Dieter Urban - Polymer Dispersion and Their Industrial Applications - 2002 PDF

Polymer Dispersions and Their Industrial Applications.
Edited by Dieter Urban and Koichi Takamura

Copyright 2002 Wiley-VCH Verlag GmbH & Co. KGaA
ISBNs: 3-527-30286-7 (Hardback); 3-527-60058-2 (Electronic)
Polymer Dispersions
and Their Industrial Applications
Edited by Dieter Urban and
Koichi Takamura
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura
Polymer Dispersions
and Their Industrial Applications
edited by Dieter Urban and

Koichi Takamura
IV
Editors
Dr. Dieter Urban
Dr. Koichi Takamura
BASF Corp.
11501 Steele Creek Road
Charlotte, NC 28273, USA
This book was carefully produced. Nevertheless, editors, authors and

publisher do not warrant the information
contained therein to be free of errors.
Readers are advised to keep in mind that
statements, data, illustrations, procedural
details or other items may inadvertently
be inaccurate.
Library of Congress Card No.:
applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is

available from the British Library.
Die Deutsche Bibliothek CIP Cataloguingin-Publication Data
A catalogue record for this publication is

available from Die Deutsche Bibliothek
2002 Wiley-VCH Verlag GmbH,
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.
Scanning electron
micrograph of a hollow sphere created
by the deposition of 7.9 m polystyrene
particles on a nitrogen bubble during
their preparation in the microgravity
environment of the Space Shuttle
Challenger (courtesy of the Emulsion
Polymers Institute, Lehigh University,
Bethlehem, PA, USA).
Cover photograph
Printed in the Federal Republic of Germany

Printed on acid-free paper
Typesetting
TypoDesign Hecker GmbH,
Leimen
Printing betz-druck GmbH, Darmstadt
Binding Grobuchbinderei J. Schffer
GmbH & Co. KG, Grnstadt

ISBN 3-527-30286-7
Contents
Preface
XIII
Introduction
1.1
1.2
1.3
1.4
1.5
Names and Definitions 1

Properties of Polymer Dispersions 3
Important Raw Materials 8
Commercial Importance of Polymer Dispersions
Manufacturers of Polymer Dispersions 12
References 14
10
Synthesis of Polymer Dispersions 15
2.1
2.2
2.2.1
2.2.2
2.2.3
2.2.4
2.2.5
2.2.6
2.3
2.3.1
2.3.2
2.3.3
2.3.4
Introduction 15
Chemistry 17
Mechanism of Emulsion Polymerization 17
Major Monomers 23
Functional Monomers 26
Surfactants 27
Initiator Systems 30
Other Ingredients 32
Manufacturing Processes 34
Types of Process 34
Influence of Process Conditions on Polymer/Colloidal Properties
Equipment Considerations 39
Safety Considerations 40
References 40
Characterization of Aqueous Polymer Dispersions 41
3.1
3.2
3.2.1
3.2.2
3.2.3
3.2.4
Introduction 41
Polymer Dispersions 42
General Characterization of Dispersions 42
Characterization of Polymer Particles 48
Residual Volatiles 56
Aqueous Phase Analysis 57
37
VI
Contents
3.3
3.3.1
3.3.2
3.3.3
Polymer Films 58
Film Formation 59
Macroscopic Characterization of Polymer Films
Microscopic Characterization of Polymers 68
References
72
60
Applications in the Paper Industry 75
4.1
4.2
4.3
4.4
4.4.1
4.4.2
4.4.3
4.4.4
4.4.5
4.5
Introduction 75
The Paper Industry 76
Surface Sizing 79
Paper Coating 81
Coating Techniques 84
Pigments used in Coating Colors 86
Co-binders and Thickeners used in Coating Colors
Binders used in Coating Colors 90
Test Methods 97
Concluding Remarks 100
Acknowledgments 100
References 101
Applications for Printing Inks 103
5.1
5.1.1
5.1.2
5.2
5.2.1
5.2.2
5.2.3
5.2.4
5.2.5
5.3
5.3.1
5.3.2
5.3.3
5.4
5.4.1
5.4.2
5.5
5.5.1
5.5.2
5.5.3
5.6
5.6.1
5.6.2
5.7
Introduction 103
Flexographic Ink 104
Gravure Ink 106
Ink Composition 106
Pigment Dispersion 108
Emulsion Vehicle 109
Solution Vehicle 112
Waterborne Wax Emulsions and Powders 113
Ink Additives 113
Physical Properties and Test Methods 114
Typical Properties 114
Application Tests 115
Test Method Abstracts 115
Inks for Flexible Substrates (Films) 117
Surface Print Film 118
Lawn and Garden Bags 118
Inks for Paper Board Substrates 118
Folding Cartons 118
Direct Print Corrugated Packages 119
Pre-print Corrugated Packages 119
Inks for Poly-coated Board 120
Milk Cartons 120
Cup and Plate 120
Inks for Paper Products 120
87
Contents
5.7.1
5.7.2
5.7.3
5.7.4
Multiple Wall Bags 121

Gift Wrap and Envelopes
Newspapers 121
Towel and Tissue 122
References 122
121
Applications for Decorative and Protective Coatings 123
6.1
6.1.1
6.1.2
6.1.3
6.2
6.2.1
6.2.2
6.2.3
6.2.4
6.2.5
6.3
6.3.1
6.3.2
6.3.3
6.3.4
6.4
6.4.1
6.4.2
6.4.3
6.5
6.5.1
6.5.2
6.5.3
6.6
6.6.1
6.6.2
6.6.3
6.7
6.7.1
6.7.2
6.7.3
6.8
6.8.1
6.8.2
6.8.3
6.8.4
6.8.5
6.8.6
Introduction 123
Market Overview 123
Coating Industry Trends 124
Coatings Provide Decoration and Protection 124
Overview of Coating Formulations 125
Volume Solids and Pigment Volume Content 125
Polymer Matrix 127
Film Formation 128
Typical Polymer Compositions 129
Pigments, Extenders, and Additives 132
Decorative Coatings 137
Emulsion Polymers in Decorative Coatings 137
Polymer Compositions used for Emulsion-based Decorative Coatings 137
Regional Distinctions in Decorative Coatings 138
Market Size of Decorative Coatings 138
Interior Decorative Coatings 139
Key Performance Features 139
Interior Decorative Coating Formulations 140
Standard Application and Performance Tests 142
Exterior Decorative Coatings 146
Exterior Decorative Coating Formulations 147
Elastomeric Wall Coatings 149
Typical Elastomeric Wall Coating Formulations 150
Primer Coatings 151
Primer Formulations 152
Protective and Industrial Coatings 154
Copolymers used in Protective and Industrial Coatings 154
Market Size 155
Industrial Maintenance Coatings 155
Formulation Characteristics for Industrial Maintenance Coatings 156
VII
VIII
Contents
6.9
6.9.1
6.9.2
6.9.3
6.9.4
Traffic Marking Paints 158

Description of Traffic Paint Market 158
Typical Traffic Paint Formulation 159
References 161
Applications for Automotive Coatings 163
7.1
7.1.1
7.2
7.2.1
7.2.2
7.2.3
7.3
7.3.1
7.3.2
7.3.3
7.3.4
7.3.5
7.3.6
7.4
7.5
7.6
7.6.1
7.7
Introduction 163
History of Automotive Coating 164
Automotive Coating Layers 166
Electrocoat 170
Primer 172
Basecoat 173
Properties of Water-borne Binders used for Automotive Coatings
Emulsion Polymers 176
Microgels 177
Miniemulsions 177
Selection of Monomers, Initiators, and Surfactants 178
Secondary Acrylic Dispersions 179
Secondary Polyurethane Dispersions 179
Rheology 181
Crosslinking 183
Application Properties 185
Metallic Effect 186
Environmental Aspects and Future Trends 186
References 187
Applications in the Adhesives and Construction Industries 191
8.1
8.2
8.2.1
8.2.2
8.2.3
8.3
8.3.1
8.3.2
8.3.3
8.4
8.4.1
8.4.2
8.4.3
8.4.4
8.4.5
8.4.6
Introduction 191
Pressure-sensitive Adhesives 193
Self-adhesive Labels 194
Self-adhesive Tapes 207
Test Methods 210
Laminating Adhesives 217
Flexible Packaging 217
Glossy Film Lamination 219
Furniture and Automotive 222
Construction Adhesives 224
Floor-covering Adhesives 224
Sub-floor and Wall Mastics 231
Sealants 233
Ceramic Tile Adhesives 238
Polymer-modified Mortars 241
Waterproofing Membranes 244
176
Contents
8.4.7
Elastomeric Roof Coatings

Acknowledgments 250
References 251
247
Applications in the Carpet Industry 253
9.1
9.2
9.3
9.4
9.5
9.5.1
9.5.2
9.5.3
9.5.4
9.5.5
Introduction 253
History of Carpet 253
Present Day Carpet Business 255
Carpet Backing Binders 256
Carpet Laminating 259
Background 259
Carpet Terminology 260
Back-coating Applications 261
Back-coating Formulations and Ingredients 262
Industry Issues 264
References 266
10
Non-wovens Application 267
10.1
10.2
10.2.1
10.2.2
10.3
10.4
Introduction 267
Manufacturing Systems 270
Web Formation 271
Web Consolidation 272
Polymer Dispersions for Chemical Bonding
Application Test Methods 275
References 281
11
Applications in the Leather Industry 283
11.1
11.2
11.3
11.3.1
11.3.2
11.3.3
11.3.4
11.3.5
11.3.6
11.3.7
11.4
11.4.1
11.4.2
11.4.3
11.5
11.5.1
11.5.2
11.5.3
Introduction 283
Market Situation 284
Leather Finishing 286
Modern Finishing 287
General Construction of Finishing Coats
Spray Dyeing 287
Grain Impregnation 287
Base Coat 287
Pigment Coat 288
Top Coat 288
Application Methods 288
Spraying 289
Roll Coating 289
Curtain Coater 289
Binders 291
Polyacrylate Dispersions 291
Polybutadiene Dispersions 291
Polyurethane Dispersions 292
273
287
IX
Contents
11.6
11.6.1
11.6.2
11.6.3
11.6.4
11.7
11.7.1
11.7.2
11.7.3
11.7.4
11.7.5
11.7.6
11.7.7
11.7.8
11.7.9
Production of Selected Leather Articles 292

