 237
7.3.3 Spatially Variable Diffusion Coefficient 240
7.3.4 Boundary Conditions 241
7.3.5 One-Dimensional Diffusion in Cylindrical and Spherical
Geometry 243
7.3.6 Multidimensional Diffusion 245
References 246

8 Solution of the Diffusion Equation for Multilayer Packaging 247

Valer Tosa and Peter Mercea
8.1 Introduction 247
8.2 Methods for Solving the Diffusion Problem in a Multilayer (ML)
Packaging 248
8.3 Solving the Diffusion Equation for a Multilayer Packaging in
Contact with a Foodstuff 251
X Contents

8.4 Development of a User-Friendly Software for the Estimation of

Migration from Multilayer Packaging 256
References 261

9 User-Friendly Software for Migration Estimations 263

Peter Mercea, Liviu Petrescu, Otto Piringer and Valer Tosa
9.1 Introduction 263
9.2 MIGRATEST#Lite – A User-Friendly Software for Migration
Estimations 266
9.2.1 Basic Features of MIGRATEST#Lite and Input Data Menus 266
9.2.2 Estimation of Migration with MIGRATEST#Lite 276
9.2.3 Output Information Delivered by MIGRATEST#Lite 278
9.2.4 Case Examples Computed with MIGRATEST#Lite 278
9.2.5 Migration Estimations with the MIGRATEST#EXP Software 281
9.2.6 Case Examples Computed with MIGRATEST#EXP 287
References 296

10 Permeation of Gases and Condensable Substances Through

Monolayer and Multilayer Structures 297
Horst-Christian Langowski
10.1 Introduction: Barrier Function of Polymer-Based
Packaging 297
10.2 Permeation Through Polymeric Materials 302
10.2.1 Substance Transport Through Monolayer Polymer Films 303
10.2.2 Substance Transport Through Multilayer Polymer Films
(Laminates) 305
10.2.3 Units for Different Parameters 307
10.3 Substance Transport Through Single and Multilayer Polymer
Substrates Combined with One Inorganic Barrier Layer 307
10.3.1 Numerical Modeling 307
10.3.2 Simplification: Barrier Improvement Factor 311
10.3.3 Multilayer Polymer Substrates Combined with One Inorganic
Layer 313
10.3.4 Polymer Substrates Combined with an Inorganic
Barrier Layer and Other Polymer Layers on Top of
the Inorganic Layer 314
10.3.5 Temperature Behavior of the Structures Shown Above 316
10.3.6 Substance Transport Through Thin Polymer Layers Having
Inorganic Layers on Both Sides 317
10.5 Substance Transport Through Polymers Filled with
Particles 320
10.6 Experimental Findings: Polymer Films and One Inorganic
Barrier Layer 321
10.6.1 Structures and Defects in Inorganic Barrier Layers on Polymer
Substrates 323
 Contents XI

10.6.2 Comparison of Model Calculations and Experimental Results for

Combinations of Polymer Films and One Inorganic Barrier Layer 324
10.6.3 Apparent Additional Transport Mechanisms for Water Vapor 327
10.6.4 Properties of Systems with at least One Inorganic Layer
Embedded Between to Polymer Layers or Films 332
10.7 Experimental Findings: Combinations of Polymer Films and More
Than One Inorganic Barrier Layer 332
10.8 Experimental Findings: Polymers Filled with Platelet-Shaped
Particles 333
10.9 Experimental Findings: Permeation of Flavors Through Mono- and
Multilayer Films and Combinations with Inorganic Barrier
Layers 338
10.10 Conclusions 342
References 342

11 Migration of Plastic Constituents 349

Roland Franz and Angela Störmer
11.1 Definitions and Theory 349
11.1.1 Migration, Extraction, and Adsorption 349
11.1.2 Functional Barrier 350
11.1.3 Legal Migration Limits and Exposure 350
11.1.4 Parameters Determining Migration 352
11.2 Indirect Migration Assessment 354
11.2.1 Worst-Case (Total Mass Transfer) Assumption 355
11.2.2 General Considerations: Taking Solubility and/or Low Diffusivity of
Certain Plastics into Account 357
11.2.3 Migration Assessment of Mono- and Multilayers by Application of
Complex Mathematical Models 359
11.2.4 Multilayers 359
11.3 Migration Experiment 361
11.3.1 Direct Migration Measurement in Conventional and Alternative
Simulants 361
11.3.2 Accelerated Migration Tests: Alternative Migration Tests 362
11.3.3 Choice of Appropriate Test Conditions 365
11.3.3.1 Food Simulants 365
11.3.3.2 Time–Temperature Conditions 367
11.3.3.3 Surface-to-Volume Ratio 369
11.3.3.4 Migration Contact 370
11.4 Analysis of Migration Solutions 372
11.4.1 Overall Migration 372
11.4.1.1 Aqueous and Alternative Volatile Simulants 372
11.4.1.2 Olive Oil 372
11.4.1.3 Modified Polyphenylene Oxide (Tenax1) 373
11.4.2 Specific Migration 374
11.4.2.1 Vinyl Chloride EU Directives 374
XII Contents

11.4.2.2 EN 13130 Series 374

11.4.2.3 Further Standard Methods 375
11.4.2.4 Methods of Analysis in Petitions to the European Commission 376
11.4.2.5 Methods in Foods (Foodmigrosure Project) 377
11.5 Development of Methods, Validation, and Verification 378
11.5.1 Establishing (Juristically) Valid Performance of Methods 378
11.5.2 A Practical Guide for Developing and Prevalidation of Analytical
Methods 380
11.5.3 Validation Requirements for EU Food Contact Petitions and US
FDA Food Contact Notifications 387
11.5.4 Determination of the Detection Limit 387
11.5.5 Analytical Uncertainty 389
11.5.6 Use of the Precision Data from Fully Validated Methods 390
11.6 Sources of Errors 394
11.6.1 Highly Volatile Migrants 394
11.6.2 Reaction with Food/Simulant Constituents 395
11.6.3 Migrants in Reactive Processes (e.g., Primary Aromatic Amines
from Adhesives) 397
11.7 Migration into Food Simulants in Comparison to Foods 400
11.8 Consideration of Non Intentionally Added Substances (NIAS) and Other
not Regulated Migrants 407
References 409

12 US FDA Food Contact Materials Regulations 417

Allan Bailey, Layla Batarseh, Timothy Begley and Michelle Twaroski
12.1 Introduction 417
12.2 Regulatory Authority 417
12.2.1 Federal Food, Drug and Cosmetic Act (FFDCA) 417
12.2.2 National Environmental Policy Act (NEPA) 421
12.3 Premarket Safety Assessment 422
12.3.1 Introduction 422
12.3.2 Chemistry Information 422
12.3.2.1 Migrant Levels in Food 423
12.3.2.2 Packaging Information 423
12.3.3 Toxicology Information 426
12.3.3.1 Safety Assessment 427
12.3.3.2 General Considerations 431
12.3.4 Environmental Information 432
12.3.4.1 Claim of categorical exclusion 432
12.3.4.2 Environmental Assessment (EA) 434
12.3.4.3 Polymeric Food Packaging Materials 435
12.3.4.4 Inadequacies in EAs 436
12.4 Final Thoughts 437
12.5 Conclusions 438
References 438
 Contents XIII