Shoe Upper Leather 292
Apparel Leather 293
Automotive Leather 294
Furniture Leathers 295
Test Methods in Leather Finishing 296
Flexing Endurance 297
Rub-fastness 298
Dry and Wet Adhesion 299
Fastness to Ironing 299
Hot Air Fastness 299
Aging resistance 299
Fogging test 300
Light-fastness 300
Hot light aging 300
References 300
12
Applications for Asphalt Modification 301
12.1
12.2
12.2.1
12.2.2
12.3
12.3.1
12.3.2
12.3.3
12.3.4
12.3.5
12.4
12.5
Introduction 301
Hot Mix Asphalt Paving 303
Asphalt Specification 304
In-line Injection (Pump-in) 311
Paving with Asphalt Emulsion 313
Applications of Asphalt Emulsions 314
Asphalt Emulsion Tests 317
Polymer Honeycomb Structure in Cured Asphalt Emulsion 317
Asphalt Emulsion Residue Characterization 319
Application Tests for Chip Seal and Microsurfacing 321
Eco-efficiency Analysis 323
Concluding Remarks 326
Acknowledgement 326
References
326
13
Applications of Redispersible Powders
13.1
13.2
13.3
13.4
13.4.1
13.4.2
13.4.3
13.4.4
13.4.5
13.4.6
13.5
Introduction 329
Manufacturing of Redispersible Powders 330
Dry Mortar Technology 332
Markets and Application Areas of Redispersible Powders 333
Adhesives for Ceramic Tiles 334
Tile Grouts 340
Exterior Insulation and Finish Systems and Top Coats 341
Self-leveling Underlayments 345
Patch and Repair Mortars 346
Waterproof Membranes 350
Summary 353
329
Contents
References
354
14
Applications for Modification of Plastic Materials 355
14.1
14.2
14.2.1
14.3
14.3.1
14.3.2
14.4
14.4.1
14.4.2
Introduction 355
Emulsion Polymerization and Isolation Technology 356
Isolation Technology 357
Processing Aids 358
Processing Aids for PVC 359
Processing Aids for Other Resins 366
Impact Modifiers 367
Impact Modifiers for PVC 368
Engineering Resins 375
Acknowledgment 378
References 379
15
Applications for Dipped Goods 383
15.1
15.2
15.3
15.4
15.4.1
15.4.2
15.4.3
15.4.4
15.5
15.5.1
15.5.2
Introduction 383
Polymers Used by the Dipping Industry 384
Principles of Dipping 385
Dipping Synthetic Polymer Emulsions in Practice 386
Former Design 386
Mix Design 388
Coagulant 390
The Dipping Process 390
The Testing of Synthetic Gloves 395
Non-safety-critical Gloves 395
Safety-critical Gloves 396
References 398
Index 399
XI
Preface
Aqueous polymer dispersions are important raw materials used in a variety of industrial processes. They consist of very small polymer particles dispersed in water
and appear as milky fluids. When finally processed and providing the function for
which they were selected, they are barely visible. Polymer dispersions are used to
protect metal, wood, and leather against water and microorganisms, and are used as
binders for pigments, fillers, and fibers and to finish the surfaces of metal, wood or
paper. Protecting, binding, and finishing are the essential effects achieved by use of
polymer dispersions.
In most applications the water will be evaporated and a functional polymer remains. This can be hard or tacky, plastic or elastic, transparent or opaque. Accordingly, they are used for coatings or as adhesives, for binders or foams, for clear coat
varnishes or opacifiers. It is even possible to reconcile these classically contradictory
properties by proper design of a single dispersion or by mixing several.
Even small amounts of polymer dispersion are able to improve considerably the
properties of different binders, e.g. starch, bitumen, or cement.
The huge variety of applications continues into the area of solid plastic materials
impact modifiers are added to improve the properties of plastic materials. Dipping
goods, e.g. gloves, and latex foams for mattresses are polymeric materials which are
made directly from polymer dispersions.
Finally, there are also applications in which polymer dispersions remain in their
liquid form they are used as drug carriers, in medical diagnosis, and in liquid soap.
This book focuses on the applications of aqueous polymer dispersions. The chapters on synthesis and characterization should be regarded as an introduction and
should aid understanding of the applications. The applications of aqueous polymer
dispersions have developed differently, both historically and regionally. Regulatory
issues have contributed to these differences. The strongest development of polymer
dispersions occurred in Europe and North America in the middle of the 20th century. The differences between these two regions are emphasized.
We are specially grateful to all the authors who helped us make this global comparison and acknowledge the authors companies, for approving and supporting this
work.
Charlotte, North Carolina, USA
Dieter Urban
Koichi Takamura
XIII
List of Authors
Peter Blanpain
Dr. Christoph Hahner
7834 Covey Chase Drive

Wacker Polymer Systems, L. P.

3301 Sutton Road
Adrian, MI 49221, USA
Dr. Mary Burch
Rohm & Haas Company

727 Norristown Road
Spring House, PA 19477, USA
Dr. Chuen-Shyong Chou
Rohm & Haas Company

Rt. 413 and Old Rt. 13
Bristol, PA 19007, USA
Dr. Dieter Distler
BASF Aktiengesellschaft
GKD - B1
D-67056 Ludwigshafen, Germany
Dr. Johannes Peter Dix
EVL/I G100
Dr. Luke Egan
BASF Corporation
Dr. Onno Graalmann
BASF Nederland B.V.

Westervoortsedijk 71
NL-6827 AV Arnhem, The Netherland
Dr. Sunitha Grandhee
BASF Corporation
26701 Telegraph Road
Southfield, MI 48034, USA
Richard Groves
Synthomer LTD
Central Road, Templefields,
Harlow, Essex, CM20 2BH, UK
Dr. Do Ik Lee
The Dow Chemical Company

1604 Building
Midland, MI 48674, USA
Dr. Hermann Lutz
Wacker Polymer Systems GmbH&CoKG

Johannes-Hees-Str. 24
D-84489 Burghausen, Germany
Dr. Werner Kirchner
EV/CS H201
Andrew Lanham
Synthomer Ltd.
Dr. Brough Richey
Rohm & Haas Company

727 Norristown Road
Spring House, PA 19477, USA
Dr. Jrgen Schmidt-Thmmes
GKD/S B1
Dr. Elmar Schwarzenbach
EDP/MB H201
Richard Scott
BASF Corporation
475 Reed Road NW
Dalton, GA 30720, USA
XV
XVI
J. Arthur Smith
BASF Nederland B.V.

Westervoortsedijk 71
NL-6827 AV Arnhem, The Netherland
K. Spenceley
Synthomer Ltd.
Barna Szabo
Flint Ink Corporation

4600 Arrowhead Drive
Ann Arbor, MI 48105, USA
Dr. Koichi Takamura
BASF Corporation
Jim Tanger
BASF Corporation
Michael A. Taylor
BASF Corporation
Dr. Dieter Urban
BASF Corporation
Dr. Jane E. Weier
Rohm & Haas Company

Rt. 413 and Old Rt. 13
Bristol, PA 19007, USA
Dr. Harm Wiese
GKD/N B1
Marilyn Wolf
BASF Corporation
Color Plates
Color Plates
Fig. 1-3
Particle
morphologies.
Raspberry structure
Core/shell structure
Acorn structure
Uncoated grade,
supercalendered
Coated grade,
supercalendered
Fig. 4-7
Effect of coated paper on offset printing.
XVII
XVIII
Color Plates
Coated
gravure
paper
Uncoated
gravure
paper
Fig. 4-8
Effect of coated paper on rotogravure printing.
Coating head
Steam
Dryer
Laminating
station
Release
liner
Schematic representation
of PSA label coater.
Backing
Fig. 8-9
Unwind
Rewind
Latex Polymer
Network
Photomicrograph demonstrating spontaneous

formation of polymer
network upon curing
of the CRS-2 asphalt
emulsion modified
with 3 % cationic SBR
latex.
Fig. 12-15
50 m
Introduction
Dieter Urban and Dieter Distler
1.1
Names and Definitions
Most precisely the subject of this book is called aqueous synthetic organic polymer
colloids. The term polymer colloid defines a state of subdivision in which polymolecular particles dispersed in a medium have at least in one direction a dimension of
roughly between 1 nm and 1000 nm [1]. The term organic needs to be added to exclude inorganic polymers like silica. To be more precise the term synthetic will be
added, if organic polymers of natural origin like natural rubber should be excluded.
Finally, the term aqueous ensures that the continuous medium is only water, excluding e.g. organic solvents. However, depending on the language, the geographical region and the field of application there are many other names commonly used (Fig. 1-1).
In general the term dispersion characterizes a two phase system consisting of
finely dispersed solid particles in a continuous liquid phase. An example of a dispersion is whitewash, calcium hydroxide above the solubility limit in water. If the finely
dispersed phase and the continuous phase, both are liquid, the term emulsion
will be used. An example is milk, which essentially consists of fat droplets in water;
the droplets are stabilized by proteins. In both cases, in dispersions and emulsions,
the continuous phase is therefore a liquid; in all of our examples, the liquid is water.
In dispersions, the finely disperse substance is solid, while in emulsions it is liquid.
Dealing with organic polymers being the dispersed substance it is difficult to define precisely whether they are solid or liquid. Depending on the glass transition
temperature (Tg) and chain length, polymers are viscous liquids at low Tg and low
molecular weight or they will be tough to brittle solids, if Tg and molecular weight
are high. The temperature and stress duration are other important factors. At temperatures below the glass transition temperature or in the case of very short stress
duration, polymers behave like glasses, while above this temperature or in the case of
long stress times, they are viscous or elastic materials. This behavior of polymers between liquid and solid is one reason why aqueous synthetic organic polymer colloids
are referred to as dispersions (Danish, Dutch, Finnish, German, Greek, Hungarian,
Japanese, Korean, Norwegian, Polish, Portuguese, Romanian, Russian, Spanish,
1 Introduction
Fig. 1-1
colloids.
Commonly used names for aqueous synthetic organic polymer
1.2 Properties of Polymer Dispersions
Swedish, Turkish) and emulsions (Arabic, Chinese, English, Indonesian, Italian,