13 Community Legislation on Materials and Articles Intended to Come into

Contact with Foodstuffs 441
Luigi Rossi
13.1 Introduction 441
13.2 Community Legislation 442
13.2.1 Directives/Regulations Applicable to all Materials and Articles 442
13.2.1.1 Framework Directives/Regulation 442
13.2.1.2 Regulation on Good Manufacturing Practice 445
13.2.2 Directives Applicable to One Category of Materials and Articles 446
13.2.2.1 Directive on Regenerated Cellulose Film 446
13.2.2.2 Directive on Ceramics 447
13.2.2.3 Directive on Plastics Materials 448
13.2.2.4 Field of Application 448
13.2.2.5 EU List of Authorized Substances 449
13.2.2.6 Restricted Use of Authorized Substances (OML, SML, QM,
and QMA) 450
13.2.2.7 Authorization of New Substances 451
13.2.2.8 Directives on the System of Checking Migration 452
13.2.2.9 Functional Barrier 454
13.2.2.10 Fat (Consumption) Reduction Factors 455
13.2.2.11 Declaration of Compliance 456
13.2.2.12 Specific Rules for Infants and Young Children 457
13.2.2.13 Special Restrictions for Certain Phthalates now Authorized
at EU Level 457
13.2.2.14 Simulant for Milk and Milk Products 458
13.2.2.15 Other Complementary Community Initiatives 458
13.2.3 Directives Concerning Individual or Groups of Substances 459
13.2.3.1 Directives on Vinyl Chloride 459
13.2.3.2 Directive on MEG and DEG in Regenerated Cellulose Film 459
13.2.3.3 Directive on Nitrosamines in Rubber Teats and Soothers 459
13.2.3.4 Regulation on the Restriction of Use of Certain Epoxy
Derivatives 459
13.2.3.5 Directive on the Suspension of the Use of Azodicarbonamide
as Blowing Agent in Plastics 460
13.2.3.6 Regulation on Some Plasticizers in Gaskets in Lids 460
13.3 National Law and European Mutual Recognition 460
13.3.1 Future Commission Plans 462
13.4 National Legislations and Council of Europe Resolutions 462
13.5 Conclusions 462

14 Packaging Related Off-Flavors in Foods 465

Albert Baner, Francois Chastellain and André Mandanis
14.1 Introduction 465
14.2 Sensory Evaluation 466
14.3 Identification of Off-Flavor Compounds 468
XIV Contents

14.4 Physical Chemical Parameters Determining Off-Flavors 469

14.5 Derivation of Threshold Concentrations of Sensory-Active
Compounds 474
References 494

15 Possibilities and Limitations of Migration Modeling 499

Peter Mercea and Otto Piringer
15.1 Correlation of Diffusion Coefficients with Plastic Properties 501
15.2 The Partition Coefficient 511
References 521

Appendices 523

Appendix I 525
Peter Mercea
References 552

Appendix II 557
References 589

Appendix III 591

A Selection of Additives Used in Many Plastic Materials 591

Index 607
 XV

Preface

This second edition confirms that in an active field like the interaction of plastic
packaging with food and pharmaceuticals such a book can only be a work in
progress. In just seven years after the first edition was published enough significant
new research and learning has taken place to necessitate an update. Most chapters in
the second edition have been rewritten to reflect advances in the estimation of
physical and chemical interaction parameters like diffusion and partition coeffi-
cients as well as new developments and methods for estimating diffusion and
migration with user friendly software. We have also incorporated new state of the
art material on permeation, migration testing, regulatory development and off-
flavors.
The goal of the second edition remains to provide a practical and accessible
treatment of plastic packaging interactions with food and pharmaceuticals that fills
the gap between the many general food packaging books and ones that are very
mathematical and theoretical.
The interaction between plastics and foods and pharmaceuticals remains a very
active field and recent trends continue to shape research and development in this
area. This makes it more important than ever to understand the interactions
between food/pharmaceuticals and plastic packaging as plastic packaging usage
and range of application continues to expand every year.
At the same time more plastics are being used there is increased regulatory
scrutiny of all chemicals in general including those used in food packaging. No
longer are chemicals being monitored and regulated just on the bases of their acute
and chronic toxicities but also their environmental and endocrine disruption activ-
ities at trace levels far below those previously evaluated. Regulatory activity and
chemical monitoring has been made easier and more widely available by affordable
and increasingly powerful analytical techniques with the ability to detect ever lower
levels of substances. These factors amount to more stringent control and monitoring
of potential migration of substances from plastic packaging into foods and pharma-
ceuticals. Economic trends such as the growing global trade in packaging where
some packaging is coming from markets with little food packaging chemical safety