Malay). Another reason for the use of emulsion or emulsion polymer comes from the
most important production process for these products, the emulsion polymerization.
The products are referred to as emulsion polymers or simply emulsions.
In contrast to this the name latex (Latin: latex, liquid; Greek: , droplet) is derived from the naturally occurring rubber milk and is most widely used for aqueous
synthetic organic polymer colloids, especially for the substitution products of natural
latex, butadiene-styrene copolymer emulsions.
The Union for Pure and Applied Chemistry recommends two names: Latex and
polymer dispersion [2]. Latex is defined as A colloidal dispersion of polymer particles in an aqueous medium. The polymer may be organic or inorganic. Since
we will not cover inorganic dispersions, this book should have been called Organic
Latices and Their Industrial Applications, which seems to be a pleonasm because
the use of latex is generally associated with organic material. Polymer dispersion is
defined as A dispersion in which the disperse phase consists of polymer particles.
The continuous phase can be a liquid, solid or gas. If we want only water to be the
continuous phase, aqueous is added. In industrial applications non-aqueous polymer dispersions are negligible. Therefore this book has been called Polymer Dispersions and Their Industrial Applications. However, according to the preference of
the authors the terms polymer dispersion, dispersion, emulsion polymer,
emulsion and latex are used synonymously.
1.2
Properties of Polymer Dispersions
The aggregate state of a polymer dispersion is thermodynamically unstable. The very

large internal surface area of up to 100 m2 mL1 of dispersion requires stabilization
of the particle surfaces in order to suppress phase separation and coagulation. Driving force for the agglomeration of particles is the gain of energy by reducing the internal surface. Finally a polymer block and a substantially polymer-free water phase
will be formed. This coagulation can be accelerated by salts, acids, solvents, freezing,
shear, etc.
To obtain highly stable polymer dispersions, the particles are usually provided
with ionic groups, for example by adsorption of anionic or cationic surfactants, or by
incorporation of ionic groups into the polymer. Another, nonionic type of stabilization takes place via hydrophilic groups on the particle surface, for example by aminoor hydroxyl-containing monomers or protective colloids. Polymer dispersions used
in industry usually are stabilized by both mechanisms (ionic and nonionic). The special nature of the particle surface, which differs from the particle interior, plays an
important role in all applications.
Industrially important polymer dispersions usually contain 4060 % of polymer
in water. Each mL of dispersion contains about 1015 particles with diameters of
50500 nm. One particle contains 110 000 macromolecules, and each macromolecule contains about 100106 monomer units (Fig. 1-2).
1 Introduction
Fig. 1-2
What is a polymer dispersion?
These figures give an impression of the possible variation, if just the molecular
weight (or molecular weight distribution) and particle size (or particle size distribution) of homo-polymers will be considered. The random incorporation of various
monomers in the chains, the possibility of cross-linking between the polymer chains
and finally separated phases of different polymers in a particle allow a virtually unlimited variety in this product class.
Polymer dispersions normally consist of spherical particles. The dispersed particles scatter the light and are the cause of the milky appearance. This Mie scattering is
utilized for particle size measurement. Very small polymer particles hardly scatter
visible light at all, those polymer dispersions have a translucent appearance. If all the
particles are of the same size, the term monodisperse dispersions will be used.
They are frequently recognized from a certain particle size merely from the iridescent appearance, which is caused by Bragg scattering at a crystalline superstructure
of close packing of the particles.
Polymer dispersions with a heterogeneous particle structure a special particle
morphology consisting of a number of phases have recently become of interest. Examples are particles with a core/shell structure or two coexistent polymer phases,
particles with a raspberry structure, etc. The particle morphology may be thermodynamically preferred; in the case of polymers with reduced chain mobility or even in
the case of relatively low cross-linking, it is mostly kinetically controlled morphologies that are frozen. This enables product properties with even contradictory requirements to be achieved better, for example low film formation temperature, but maximum blocking resistance or hardness of the polymer (Fig. 1-3).
The flow behavior is also an important parameter. The flow property of polymer
dispersions is a particular advantage of this aggregate state. Dispersions can have a
polymer content which is a multiple higher than polymer solutions, yet still be freeflowing. Besides the polymer content, particle size, particle size distribution and
electrolyte content, the viscosity is also affected by dissolved constituents in the aqueous phase. The water phase of many polymer dispersions contains a whole range of
water-soluble oligomers, auxiliaries and additives which contribute to the application
properties as well.

Fig. 1-3
Particle
morphologies.
Raspberry structure
Core/shell structure
Acorn structure
To obtain readily free-flowing dispersions with low viscosity at high polymer contents of >60 % by volume, very broad or bimodal particle size distributions are needed (Fig. 1-4).
Electron photomicrograph of a bimodal polymer

dispersion.
Fig. 1-4
This can be achieved during the polymerization or by partial agglomeration, for example, by means of a shear gradient, by freezing or by addition of an agglomeration
aid, so that significantly larger agglomerates are present alongside the small primary
particles.
The viscosity of polymer dispersions is usually dependent on the shear rate. A distinction is made between pseudoplastic behavior (viscosity decreases with increasing
shear), possibly with a flow limit, thixotropic behavior (viscosity decreases with in-
1 Introduction
creasing shear time) and dilatant behavior (viscosity increases with increasing
shear). The rheology of concentrated polymer dispersions is complex, often being dependent on the shear rate and previous history.
Owing to the content of surface-active substances, the foaming behavior is an important property for many applications. Antifoam agents reduce foaming, while further emulsifiers and rheology modifiers increase the foaming or stabilize the foam
once formed.
The biodegradability of many additives makes the dispersions susceptible to attack
by microorganisms (bacteria, yeast). Most dispersions are therefore provided with
biocides.
In most applications, the water is evaporated from the dispersions. Depending on
the composition and/or processing temperature, a polymer film or powder is formed.
The properties of the polymer now come into play:
strength, elongation at break, elasticity, transparency, solvent and environmental
resistance, glass transition temperature, tack, etc.
These properties are determined by the chemical composition of the copolymers,
the molecular weight and the molecular weight distribution, by the morphology of
the polymer particles and by the morphology of the polymer film.
Important polymer classes are:
Styrene/butadiene dispersions are used for their elastic properties since molecular
weight and cross-linking of the polymer can be adjusted widely by choosing the degree of conversion and the amount of chain transfer agents. They are used as synthetic rubber for tires and molded foam. When styrene is replaced by acrylonitrile,
elastic and solvent resistant polymers are obtained, which are used for dipping
goods. Carboxylated styrene/butadiene (XSB) dispersions contain acrylic, methacrylic, maleic, fumaric or itaconic acid. The carboxylic groups provide stabilization of the
polymer particles and a good interaction with fillers (calcium carbonate, clay) and
pigments. The main applications are paper coating and carpet backing. The remaining 1,2 and 2,3 double bonds of butadiene favor autoxidation of the polymer, it becomes yellow and brittle. This is prevented by adding antioxidants. This polymer
class is resistant to hydrolysis at all pH values since it does not contain ester units
which tend to hydrolyze especially at very high pH.
Acrylic dispersions (pure acrylics and styrene acrylics) are extremely versatile. The
big variety of available acrylic and methacrylic esters together with styrene offer
almost unlimited opportunities to choose for the glass transition temperature and
the hydrophilic/hydrophobic properties. Acrylic esters tend to form cross-linked
polymers by abstraction of the -hydrogen atom, methacrylic esters in contrast form
polymer chains which are not cross-linked. Acrylics are resistant against oxidation by
air and degradation by light. The main application areas are coatings and adhesives.
Vinyl acetate dispersions are widely used for coatings and adhesives as well. To
stabilize the polymer particles often polyvinyl alcohol is used as protective colloid.
Most common co-monomers are ethylene, versatic esters, vinyl chloride or acrylic esters. The polymer dispersions are spray dried to obtain a polymer powder, which is
widely used in construction industry. Ethylene/vinyl acetate copolymers form elastic
films and are fairly resistant to oxygen and light.
Polymer dispersion with a high content of vinylidene chloride form polymer films
with crystalline areas. These PVDC films are highly impermeable for both, oxygen
and water vapor, and are used as barrier coatings in packaging materials, especially
for food packaging (Fig. 1-5).
Permeability
of polymer films.
Fig. 1-5
Polymer dispersions with a high amount of acrylic/methacrylic acid convert to