Plastic Packaging. Second Edition. Edited by O.G. Piringer and A.L. Baner
Copyright Ó 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31455-3
XVI Preface

regulation and/or enforcement requires increased vigilance and monitoring of

packaging sourced from these areas.
All these regulatory and economic trends are against a backdrop of increasing
environmental, health and safety awareness among media savvy consumers. Today’s
consumers have many product choices available to them and consumer product
companies must ensure the quality and safety of their food products or risk losing
their business. Finally, there is an increasing desire for companies and consumers
alike to operate and live in a more sustainable manner so that both are looking for
ways to reduce, recycle and reuse plastic packaging and to substitute traditional
petrochemical based plastics with newer biopolymer based plastics. All of these
trends make an understanding of the interactions between plastics and food and
pharmaceuticals critical to their optimal use and safety as packaging materials.
This book is surely not the last word on the subject of plastic packaging interaction
and largely reflects the point of view of its authors. We do hope that this work will be
of practical use to people concerned with plastic packaging interactions as well as
providing a starting point and stimulation for continued research in this field.

December 2007

A. L. Baner O. G. Piringer
St. Louis, MO (USA) Munich, Germany
 XVII

List of Contributors

Allan B. Bailey Titus A. Beu

Food and Drug Administration University Babes-Bolyai
Center for Food Safety and Applied Faculty of Physics
Nutrition Kogalniceanu 1
5100 Paint Branch Parkway 3400 Cluj-Napoca
College Park Romania
Maryland 20740
USA Johannes Brandsch
Fabes Forschungs-GmbH
Albert L. Baner Schragenhofstraße 35
Nestle Purnia Petcare PTC 80992 München
Checkerboard Square Germany
St. Louis, MO 63164
USA Francois Chastellain
Nestec S.A.
Layla Batarseh Avenue Nestle 55
Food and Drug Administration 1800 Vevey
Center for Food Safety and Applied Switzerland
Nutrition
5100 Paint Branch Parkway Roland Franz
College Park Fraunhofer-Institut für
Maryland 20740 Verfahrenstechnik und Verpackung
USA Abteilung Produktsicherheit und
Analytik
Timothy H. Begley Giggenhauserstraße 35
Food and Drug Administration 85354 Freising
Center for Food Safety and Applied Germany
Nutrition
5100 Paint Branch Parkway
College Park
Maryland 20740
USA

Plastic Packaging. Second Edition. Edited by O.G. Piringer and A.L. Baner
Copyright Ó 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31455-3
XVIII List of Contributors

Horst-Christian Langowski Jan Pospíšil

Technische Universität München Academy of Sciences of the Czech
Wissenschaftszentrum Weihenstephan Republic
für Ernährung, Landnutzung und Institute of Macromolecular Chemistry
Umwelt Department of Polymer Materials
Weihenstephaner Steig 22 Heyrovsky Square 2
85350 Freising-Weihenstephan 162 06 Prague 6
Germany Czech Republic

André Mandanis Luigi Rossi

Nestle Research Center European Commission
Vers-chez-les-Blanc Office 4/17
1000 Lausanne 26 Rue de la Loi (B232 4/17)
Switzerland 1049 Brussels
Belgium
Peter Mercea
Filderstraße 17 Angela Störmer
70180 Stuttgart Fraunhofer-Institut für
Germany Verfahrenstechnik und Verpackung IVV
Giggenhauserstraße 35
Stanislav Nešpu°rek 85354 Freising
Academy of Sciences of the Czech Germany
Republic
Institute of Macromolecular Chemistry Valer Tosa
Department of Polymer Materials National Institute for Research and
Heyrovsky Square 2 Development of Isotopic and
162 06 Prague 6 Molecular Technologies
Czech Republic P.O. Box 700
400293 Cluj-Napoca
Liviu Petrescu Romania
Fabes Forschungs GmbH
Schragenhofstraße 35 Michelle Twaroski
80992 München Food and Drug Administration
Germany Center for Food Safety and Applied
Nutrition
Otto Piringer 5100 Paint Branch Parkway
Fabes Forschungs GmbH College Park
Schragenhofstraße 35 Maryland 20740
80992 München USA
Germany
 j1

1
Preservation of Quality Through Packaging
Albert Baner and Otto Piringer

Plastics are defined as processable materials based on polymers. These materials can
be transformed into finished products, such as bottles, containers, films, hoses,
coatings, lacquers, etc. As a result of today’s multitude of plastic applications there is a
corresponding enormous variety of plastic materials. The polymer matrix as well as
the incorporated plastic additives can be made to differ in such a variety of ways with
respect to their chemical composition and structure that one finds or can develop a
tailor made product for every application.
Packaging is one major field of application for plastic materials. The development of
self-service stores with their large variety of products is unimaginable without plastics.
The most important function of a packaging material is the quality preservation of
the packed goods. Among these goods, foods hold a place of special importance due to
their principal chemical instability. This instability is also the characteristic for other
products containing active substances, in particular pharmaceuticals.
In order to fulfill the task of quality assurance of the packed product with minimal
impact both on the product and on the environment, the packaging must be
optimized by taking into consideration various criteria. This book provides assistance
in package optimization functions. Special emphasis is given for mass transport
between plastic materials and packed goods and the consequences of such interaction
for quality assurance and legislation.

1.1
Quality and Shelf-Life

Products being offered on the market can, thanks to the currently available manufactur-
ing and preservation methods as well as the various transportation modes, come from
all regions of the country, continent and other continents together.
Many products consist of numerous ingredients which have a relatively low
chemical stability. Such labile goods are exposed to numerous spoilage possibilities
and one of the most important factors leading to longer shelf-lives is their packaging.

Plastic Packaging. Second Edition. Edited by O.G. Piringer and A.L. Baner
Copyright Ó 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31455-3
j 1 Preservation of Quality Through Packaging
2

In order to describe what a product shelf-life is or what it means in terms of quality

retention and measurement, the word “quality” must be defined. Whatever from a legal
standpoint in different countries is used as definition, the quality (Q) determining
properties of a product are in principle based on the product’s components. Thus Q can
be described as a function of the chemical composition of the product:
Q ¼ f ðc 1 ; c 2 ; . . . ; c i ; . . . ; c n Þ ð1:1Þ
Let ci designate the concentration of a specific component i in the product and n the
number of different components. If Qi is defined as a function of the concentration of
component i, then the change in quality DQi over the time interval Dt becomes a function
of the concentration change Dci in this time interval. In this case it is not necessary to
know the change in concentration of all n ingredients and their change with time. If for
example the change in concentration with time of ingredient i can be measured, then
maybe this variation can be correlated with a quality change (Figure 1.1). Even though at
constant concentrations (curve 1) there is no quality change taking place with respect to i,
an increase in concentration (curve 2), for example resulting from mass transport of a
plastic component into the product, leads to quality loss. There are of course cases
where an increase in ingredient concentration during storage can lead to improvement
in quality, for example, during the ripening processes of cheeses or alcoholic beverages.
A reduction in quality also takes place through the loss of an ingredient (curve 3), for
example diffusion of aromatic compounds through the packaging and into the
atmosphere.
For various product ingredients or undesirable foreign substances, limits can be
assigned (shaded field in Figure 1.1) outside which a significant quality reduction can
occur compared to the initial quality. The importance of individual ingredients for
product quality can vary considerably and therefore also the width of the allowable
concentration. The importance and allowable concentration range are determined by
the component’s chemical structure.

Figure 1.1 Concentration variation with time of food ingredients.