aqueous solutions or gels when pH is increased. They are used as thickeners.
Films made from polyurethane dispersions combine elastic properties with high
tensile strength.
Polystyrene dispersions have a glass transition temperature of 105 C. They are
used in paper coating to improve gloss, in liquid soaps to provide opacity and in
medical diagnosis as carrier for active ingredients.
Films of acrylic dispersions, which are cross-linked with metal ions and re-dispersible with an aqueous solution of ammonia, are used as temporary protective
films.
All those examples elucidate that polymer dispersions are used in both big volume
and small volume applications. They are both commodities and specialties. And the
use of polymer dispersions is increasing worldwide. The main reasons for this are:
the variety of polymer properties achievable by emulsion polymerization is virtually
unlimited, emulsion polymerization is an inexpensive production process for these
products, the fluid form of polymer dispersions is easy to handle, and water is environmentally friendly.
The complex colloidal and chemical behavior of polymer dispersions is an interesting working area for many scientific disciplines and is important for many applications. In addition to excellent reviews [313], a whole range of periodicals focuses
on polymer dispersions [1418].
1 Introduction
1.3
Important Raw Materials
The most important production process for polymer dispersions is emulsion polymerization [19]. This process is started by preparing a monomer emulsion consisting of monomer droplets in water. The monomer droplets are stabilized by emulsifiers and/or protective colloids. When adding an initiator polymerization is started
converting the monomers into polymer particles (Chapter 2).
The production of polymer dispersions by emulsion polymerization requires deionized water, free-radical-polymerizable monomers, emulsifiers and/or protective
colloids and initiators. Further auxiliaries, such as chain transfer agents, buffers,
acids, bases, anti-aging agents, biocides, etc., can be used.
The most important source of the main monomers used or their precursors is petroleum chemistry, with the steam cracker as reactor. Liquid hydrocarbons (naphtha
or liquefied natural gas LNG) are broken down (cracked) into short-chain hydrocarbons at 800850 C with addition of steam as diluent (Fig. 1-6) [20].
Fig. 1-6
Steam cracker products.
There are currently about 200 steam crackers worldwide. In Europe, Latin America and South-East Asia, the starting material is mostly naphtha, while in North
Africa, the Middle East and North America, predominantly ethane and propane from
natural gas are used. The largest plants have an annual capacity of more than 800 000
tons of naphtha.
Ethene, the most important petrochemical feedstock today, reached a world capacity of about 80 million tons per year in 1995. Almost half is polymerized to give polyethylene. It plays only a secondary role for emulsion polymerization in vinyl acetateethene copolymers and in polyethylene waxes. It is important, however, in this connection as a feedstock for the production of vinyl chloride, styrene and vinyl acetate.
1.3 Important Raw Materials
Propene cannot be polymerized by means of free radicals. It is, however, a feedstock for acrylic acid, acrylates and acrylonitrile.
Butadiene is extracted from the C4 fraction from the steam cracker, and can be
used directly for emulsion polymerization.
The principal monomers butadiene, styrene, vinyl acetate, (meth)acrylates and
acrylonitrile essentially determine the material properties of films made from the
corresponding dispersions: the glass transition temperature, the water absorption
capacity, the elasticity, etc. Auxiliary monomers, which are only used in a small proportion, usually <5 %, control important properties such as colloid-chemical stabilization (acrylic acid, methacrylic acid, acrylamide, methacrylamide), crosslinking
within the particles (difunctional acrylates, divinylbenzene, etc.) or hydrophilic properties (OH-containing monomers, such as hydroxyacrylates). Reactive monomers
which still contain a latently reactive group even after incorporation into the polymer, for example glycidylmethacrylate or N-methylol(meth)acrylamide, can form a
network between various particles and polymer molecules after film formation.
These specific polar groups are frequently not distributed homogeneously over the
particle cross-section, but are preferentially moved to the area of greatest effectiveness, for example the particle surface.
Besides the monomers, the emulsifiers are important constituents. Emulsifiers
(surfactants) consist of a long-chain hydrophobic group (dodecyl, hexadecyl or alkylbenzene) and a hydrophilic end group.
The hydrophilic group may be anionic (sulfate, sulfonate, sulfosuccinic acid, phosphate, carboxylate) or cationic (quaternary ammonium salts) or have a zwitterionic
structure (betaine groups).
In addition, there is a whole series of nonionic emulsifiers and protective colloids,
which are frequently used in combination with ionic emulsifiers. Ethylene oxidepropylene oxide block copolymers, amphiphilic 2- and 3-block copolymers, polyvinyl
alcohols, polyvinyl-pyrrolidone, alkylpolyglycol ethers, etc.
For the polymerization to start and maintain, a free-radical initiator which forms
free radicals at elevated temperatures (60100 C) is needed, for example sodium
peroxodisulfate, hydrogen peroxide, organic peroxides or azo compounds, or a redox
system, for example hydrogen peroxide/ascorbic acid with Fe2+ salts.
The polymerization can also be initiated by UV, -rays, electron beams or strong
sound or shear fields, although these, apart from UV initiation, have not yet been
used in practice.
The combination of initiator- and surface-active properties (inisurf) or surfaceactive and monomer properties (surfmer) in a single molecule is possible, but is so
far mainly of academic interest.
10
1 Introduction
1.4
Commercial Importance of Polymer Dispersions
Polymers were discovered in the 1920s. During World War II large industrial scale
production was established and since the 1950s production and use of polymers have
grown strongly (Fig. 1-7).
Million Metric tons
200
180
189
160
140
120
114
100
80
60
68
40
20
0
Fig. 1-7
1960
32
1970
1980
1990
2000
Growth of plastics production.
This growth is ongoing, and production of synthetic polymers has reached about
189 million metric tons with a total value of more than US$ 200 billion worldwide by
the year 2000. This growth is due to two factors: the ability of polymers to combine
properties such as light weight, strength, electrical insulation, etc., and the extremely low energy content (as product and in production). The possibility of energy recovery, recycling of the raw material or even of the polymer after use conserves resources. We encounter a wide range of polymers every day in the form of fibers, materials, films, etc., in virtually all products we use in everyday life. Combinations of
the various product classes make a significant contribution toward the variety of end
products made of plastic materials and synthetic fibers. The variety of functional
polymers is even greater than for plastics and fibers. Functional polymers are used
as polymer solutions, polymer dispersions or polymer powders. They essentially perform the functions of protecting, binding, bonding and finishing.
The major polymer classes polyolefins, polyvinyl chloride and polystyrene are
defined by their monomers; ethene, propene, vinyl chloride and styrene (Fig. 1-8).
These three groups together account for 64 % of synthetic polymers. The class of
polymer dispersions is only described by the state of aggregation, but not by the
chemical composition. In the chapters dealing with applications, we will also see that
for a particular application a number of polymer classes are suitable; the specific
1.4 Commercial Importance of Polymer Dispersions
PVC 14%
Polyolefin 43%
Polyester 14%
Polystyrene 7%
Polyurethane 4%
Other 14%
Fig. 1-8
Polymer Dispersions (dry) 4%
Production by polymer class [21].
state of aggregation of the dispersions is consequently often more important than

the monomer combinations. 4 % polymer dispersions correspond to about 7.5 million metric tons (dry) polymer, or 15 million metric tons (wet), assuming an average
polymer content of 50 %. The most important dispersion, natural latex from Hevea
brasiliensis with about 6 million metric tons (dry), is, as a natural product, not included here. The majority is coagulated and used predominantly in the tire industry, only
about 15 % is sold as latex with a solids content of 60 %. These figures also omit impact modifiers for plastics. They are not sold as dispersions, but further processed directly by the manufacturers. About 1 million metric ton (dry) of impact modifiers is
produced worldwide.
The most important product classes of polymer dispersions are butadiene-styrene
copolymers, vinyl acetate homopolymers and copolymers, and polyacrylates. Other
polymer dispersions contain copolymers of ethylene, styrene, vinyl ester, vinyl chloride, vinylidene chloride, chloroprene and polyurethane (Fig. 1-9).
11
12
1 Introduction
Vinylacetate 28%
Acrylate 30%
Other 5%
Styrene Butadiene 37%
Fig. 1-9
Aqueous polymer dispersions by product class.
1.5
Manufacturers of Polymer Dispersions
Worldwide there are far more than 500 companies producing and offering polymer
dispersions. However, only 20 companies account for about half of the global market. The leading 3 suppliers BASF, DOW Chemical, Rohm and Haas have an annual production capacity of more than 1 million metric tons (wet) and cover about
20 % of the world market. In Fig. 1-10 major suppliers of polymer dispersions are
listed in alphabetical order. The product lines are defined by the main monomers
used. Acrylic dispersions include pure acrylics and styrene acrylics, specialty dispersions consist of monomers like vinyl pyridine, vinyl chloride, vinylidene chloride,
chloroprene, etc.. The product lines as well as the information about the main application areas and the trade names were mainly taken from the companys web
sites [2249].
1.5 Manufacturers of Polymer Dispersions

Company
Product lines
Applications
Air Products [1-22]
VAc, EVA, A
Asahi Kasei [1-23]

Avecia[1-24]
A, Sp
A, PU
BASF [1-25]
A, SB, PU, Sp
Clariant [1-26]
Dow [1-27]
VAc, EVA, A,
SB, A, VAc,
PU,
A, VAc
Adh, Coat, Con, I/GA, Pap, Tex Airbond, Airflex, Flexbond, Flexcryl,
Valbond, Valtac, Vancryl, Vinac
Adh, Coat
Polytron, Sun Wrap
Adh, Coat, I/GA
NeoCryl, NeoRes, NeoPac,
NeoRad, Haloflex
Adh, Coat, Con, Pap, Tex
Acronal, Basonal, Butofan, Butonal,
Diofan, Emuldur, Luhydran, Luphen,
Styrofan, Styronal
Adh, Coat, Con, Tex
Mowilith, Mowiplus, Appretan
Coat, Con, Pap, Tex
Dow Latex, UCAR Latex
Eastman Chem. [1-28]

Elf Atochem [1-29]
Enichem [1-30]
Goodyear [1-31]
BFGoodrich [1-49]
now Noveon
JSR Corporation [1-32]
S.C. Johnson [1-33]
Mitsubishi Chem [1-34]
A, EVA, VAc
SB, NB
A, SB, Sp
A, NB, SB, PU,
Sp
National Starch [1-35]
A, SB
A, PU
A, EVA, VAc,
PU
A, EVA, VAc,
Nitriflex [1-36]
NB, SB, Sp
Trade names
Adh, Coat, I/GA
Eastek, Eastarez, Waterborne

Polymer
Adh, Coat, Con, I/GA, Pap, Tex Repolem
Adh, Pap, Tex
Intex, Europrene, Latice
Adh, Coat, Con, Tex
Pliolite, Pliotec
Adh, Coat, Con, Tex
Aqueous XPD, Carbotac, Carboset,
Carbobond, Goodrite, Hycar,
Hystrech, Sancure, Vycar
Adh, Coat, Con, Pap
Glasca, Dynaflow
Adh, Coat, I/GA
Joncryl, SCX
Rikabond
Adh, Coat, Con, I/GA, Pap, Tex Vinamul, Dur-o-set, Dur-o-cryl,
Nacrylic, Resyn
Nitrilatex
Adh, Tex
Zeon Corp. [1-37]
A, SB, NB
Adh, Coat, Con, I/GA, Pap, Tex Nipol
Omnova [1-38]
A, SB, NB,
VAc, Sp
Polymer Latex [1-39]
Revertex [1-42]
Rhodia [1-43]
Rohm&Haas [1-44]
A, NB, SB, PU,