Another random document with
no related content on Scribd:
make it. That little moment of hesitation had been fatal; even as he
crouched to spring, the last wagon rolled from beneath him.
Hugh heard a yell of anger. As if dumbfounded, Gamba stood on the
point of rock shaking his fists in impotent rage at the train carelessly
lumbering on its way.
It grew dark quite suddenly. Hugh heard the puffing of the engine,
and saw a cloud of steam with an under-glow of orange. In spite of
his bruises he was feeling extravagantly happy. How lucky to have
jumped on the train! At the rate they were going he would be in
Agaccio in an hour. He breathed freely now. Freedom, safety lay
ahead. Soon, very soon, he would be on the boat for Marseilles.
Then ho! for Paris.... What was the matter? They were slowing up.
Yes, they were stopping at a station. He hoped it would not be a long
stop. In any case he must be well ahead of his pursuers by now ...
that is, if they had not given up the pursuit. There in the dusk he lay
between the two great logs, and once more congratulated himself on
his escape. The air was rich with the perfume of pines, and the stars
were like glow-worms in the fields of heaven.
Hark! What was that? He was horribly nervous. As he strained his
ears, he fancied he heard the distant beat of galloping hoofs. They
came nearer. He heard them drumming on the road that ran beside
the railway track. He might have known it; his enemies were racing
to cut him off. Had they arrived at the station before the train, they
could have easily captured him. What an escape! And now they were
drawing closer. When they got too close, he would take to the forest.
Then the awful nerve-racking hunt would begin again.
In imagination he saw them, spurring and lashing their horses,
straining every nerve to reach the station before the train pulled out.
Would it never start? The drumming hoofs sounded very near
indeed. The engine-driver lighted his pipe, and made some joking
remark to the station master. At last, he turned and jumped up to his
cab. Thank God! the train was in motion.
It cleared the station and gathered speed, plunging once more into
the forest. And not a moment too soon! Hugh looked back to see
three horsemen dash into the light, leap from their horses and run
forward. Too late!...
A few miles further on the train came to another halt. Perhaps it was
imagination, but Hugh thought he heard again the sound of furious
galloping. He heaved a sigh of relief when once more they were
under way.
Soon the lights of Agaccio appeared and the train slowed up. Hugh
jumped down and made for the harbour. With a thrill of joy he
boarded the steamer, and, going forward, mingled with a crowd of
garlic-flavoured Corsicans.
When the boat cleared and blew her whistle it sounded to him like a
hoarse bellow of triumph. As she stood out to sea he looked back at
the lights of the harbour. He fancied he still heard the galloping of
exhausted horses, and the curses of three maddened men. Perhaps
they were there now, standing on the wharf, gazing in rage and
despair after the departing steamer. He hoped they were.
“Corsica, farewell!” he cried. “As long as I live I’ll never set foot on
your shores again. I’m free, free once more. And now for Paris ...
Margot....”
 CHAPTER EIGHT
MARGOT
HOW strange is the romance of destiny! Four nights before he had
lain in a cave in the hinterland of Corsica, listening to a brigand’s tale
of blood, and now, behold, he was in Paris, walking the Boulevard
Montparnasse, and searching for a certain number.
He found it, an old house sandwiched between two modern ones.
Looking up to its mansarded roof he saw a window alight, a window
with a small balcony. That must be her room. He had heard her
speak of it so often, her “Mansard of Dreams” as she called it. His
heart beat excitedly; then suddenly he saw a shadow on the blind.
Yes, it was her shadow, Margot’s. Should he go up? He thought not.
It was too late. She was probably very busy, preparing for the
morrow, her marriage morn. No, he would not bother her to-night.
While he was thus arguing with himself, his feet were carrying him to
the door. A fat concierge was giving a Pekinese spaniel an airing.
Suddenly he heard himself asking.
“Does Mademoiselle Leblanc live here?”
“Yes, monsieur. Fifth floor. Door to the right.”
It sounded like an invitation to go up, and he accepted it. As he
mounted the broken stairs, his heart beat faster. Very silly this! Why
should making a call on her so excite him? It was hard to believe that
she was there. It seemed years since he had seen her,—far back in
a somewhat uncertain past.