Sp
A, SB, Vac
A, EVA, NB,
SB, VAc, Sp
EVA, VAc
A, VAc, SB
A, VAc, PU
Solutia Inc. [1-45]

Synthomer [1-46]
UCB [1-47]
Wacker [1-48]
A
A, NB, SB
A, PU
EVA, VAc, Sp
Adh, Coat, Con, I/GA, Pap, Tex AcryGen, GenFlo, SunCryl,

AcrylGen, AcrylPrint, GenCal,
GenCryl, GenTac, OmnaBloc,
Sequabond, Sunbond
Acralen, Baystal, Baypren, Bunatex,
Lipaton, Lipolan, Plextol, Perbunan
Pap, Tex
Raisional
Adh, Coat, Con, I/GA, Pap, Tex Elvace, Pace, Plyamul, Synthemul,
Tylac
Adh
Durabond
Rhodopas, Rhodotak, Rhoximat
Adh, Coat, Con, I/GA, Pap, Tex Lucidene, Primal, Polyco, Rhobond,
Rhopaque, Rhoplex, Rovace
Adh
Gelva
Adh, Con, I/GA, Pap, Tex
Adh, Coat
Ucecryl, Ucecoat
Adh, Coat, Con
Vinnapas, Wacker SMK
Raisio Group [1-40]

Reichold [1-41]
Fig. 1-10 Major suppliers of aqueous polymers dispersions. Product lines: A acrylic dispersions, SB styrene butadiene dispersions, NB
acrylonitrile butadiene dispersions, VAc vinyl
acetate dispersions, EVA ethylene vinyl acetate
dispersions, PU polyurethane dispersions,

Sp specialty dispersions. Applications: Adh
adhesives, Coat coatings/paints, Con construction/building products, I/GA inks/graphic arts,
Pap paper, Tex carpet/textile/non-woven.
13
14
References
1 Everett, D. H., Pure Appl. Chem. 31(4),
2
3
4
5
6
10
11
12
13
14
15
16
17
579638, 1972.
IUPAC Proposal for The nomenclature
for Polymerization Processes and Polymers in Dispersed Systems. See also
ISO 12000 Plastics/rubber-Polymer dispersions and rubber latices Definitions
and review of test methods.
Blackley, D. C., High Polymer Lattices,
two volumes, MacLaren, London, 1966.
Warson, H., The Application of Synthetic
Resin Emulsions, Benn, London, 1972.
Piirma, I., Emulsion Polymerisation,
Academic Press, New York, 1982.
Blackley, D. C., Emulsion Polymerisation,
Theory and Practice, Applied Science,
London, 1975.
Hlscher, F., Dispersions of Synthetic
High Polymers, Part I, Properties, Preparation, Testing, Springer, Berlin, 1969.
Reinhard, H., Dispersions of Synthetic
High Polymers, Part II, Use, Springer,
Berlin, 1969.
Buscall, R., Corner, T., Stagemann,
J. F., Polymer Colloids, Elsevier Applied
Science, London, 1985.
Athey, R. D., Emulsion Polymer Technology, Marcel Dekker, New York, 1991.
Poehlein, G., Encyclopedia of Polymer
Science and Engineering; Volume 6,
Emulsion Polymerisation, J. Wiley,
New York, 1986.
Lovell, P. A., El-Asser, M. S., Emulsion
Polymerisation and Emulsion Polymers, J.
Wiley, New York, 1997.
Asua, J. M., Polymeric Dispersions:
Principles and Applications, (NATO
ASI Series E: Appl. Science, Vol. 335),
Kluwer Academic Publishers, Dordrecht,
1997.
Colloid Polym. Sci., Steinkopf.
Colloids Surf., Elsevier.
J. Colloid Interface Sci., Academic Press.
Langmuir, ACS Journal of Surfaces and
Colloids, American Chemical Society.
18 J. Dispersion Sci. Technol., Coden.

19 Gilbert, R., G., Emulsion Polymerisation,
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
A Mechanistic Approach, Academic

Press, London, 1995.
Weissermel, K., Arpe, H.-J., Industrial
Organic Chemistry, Major Organic
Precursors and Intermediates, Verlag
Chemie, Weinheim, 1994.
P. Baum, J. Engelmann, Nachrichten
aus der Chemie, 49/3, 368f, 2001.
http://www.airproducts.com
http://www.asahi-kasei.co.jp/asahi/
english/kasejusi.htm
http://www.avecia.com/neoresins/
http://www.basf.de/de/dispersionen/
products
http://www.clariant.com
http://www.dow.com/emulpoly/
index.html
http://www.eastman.com/
http://www.atofina.com/
http://www.enichem.it/english/
http://www.goodyear.com/
http://www.jsr.co.jp/main/english/
http://www.scjohnsonwax.com/
http://www.m-kagaku.co.jp/
http://www.Vinamulpolymers.com/
http://www.nitriflex.com.br/
http://www.zeon.co.jp/
http://www.omnova.com/
http://www.polymerlatex.de/
http://www.raisiogroup.com/
http://www.reichhold.com/
http://www.revertexfinewaters.com/
http://www.rhodia.com/
http://www.rohmhaas.com/
http://www.solutia.com/
http://www.synthomer.com/
http://www.ucb.be/
http://www.wacker.com/vip/
produktion/wacker/website/polymersystems/index_en.html
http://www.bfgsolutions.com
Synthesis of Polymer Dispersions

Mike A. Taylor
2.1
Introduction
The intent of this chapter is to give a short overview of the chemistry and manufacturing processes involved in the synthesis of emulsion polymers. While the equipment used in preparing an emulsion polymer is relatively simple, and the mechanism of the important reactions are fairly well understood, the development of new
and improved products is often still carried out in a somewhat empirical fashion.
Recipe and process conditions can frequently be designed, based on a theoretical
knowledge, to produce specific polymeric and colloidal properties, but there are still
large gaps in the knowledge needed to translate this into application behavior. In
general, scale-up from laboratory to manufacturing gives good duplication of polymeric and colloidal properties, and laboratory equipment normally consists of simple stirred reactors, usually glass for non-pressure polymerizations, with a means of
maintaining temperature control of the exothermic reaction. With non-pressure reactors, ingredients may be added under gravity, while pumps or inert gas pressure
may be used for pressurized systems. Two important process features that are not reproduced well between small and large-scale reactors are heat transfer and shear.
Laboratory reactors, with their large cooling surface to volume ratio and the large
heat capacity of the reactor relative to the contents, do not normally pose any problems for cooling. In fact, heat losses often exceed heat generated by the reaction, necessitating heat input to maintain reaction temperature. Heat transfer, on the other
hand, often limits production rates in large-scale reactors. In order to achieve a similar degree of mixing in vessels of different sizes, the most important scale-up criteria is usually to maintain the same power input per unit volume. Unfortunately, this
translates to a higher agitation speed as reactor size reduces, a consequence of which
is increased shear on the emulsion. Therefore, for the study of process characteristics, laboratory reactors have significant limitations.
Figures 2-1 and 2-2 show modern laboratory facilities for non-pressure and pressure emulsion polymerization. Both batch and semi-batch reactions are regularly
carried out on laboratory scale. The larger quantities involved in continuous poly-
15
16
2 Synthesis of Polymer Dispersions

Typical laboratory
apparatus for emulsion
polymerization at atmospheric
pressure (photograph courtesy
BASF Corporation).
Fig. 2-1
Laboratory equipment
for emulsion polymerization at
high pressures (photograph
courtesy BASF Corporation).
Fig. 2-2
merization generally rule out this process for laboratory scale reproduction, although
the kinetics of a chain of multiple continuous stirred-tank reactors can be simulated
with a batch reaction (Sect. 2.3.1). Reactions at low temperatures require the provision of refrigerated coolant.
A simple recipe, which could be used to demonstrate the influence of ingredients
and process on polymer and colloidal properties, is shown in Tab. 2-1. Subsequent
sections of this chapter give greater detail on materials used to produce emulsion
polymers.
This recipe could be utilized for investigating both batch and semi-batch emulsion
polymerization at a range of temperatures. With just these two monomers and one
functional monomer, a very wide range of polymers with significant differences in
polymer and latex properties can be produced (soft/hard, low/high molecular
weight, tacky/non-tacky, stable/unstable, etc.)
2.2 Chemistry
Tab. 2-1 Model system for the study of some aspects of emulsion
polymerization.
Ingredient
Quantity
(phm1)
Influence
Water
Styrene
100150
095
n-Butyl acrylate
095
Methacrylic acid
05
Sodium lauryl sulfate
0.53.0
Ammonium persulfate
0.11.0
t-Dodecyl mercaptan
Divinylbenzene
01.0
00.5
Solids content; viscosity