He found himself at the door, knocking. How his confounded heart
was knocking too! Damn! He could hear her moving about inside.
Perhaps she thought it was some one else. Perhaps when she saw it
was he, she would be disappointed. She was taking a long time to
open the door. He felt a great longing come over him, a great
tenderness. He would take her in his arms, kiss her, overwhelm her
with passionate caresses.
He did none of these things. When the door opened, he was the
punctilious, rather cold, young man she had always known.
“Good evening,” he said politely.
“You!”
She stood staring at him; her blue eyes big in her pale face; her
hands up to her heart as if to still its tumult. She wore a loose black
peignoir that showed off by contrast the pearly whiteness of her skin.
Against the background of her pale gold hair her face was delicately
sweet. For the hundredth time she reminded him of a lily.
“It is, indeed, you?”
She took both his hands and pulled him gently into the room. She
had pinned up her hair rather hastily, and it came tumbling about her.
As she raised her hands again to pile it about her head, he stopped
her.
“No, leave it like that. It was like that the first time I saw you. I will
always think of you that way.”
She let it fall, a shimmering cape around her.
“I’m sorry,” she said faintly, “to receive you in this poor shabby room.
Please sit down on that chair. It’s my only one.”
He took it. She herself sat down on the edge of the bed, facing him.
“I hurried to get here,” he told her awkwardly. “I wanted to be present
at the ceremony,—even if only as a spectator in the background.”
“What ceremony?”
“Your wedding, to-morrow.”
“Why, didn’t you know? I wrote to tell you I’d refused him.”
“I didn’t get the letter. You refused him.... Why?”
“I don’t know. I suppose I didn’t care enough for him. I don’t think
shall ever marry.”
“And what are you doing now?”
“Working,—with Jeanne. We are taking a shop. I thought it was she
when you knocked.”
“Are you happy?”
“Yes, happier than I have ever been in my life.”
“And I am more miserable.”
“You! Why?”
“Because ... I’m lonely. Look here, Margot, I want you. I only realized
how much I needed you after you went away—how much you mean
to me. I say, Margot, I suppose I’m a stiff, cold sort of a chap. I can’t
do the sentimental stuff. I can’t make pretty speeches, but I really do
care for you.”
“As a sister?”
“No, an awful lot more than that! I can’t do without you, dear. I know
it now. I knew it the moment I’d thought I’d lost you. Don’t tell me I’ve
lost you, Margot.”
He leaned forward, staring anxiously into her eyes. She sat quite
still, her breath coming fast.
“Marry me, Margot,” he faltered, “Me!”
She seemed made of ice. “That’s very kind of you,” she said.
“Not at all, Margot. Believe me, I’m not kind. I’m humble. I’m
pleading. I’ll get down on my knees if you like.”
“No, please don’t.”
“Look here....” He suddenly leaned forward. He took a handful of her
shining hair and twisted it into a great golden rope, then wound it
around her white throat.
“Margot,” he said savagely, “if you don’t say yes, I’ll strangle you
right here. Say yes.”
“Is it to save my life I must say yes?”
“Your life—and mine.”
“Well, if it’s to save yours, too.... Yes!”
The tension was over. He rose. He was radiant. He laughed.
“I’ll see the British Consul to-morrow; and we’ll get hitched up in a
few days. Now I’m going. I want to be alone, to realize my
happiness, to sing to the stars. I want to celebrate, to get drunk.
Margot, may I get drunk to-night?”
“What!”
“With joy I mean. I want to sit in a café by myself and let my
happiness soak in gradually. I want to smile like an idiot over a café
crême and have people look at me twice, and say, ‘Mais ... il est fou,
ce gars la....’ I want to laugh loudly at the moon, and dance the can-
can by the Carpeaux fountain. Oh Margot, Margot....”
Down in the street a passing sergent de ville who happened to look
up at the lighted mansard window, saw two separate shadows on the
blind. The masculine shadow reached out to the feminine one, then
the two shadows became one.
“Ah! Ces amoureux!” he remarked with a shrug as he went on his
way.
 CHAPTER NINE
AND LAST
A YEAR later Hugh sat at his desk, reading the following letter:
My Dear Chap:
I wrote to you in Menton, and the letter came back. But the
other day a man in the office saw you in Paris and gave
me your address. He also gave me a very good account of
you; I am glad, for I have often felt anxious about you. I
hope now that you have again taken up the burden of the
wage-earner, you are not finding it too heavy. I’ve become