Glass transition temp;
minimum film-forming
Glass transition temp;
minimum film-forming
Colloidal stability; viscosity;
reaction kinetics
Particle size; colloidal stability;
reaction kinetics
Particle size; colloidal stability;
viscosity; reaction kinetics;
molecular wt.
Molecular wt.; reaction kinetics
Cross-linking/gel
1 Parts per hundred parts of monomer
2.2
Chemistry
2.2.1
Mechanism of Emulsion Polymerization
Strictly speaking, emulsion polymerization can take place in a system with only three
components, a monomer that forms the structure of the polymer, water that acts as
the continuous medium in which the polymer particles are dispersed, and an initiator that produces free radicals which start and maintain the polymerization process.
However, at the very least the system will almost invariably contain a fourth ingredient, surfactant, which can provide the initial site, from which polymer particles subsequently grow, and/or give stability to the growing particles. In addition, most commercial recipes would normally include other ingredients to impart specific properties to the final polymer or emulsion, for example, a modifier to control the molecular weight of the polymer or a cross-linking agent to control the amount of gel. In
many cases, ingredients used to control polymerization behavior will also exert their
own influence on application properties of the final emulsion. Particularly, surfactants, while often determining the number of particles and their stability, can also
have significant effects on such properties as adhesion, rheology, filler tolerance and
many others. The overall formulation of an emulsion polymer is therefore often a
compromise to obtain an optimum balance of properties. Rarely can the best of
everything be achieved.
The basic building block of any polymer is the monomer, characterized as a molecule containing at least one carbon-carbon double bond, C=C, and which, through a
17
18
free radical mechanism, can add on to itself, ultimately forming very large molecules
of repeating units. Many different monomers (Sect. 2.2.2) are in use commercially
for producing emulsion polymers, either as the sole monomer or, more usually, as
combinations of monomers to give specifically desired properties. Polymerization is
started when a free radical, originating from the decomposition of the initiator
(Sect. 2.2.5), comes into contact with a monomer molecule and adds on at the site of
the C=C double bond. This creates a monomer unit that is then itself a free radical
and can in turn add on to another monomer molecule. The process continues, building up long chains of monomer units, until the free radical at the end of the chain
comes into contact with some species other than a monomer molecule, normally another free radical, at which time the growing polymer chain is terminated. The free
radical that terminates the chain can be an original radical, from the decomposition
of the initiator, or a polymeric radical when the ends of two propagating chains
terminate each other. Other species, such as inhibitors and short-stopping agents if
present, can also cause termination to occur. These three main stages of polymerization are termed initiation, propagation and termination and can be denoted schematically as follows:
Initiation
Propagation
2R (decomposition of initiator)
M + R RM
RM(n) + M RM(n + 1)
or transfer to polymer leading to branching

Termination
or
RM(n) + RM(m)R RM(n) + RM(m)R

RM(n + 1) + R RM(n + 1)R
RM(n) + RM(m) RM(n + m)R
In such a system, the average molecular weight of the polymer chains is controlled
primarily by the temperature of polymerization and the quantity of initiator. To exert
additional control over molecular weight, a molecular weight modifier (chain transfer agent) is used. With chain transfer, a growing polymer chain is terminated but at
the same time another radical is generated which can initiate polymerization of a
further monomer unit, thus starting another polymer chain. Widely used chain
transfer agents are the mercaptans, RSH, where R is typically a twelve to fourteen
hydrocarbon (t-dodecyl or n-dodecyl being the most common).
Chain Transfer
RM(n) + RSH RM(n)SH + R
These four mechanisms are common to all types of free-radical polymerizations,

for example bulk, solution, suspension and emulsion. The difference between the
processes is the environment. In bulk polymerization there exists only one phase,
initially the monomer, then as polymerization progresses a solution of the polymer
in its own monomer. Both polystyrene and poly(methyl methacrylate) are produced
in large quantities by bulk polymerization. Solution polymerization is similar in that
there is only one phase present, but in this case the monomer is diluted with a fully
miscible solvent and the final polymer is in solution in the solvent. Polyacrylic acid,
with the solvent being water, is produced by this technique. In suspension polymer-
2.2 Chemistry
ization, the monomer is dispersed in droplet form in a continuous medium that is

usually water. The size of the droplets is typically in the range ten to one hundred microns. This process would be favored where an aqueous based polymer is required,
but where the polymer is insoluble in the monomer. Polyvinyl chloride dispersions
are made in this way.
Emulsion polymerization is also carried out in a continuous water phase, but in
this case the site of polymerization is a far smaller entity than dispersed monomer
droplets, as is the size of the final polymer particles. Harkins [1, 2] developed a quantitative theory describing emulsion polymerization in an ideal system. This early
model is still basically accepted today, and is described briefly as follows. In this
process, monomer is solubilized within clusters of surfactant molecules, termed
micelles, which form the nucleus of the polymer particle. or a pre-formed polymer
particle of very small size, usually less than 50 nm, which is used as the seed for further polymerization. In the case of micellar nucleation, many surface active agents,
when dissolved in water above a certain concentration (Critical Micelle Concentration or CMC), will form ordered clusters of molecules, with the hydrophobic portion
of the molecule oriented toward the center of the cluster and the hydrophilic portion
toward the outside. The size of these micelles is typically about 4 nm, the general
shape being either spherical or lamellar. When a sparingly water-soluble monomer
(which describes most of the monomers used in emulsion polymerization) is added
to an aqueous solution containing these micelles, it becomes distributed in three
sites; relatively large monomer droplets stabilized by surfactant molecules at the
droplet surface, monomer molecules in solution in the water, and monomer molecules that diffuse into the micelles. The inside of the micelle, with the high concentration of the hydrophobic portions of the surfactant, provides an attraction for the
hydrophobic monomer that diffuses through the water and swells the micelle. These
monomer-swollen micelles are limited in size by hydrodynamic forces and interfacial tension. The number of monomer-swollen micelles in such a system is orders of
magnitude greater than the number of monomer droplets present, and as a consequence the ratio of the surface areas is similarly large. For example, a dispersion of
50 weight percent monomer droplets in water would contain typically about 1010
monomer droplets per liter, whereas a system containing water, soap solution at a
concentration greater than the CMC, and monomer could contain 10171019
monomer-swollen micelles per liter. This represents a total surface area of the
swollen micelles approximately 105 times that of the monomer droplets. The consequence of this is that when free radicals are produced in the aqueous phase of a system containing water, surfactant and monomer, the free radical has a far greater
probability of entering a micelle and initiating polymerization than it has of entering
a monomer droplet. Also, the overall rate of polymerization, which is the rate per
particle multiplied by the number of polymerizing particles, is greatly enhanced in
the micellar system.
In most cases, the initiators used in emulsion polymerization are water soluble,
and the decomposition, either thermal or with the use of a reducing agent, to produce free radicals takes place in this phase. It is most probable that polymerization
also starts in the aqueous phase, with free radicals initiating monomer molecules in
19
20
Fig. 2-3
Emulsion polymerization [7].
solution in water. As monomer units are added on, these oligomeric radicals increase in hydrophobicity and hence the probability of entering a monomer-swollen
micelle increases. A radical which enters a micelle will then continue to add on
monomer using the reservoir within. As long as there is a source of monomer outside the micelles, such as monomer droplets, the monomer within a growing particle will be replenished by diffusion from the droplet through the aqueous phase and
into the particle, the driving force being the affinity of the monomer for the polymer.
The solubilization of the monomer in the micelles and the mechanism of growth
of the polymer particles are depicted in Fig. 2-3.
Polymerization will continue within the particle until either all of the monomer
has been depleted or another radical enters the particle and terminates the growing
chain. If termination occurs, the particle will then remain dead until another radical enters and initiates a new chain. With polymerization taking place within a particle and fresh monomer entering, the particle obviously increases in size during the
process. Stability is maintained by further adsorption of surfactant molecules at the
surface, along with other mechanisms discussed in Sects 2.2.3 and 2.2.4.
Other sparingly water-soluble ingredients, such as chain transfer agents, follow
the same route, diffusion through the aqueous phase, to enter the growing polymer
particles. Diffusion of molecules into particles is not usually a limiting step in the
overall rate of polymerization, but can be a limit on other processes (Sect. 2.2.6).
An alternative to micellar nucleation, and much practiced today in industry, is the
use of preformed polymer particles of very small and uniform size, normally less
than 50 nm, which act as the nucleus for further polymer growth. This is known as
seeded emulsion polymerization.
2.2 Chemistry
Within an individual particle, assuming an active radical is present, the rate of

polymerization is dependent on the particular monomer and the concentration of
monomer in the monomer-polymer mixture. The rate of addition of a monomer
molecule onto a growing polymer chain is known as the propagation rate of the
monomer, kp, this being temperature dependent with increasing temperature giving
increasing propagation rate. Thus in a system with N total particles, and with an av , the overall rate of polymerization
erage number of radicals per particle denoted by n
is given by:
R = k p N n [M ]
[M], the monomer concentration in the swollen particles, is normally expressed as
mol L1, giving the overall rate of polymerization in mol s1. It is evident that, with a
constant number of particles at a constant temperature, the overall rate will change
according to the average number of radicals per particle and the monomer concentration in the particle.
Smith and Ewart [3] developed an early quantitative theory to predict the rate of
polymerization in an emulsion system, where they describe three regions.
Typically there is a short induction period as the flux of free radicals builds up, following which a period occurs during which the entry rate of free radicals into particles is less than the exit rate (region 1). During this period the average number of
radicals per particle can be much less than unity. Region 2 is quickly reached, where
exit of radicals from particles becomes negligible. While the particles are small and
still have high concentrations of monomer, diffusion of radicals within the particles
and mobility of the polymer chains is unrestricted. Under these circumstances, a
maximum of one growing radical is thought to exist per particle, that is, when a radical enters a particle which already contains a growing polymer radical, termination
of the chain will occur almost instantly. On average, therefore, only one half of the total number of particles will be actively polymerizing at any given instant, that is the
average number of radicals per particle is about one half. It then remains at this value until overall conversion reaches 5060 %. As particles grow larger and the polymer/monomer ratio increases, distances within the particle become greater, viscosity of the mixture increases, and chain entanglement and cross-linking all contribute
toward reduced mobility within the particle. In this case termination is not instantaneous, and an entering radical can co-exist with an already growing chain. This gives
rise to an increase in the overall rate of polymerization in the system (region 3), and
is referred to as the gel effect. In a styrene-butadiene system, the average number of
radicals per particle does not usually exceed two, but with butyl acrylate polymerization values of twenty and higher often occur.
Figure 2-4 shows this relationship.
Monomer concentration starts off at one hundred percent in the monomerswollen micelles, then drops rapidly when polymerization begins. The polymer
formed is not infinitely swellable, the swollen size of the particles being limited by
entanglement and crosslinking of polymer within the chain and by hydrodynamic
forces and interfacial tension. Typically the weight fraction of monomer in the
monomer-polymer mixture is limited to about 0.45 maximum. As long as there is a
21