a professional ink-slinger. You remember me as a
dilettante, a trifler. I wrote whimsical essays; I cultivated an
urbane humour. Then one day in a fantastic mood I
started a burlesque of the German spy novel. I showed it
to a bloated publisher who refused to publish it as a
burlesque, but suggested that it would go as a serious
effort. He thought the public would take it that way. The
public did.
So now behold me, a popular author, a six shilling shocker
to my credit, another half-done, and many more in my
mental incubator.
Of course, on the strength of my success I resigned from
Gummage & Meek. We had saved a few thousand
pounds, so if literature proves more of a staff than a
crutch, we won’t be altogether on the rocks. Better still, a
preposterously rich bachelor brother of my wife’s has
promised to see the two boys through school and college.
In short, I find at last my dream realized. I am free to
cultivate my literary cail-yaird.
I want now to find some quiet place where I can live in a
leisurely way, polish my gems, and generally lead a
pleasant, tolerant, contemplative life. Do you, with your
 knowledge of the south of France, know of such a place?
The exchange rate now is so advantageous.
Please rub a little liniment on your strong right arm, grip
your pen with intense determination, and favour me with a
few lines.
Sincerely,
Arthur Ainger.
Hugh looked round the shabby but comfortable room he called his
den. There was a roll-top desk, crimson-curtained book shelves, a
big easy chair by the window, many unframed canvases on the
walls. His eyes rested on each article with loving satisfaction.
“Good old chap,” he said, “I’ll answer his letter right away.”
So he sat down at his desk and began:
Dear Mr. Ainger:
I am more than ashamed that I have never written to you;
but so many things have happened. To begin with I have a
modest apartment near the Luxemburg Gardens. I was
married a year ago. My wife’s a jolly good sort. You’d like
her. I intended after my marriage to get work of some kind,
but the unexpected happened. It seems I had a maternal
grandmother living in Monaco. She had quarrelled with my
mother; and though she gave consent to the marriage she
refused to be reconciled. When she died it was found she
had left everything to me. They had some trouble in
finding me, but through the old chap who brought me up,
they eventually did.
I now find myself the owner of a property in the
Condamine that nets me twelve thousand francs a year,
enough for two quiet people to jog along on quite
comfortably. After all, I’ve come to the conclusion I’m one
of those simple souls who want to slip through life with as
little trouble as possible to themselves and to every one
else.
 My hobbies are cars and painting. I am the proud
possessor of a little Buggatti in which I whiz the wife out to
Barbizon occasionally. Otherwise I attend the Ecole des
Beaux Arts and am doing quite well. In time I hope I’ll
make an averagely good artist, and occasionally sell a
croute.
I am so glad to hear of your success. The sort of books
you write are the sort I like. But then I am not exacting,
and read to take my mind off the monotony of existence.
Sometimes, you know, on a wet day when one can’t paint
and there’s no billiard table, a good yarn’s not a bad thing
to pass the time. I imagine there’s a whole lot like me.
By the way, you speak of finding a quiet corner where you
can hole up and live cheaply. I have a little cottage at
Villefranche which I can offer you. There’s not much in the
way of furniture, but you can stay there as long as you like
and what with the produce of a big garden and the fish
you can catch, the cost of life is reduced to a minimum.
Now don’t refuse....
Hugh had got this far when Margot entered. He handed her his letter
to read.
“Why,” she said indignantly, “you’ve left out the most important thing
of all.”
“Oh, yes, I quite forgot about that.”
“Forgot! Listen. The precious little darling! He’s crying for me now.”
“Yes, his lungs are better than his looks.”
“I like that. Everybody says he’s the image of you. Now, I must run.”
“All right. I’ll put him in the postscript.”
Hugh added a few more words as he listened to the subsiding wails
of his son and heir. Then throwing himself in his easy chair with a
laugh of utter happiness he lit his pipe.
THE END
 TRANSCRIBER’S NOTES:
Obvious typographical errors have been corrected.
Inconsistencies in hyphenation have been
standardized.
Archaic or variant spelling has been retained.
 *** END OF THE PROJECT GUTENBERG EBOOK THE
POISONED PARADISE: A ROMANCE OF MONTE CARLO ***

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