Typifying the
variation of average
number of radicals per
particle with conversion. (SB system).
Fig. 2-4
n - Av. radicals/particle
1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
20
40
60
80
100
% Conversion
greater quantity of monomer in the total system, the weight fraction in the particles
will remain at 0.45, with the excess in the form of monomer droplets. When the
monomer droplets have been exhausted, the weight fraction of monomer in the particles will reduce, reaching zero at one hundred percent conversion. This is depicted
in Fig. 2-5.
Weight Fraction Monomer
M/(M+P)
22
1
0.8
0.6
0.4
0.2
Typical
monomer concentration in the polymer
particles as a function
of conversion.
Fig. 2-5
0
0
20
40
60
% Conversion
80
100
It can be seen in Figs. 2-4 and 2-5 that, very shortly after the start of polymeriza and [M] become constant, usually to beyond 5060 % conversion. The retion, both n
sult of this is a constant rate of polymerization over this period. The normal type of
conversion-time curve for a batch polymerization is shown in Fig. 2-6. After a short
increases. This is followed by a
induction period, the rate of reaction increases as n
constant rate period. At around sixty percent conversion, the rate often shows an in has a greater influence than decreasing [M]. Finally the
crease, where an increasing n
decreasing monomer concentration has the biggest influence on rate, which thereafter decreases.
In his book on emulsion polymerization, Blackley [4] gives a comprehensive review of the development of the theory of the subject.
2.2 Chemistry
Conversiontime curve for a typical
batch emulsion polymerization.
100
% Conversion
Fig. 2-6
80
60
40
20
0
0
10 11
Time h
2.2.2
Major Monomers
The major monomers are considered as those that make up the bulk of the final
polymer chains, being normally greater than five percent of the final polymer composition. Not included here are the so-called functional monomers, discussed in
Sect. 2.2.3, which are generally used at levels of less than five percent of the total
composition, and which are used to impart certain special properties to the latex or
polymer.
A large number of major monomers are used in emulsion polymerization, either
by themselves to give homopolymers containing recurring monomer units of
the same type or, more frequently, as mixtures giving copolymers (two different
monomer units), terpolymers (three different monomer units) or polymers with
even higher order. Generally, free-radical polymerization is a random process with
the different monomer units distributed randomly in the polymer molecules. However, the different reactivities of free radicals with different monomers does lead to
uneven distribution of monomers throughout the polymer chains. One of the major
determining factors in the choice of a monomer is the glass transition temperature,
Tg, of the homopolymer. This is the temperature at which the polymer changes from
a glassy state to an elastomeric material, a change that takes place over a relatively
narrow temperature range. Table 2-2 lists a number of widely used major monomers
in order of increasing Tg.
The Tg of polymers made up from mixtures of different monomers can be approximated by use of the Fox equation [5]:
1 Wm1 Wm2
W
=
+
+ + mn
Tg Tg1 Tg2
Tgn
where Tg refers to the final polymer, Tg1, Tg2 refer to the individual homopolymers,
and Wm1, Wm2 are the weight fractions of the different monomers making up the
final polymer composition. It can be seen that, with 1,3-butadiene and methyl
methacrylate as monomers, a copolymer can be made with any desired Tg in the
23
24

Tab. 2-2
Some major monomers used in emulsion polymerization.
Monomer
Structure
1,3-Butadiene
n-Butyl acrylate
2-Ethylhexyl acrylate
CH2=CHCH=CH2
CH2=CHC(O)O(CH2)3CH3
CH2=CHC(O)OCH2
CH(CH2CH3)(CH2)3CH3
CH2=CHC(O)CH3
CH2=CHOC(O)CH3
CH2=CHCl
CH2=CHCN
CH2=CH(C6H5)
CH2=C(CH3) CH3C(O)OCH3
Methyl acrylate
Vinyl acetate
Vinyl chloride
Acrylonitrile
Styrene
Methyl methacrylate
Normal
b.p. (C)
Tg of homopolymer (C)
4.4
148
85
54
216
80
73
13
77
145
100
50
10
32
81
97
100
105
range 85 C to +105 C. One of the important attributes of polymers which is related to the Tg is the film-forming temperature, normally very close to the Tg. As a polymer latex dries and the water evaporates, if the polymer is at a higher temperature
than the Tg then the molecules in an individual particle have enough freedom of
movement to penetrate and intertwine with molecules in an adjacent particle. In this
way, the polymer can form a coherent film. Below the Tg, the movement of molecules is too restricted to allow this interpenetration between particles, and a coherent
film cannot form.
Of course in the design of a polymer, the choice of monomers is not only made on
the basis of the required Tg. Many other polymer properties are of importance. For
example, vinyl chloride may be used where fire retardency is required; acrylonitrile
can impart solvent resistance; acrylates tend to give good heat and light aging properties. All of the monomers listed in Tab. 2-1, apart from one, are characterized by
having only one C=C double bond, and are known as vinyl monomers. However, 1,3butadiene is a member of the diene group of monomers, characterized by having
two C=C double bonds. Isoprene is another common diene monomer. The presence
of this second double bond results in both differences in the polymerization mechanism of a diene relative to a vinyl monomer and in the subsequent behavior of the
polymer. During free-radical polymerization, the butadiene molecules become incorporated into the polymer chain through one of the C=C bonds. This can occur in
one of three different ways:
First, by a process of electron transfer, the molecule can be linked into the chain
through carbon atoms 1 and 4, the remaining C=C double bond being between carbon atoms 2 and 3. This repeat unit is called 1,4 and there are two possible isomeric
forms, cis-1,4 with the carbon atoms of the double bond both on the same side of the
backbone chain, and trans-1,4 with the carbon atoms of the double bond on opposite
sides of the chain. A third alternative, with the butadiene linked into the chain
through carbon atoms 1 and 2, has the C=C double bond hanging off the chain as a
pendant vinyl group. This incorporation is known as 1,2. Figure 2-7 shows these
three possibilities. Isoprene can be incorporated in four different ways.
2.2 Chemistry
Possible
methods of incorporation of butadiene
during free-radical
polymerization.
Fig. 2-7
cis -1,4
*
H
H
H
H
H
C
H
C
C
C
H
H
*
C
C
n
H
C
C
H
H
1,2 (pendant vinyl)
H
C
H Hn
trans -1,4
The presence of these additional C=C bonds in the polymer, generally referred to
as unsaturation, can be of benefit or it can be deleterious to polymer properties. The
double bonds in the backbone chain can be used to give controlled crosslinking between chains. The process of vulcanization uses controlled amounts of sulfur to
achieve a desired degree of crosslinking and producing a thermosetting polymer.
Also, during free-radical polymerization, the 1,2 pendant vinyl groups compete with
monomer for addition onto a growing free radical, so that crosslinking actually occurs during propagation. This can be controlled to some degree by the choice of
process conditions (Sect. 2.3.2), but cannot be completely eliminated. On the negative side, the presence of unsaturation in diene polymers leads to inferior heat and
light aging properties relative for example to acrylics, the residual double bonds being attacked by oxygen, UV radiation etc., eventually leading to yellowing and brittling of the polymer.
The general characteristics that control a polymers behavior are basic chemical
composition, crystallinity, glass transition temperature, molecular weight and distribution, gel and crosslinking. Some ways in which desired properties can be achieved
are shown in Tab. 2-3. Of course this Table only shows a few possibilities in polymer
Tab. 2-3
Some aspects of polymer design through composition.
Desired property
Possible polymer design
Stiffness
Soft hand
Tackiness
Water resistance
Use methacrylates, acrylonitrile, styrene

Use n-butyl acrylate, ethyl acrylate, butadiene
Use 2-ethylhexyl or hexyl acrylate
Use crosslinking monomers N-methylol(meth)acrylamide.
Use hydrophobic monomers like n-butyl acrylate or styrene
Crosslinking monomers and/or acrylonitrile
High Tg monomers like styrene, acrylonitrile or methyl
methacrylate
Low Tg monomers like n-butyl acrylate or butadiene
Avoid crosslinking. Use thermoplastic monomers like styrene
Use high amounts of polymerizable acids like acrylic acid
Resistance to organic solvents

High tensile strength
High elongation
Thermoformability
High alkali swellability
25
26
design. There are vast numbers of different potential combinations of monomers

available to choose from, each with variations in molecular weight, branching,
crosslinking etc., giving almost infinite possibilities in the balance of properties obtained.
2.2.3
Functional Monomers
Certain monomers are characterized as functional monomers, so called because in

addition to having the polymerizable C=C double bond they contain a functional
group such as a carboxylic acid or amide. These monomers are important because
they can impart special properties to both the polymer and the colloidal system. They
are normally used in relatively small amounts, typically 25 % of the dry polymer.
Table 2-4 lists some of the commonly used functional monomers. Acrylic and
Methacrylic acids are the most widely used monobasic carboxylic acids, with Itaconic and Fumaric acids as common dibasic acids. These acids, through the C=C bond,
participate in the free-radical polymerization and become incorporated in the main
polymer, but due to the highly polar carboxyl group (COOH) tend to be at the surface
of the polymer particles (polymer-water interface) with the carboxyl group orientated
toward the aqueous phase. The acid group is ionized in water, so that the particle
surface has a negative charge at each acid site (COO). The negative charge at the
surface imparts a high degree of stability to the polymer particles, particles repelling
each other due to the like charges. This stabilizing influence is the same as that produced by surfactants, but with the added advantage that the carboxylic acid is bound
into the polymer chains, not just adsorbed at the particle surface. To maintain overall electrical neutrality across the interface, the layer of negative ions is balanced by
an adjacent layer of cationic counterions. The ions and counterions are referred to as
the electric double layer and the thickness of this layer is very dependent on the pH
of the continuous medium. At low pH (high H + concentration) the layer is compressed and at its minimum thickness. As the pH is increased (reducing H + concentration), the layer expands outward from the particle. The thickness of this double
layer contributes to the effective diameter of the latex particle, and is one reason for
increasing viscosity as pH increases. It should be noted that the presence of watersoluble polymer in the latex could also contribute strongly to viscosity increase with
increasing pH, due to stretching of the chains.
Tab. 2-4
Commonly used functional monomers.
Functional monomer
Structure
Acrylic acid
Methacrylic acid
Itaconic acid
Fumaric acid
Hydroxyethyl acrylate
Acrylamide
CH2=CHC(O)OH
CH2=C(CH3)C(O)OH
CH2=C(C(O)OH)CH2C(O)OH
HOC(O)CH=CHC(O)OH
CH2=CHC(O)OCH2C(OH)H2
CH2=CHC(O)NH2
2.2 Chemistry
In addition to the greatly enhanced mechanical stability imparted to the emulsion

by these functional monomers, stability to electrolytes is generally improved, as is
filler tolerance of the latex. Mechanical strength of the polymer films is increased,
and in fact can be increased further by the use of, for example zinc oxide, which gives
an ionic crosslink between carboxyl groups. The presence of the carboxyl groups also
allows crosslinking through the use of urea-formaldehyde, phenol-formaldehyde,
melamine-formaldehyde and various epoxy resins. Polymerization of the acid functional monomers is usually carried out under conditions of relatively low pH. Neutralization of the acid favors partitioning in the aqueous rather than the organic
phase, reducing incorporation into the polymer and at worst, where homo-polymerization of the acid is a possibility, as with acrylic and methacrylic acids, the formation
of polyacrylic acid salts in the aqueous phase. These high molecular weight polyelectrolytes can act as very effective coagulants for the latex.
2.2.4
Surfactants
As first discussed in Sect. 2.1.1, surface-active materials are normally an essential

ingredient in emulsion polymerization. They can be used in any or all of the following roles:
micellar solubilization of monomers, forming the primary sites for nucleation
stabilization of growing polymer particles
enhancement of application properties of the finished latex
A single surfactant may satisfy all three roles, or there may be a requirement for
multiple surfactants. The optimum choice of surfactant for one role may produce
undesirable performance in other roles, and there may be positive or negative synergism exhibited when multiple surfactants are used. As with many other aspects of
emulsion polymerization, a compromise is often required in the choice of surfactant.
A key phenomenon observed with surfactants is a marked change in a number of
physical properties of an aqueous solution that takes place at a certain critical concentration. For example, with ionic surfactants, equivalent conductivity exhibits a
sharp reduction, surface tension reaches a minimum then begins to increase, interfacial tension reaches a minimum and osmotic pressure almost plateaus. Below this
concentration, surfactant molecules are in normal random solution in the water. As
the critical concentration is reached, the surfactant molecules aggregate into ordered
clusters known as micelles, normally considered to be spherical but other geometry
such as lamellar is also possible. The break in the behavior of solution properties represents the change from a true solution to a colloidal solution. The concentration of
surfactant at which this change takes place is known as the Critical Micelle Concentration (CMC), and the number of molecules of surfactant which form one micelle is
called the agglomeration number. Addition of further surfactant above the CMC all
goes toward increasing the number of micelles.
The main characteristic of a surfactant is that its molecular structure consists of
two parts, a lyophobic (solvent hating) portion and a lyophilic (solvent loving) por-
27
28
tion. When the solvent is water, these two groups are referred to respectively as hydrophobic and hydrophilic. The hydrophobic portion of a surfactant is usually a longchain hydrocarbon or oxygenated hydrocarbon, although other structures are possible. The hydrophilic group is either ionic or highly polar.
Surfactants are classified according to the nature of the hydrophilic group of the
molecule:
Anionic, where the hydrophilic group has a negative charge. Examples are carboxylic, sulfate, sulfonate and phosphate groups.
Cationic, where the hydrophilic group has a positive charge. Long chain quaternary ammonium salts and long chain amines and amine salts, with or without incorporation of ethylene oxide units.
Non-ionic, with no charge on the hydrophilic group, often polyoxyethyleneated
long chain alcohols or alkylphenols, the hydrophobic/hydrophilic balance being
controlled by the number of moles of ethylene oxide.
Zwitterionic, with both positive and negative charge on the hydrophilic group.
Anionic and cationic surfactants are not compatible with one another. Non-ionic
and zwitterionic types are compatible and can be used with either anionics or cationics. Certain zwitterionics become cationic at low pH and anionic as the pH is increased.
Some of the structures that can make up the hydrophobic group are straight or
branched long alkyl groups, long chain alkylbenzene residues, alkylnaphthalene
residues, rosins and high molecular weight propylene oxide polymers. The alkyl
groups are generally 320 carbon atoms long, and in most cases, because of the
source of the alkyl group, a particular surfactant will actually be a mixture of various
chain lengths. The properties of the surfactant depend on the length of the hydrophobic group, branching or unsaturation, the presence of an aromatic group or
the incorporation of propylene oxide units. Rosen [6] discusses the influence of different hydrophobic and hydrophilic groups in detail. Table 2-5 gives an example of
the influence of some different structures on agglomeration number and CMC. The
effect of increasing linear alkyl chain length in a series of sodium alkyl sulfonates is
Tab. 2-5
Some structural influences on surfactant properties (Rosen [6]).
Surfactant
Formula
Agglomeration
number / T (C)
CMC at 40 C
(mol L1)
Sodium octyl sulfonate

Sodium decyl sulfonate
Sodium dodecyl sulfonate
Sodium tetradecyl sulfate
Sodium hexadecyl sulfate
Sodium dodecyl sulfate
Branched sodium alkyl sulfate
Sodium dodecyl ethoxylate (2EO)
Dodecyl alcohol ethoxylate (5EO)
C8H17SO3 Na+
C10H21SO3 Na+
C12H25SO3 Na+
C14H29SO3 Na+
C16H33SO3 Na+
C12H25SO4 Na+
C12H25CH(SO4 Na+)C3H7
C12H25(OC2H4)2SO4 Na+
C12H25(OC2H4)5OH
C12H25(OC2H4)7OH
C12H25(OC2H4)8OH
25 / 23
40 / 30
54 / 40
80 / 60
1.6 101
4.0 102
1.1 102
2.5 103
7.0 104
8.6 103
1.7 103
2.8 103
5.9 105
7.3 105
9.3 105
2.2 Chemistry
seen, increasing carbon number giving rise to reducing agglomeration number and
CMC. The sulfate group is seen to give a lower CMC than the sulfonate. Inclusion of
the sulfate anion on a non-terminal carbon atom increases the CMC, and the introduction of polyethylene oxide (2 mol) into the sulfate reduces CMC. Finally, increasing the moles of ethylene oxide in the non-ionic series of polyoxyethyleneated
straight chain alcohols is seen to increase the CMC.
In emulsion polymerization, anionic and non-ionic surfactants are the most common choice during the polymerization stage. Cationics are used in polymerization
for some applications, but the use of cationics and anionics in the same equipment
is generally avoided. It is possible to produce an emulsion polymer with either an anionic or a cationic surfactant, and subsequently switch to an oppositely charged
species along with a controlled pH change. Zwitterionics are not common in
emulsion polymerization. If the surfactant is serving the dual purpose of providing
nucleation sites and subsequently stabilizing the growing particles, balancing the
two requirements can be difficult. For micelle formation, the concentration of
surfactant must be at or above its CMC. Then, as a general rule, for a specific surfactant the number of polymer particles initiated is approximately proportional to [surfactant concentration]0.6. It is therefore often the case that the amount of surfactant
required to give the desired ultimate particle size is insufficient to provide continued
stabilization as the particles grow. This can occur almost anywhere within the normal particle size range, and as a consequence it is usually necessary to add additional surfactant as polymerization progresses. Addition of too much surfactant during
polymerization can, if the CMC is exceeded, cause another family of particles to be
initiated. The difficulty of balancing nucleation and stability is exacerbated by
the fact that many factors influence nucleation, for example temperature, concentration of initiator/surfactant/electrolyte, pH and any impurities that either retard or
increase polymerization. Seeded processes significantly reduce this variation and
eliminate the requirement for the initial surfactant. Overall, with seeded processes,
the total amount of surfactant is often considerably less than with micellar nucleation.
Some common surfactants used in emulsion polymerization are:
Sodium and potassium salts of naturally occurring fatty acids (oleic, linoleic) and
rosin acids. These soaps are used in large quantities in the production of styrenebutadiene latex for both dry rubber production and latex applications. These materials are only useful at pH values greater than 7, normally being used at pH 1012.
Below pH 7, the insoluble acids are precipitated, and all stabilizing function is
lost.
Salts of sulfated linear alcohols, for example sodium lauryl sulfate, are widely used
in the emulsion polymerization of functionalized styrenebutadiene polymers and
many acrylic esters.
A range of the salts of alkylbenzene sulfonates and alkylnaphthalene sulfonates,
which give improved electrolyte stability and are not subject to hydrolysis in acid
media as are the sulfated alcohols. Sodium dodecylbenzene sulfonate is widely
used.
Salts of alkylphosphates, usually polyoxyethyleneated.
29
30
non-ionic surfactants in wide use in emulsion polymerization include polyoxyethyleneated alkylphenols and straight chain alcohols, where the length of the alkyl
group and the moles of ethylene oxide can be varied, and polyoxyethyleneated
polypropylene glycols, block copolymers where the moles of ethylene and propylene oxides can be varied to adjust the hydrophilic/hydrophobic balance.
This list is by no means exhaustive, there being an almost limitless choice of surfactants or combinations of surfactants available. From the aspect of particle stabilization during the emulsification process, and even to a large extent nucleation, the
choice of surfactant is usually not too critical. By far the biggest factor in the choice
of surfactant is the application performance of the final product. Unfortunately as a
general rule, the presence of surfactant in the final dry polymer causes reduced water resistance. Also, there is a tendency for surfactant molecules to diffuse to the
polymer/air or polymer/substrate interface, where deleterious effects (cloudiness at
the surface, loss of tack, etc.) are often caused. This again demonstrates the compromise often necessary in emulsion polymer synthesis.
In an attempt to mitigate against migration of surfactant, there are certain products available, known as polymerizable surfactants, where the molecule contains a
polymerizable C=C double bond. (This is a functional monomer because it does not
form micelles.) Examples are the Noigen and Hitenol series of products from DaiIchi Kogyo Seiyaku (polyethoxylated alkylpropenyl phenyl ethers and polyethoxylated
alkylpropenyl phenyl ether sulfates respectively).
2.2.5
Initiator Systems
The initiator system in emulsion polymerization is the source of free radicals. There
are two major types of system used, substances which thermally decompose to produce free radicals and substances which produce free radicals when part of a redox
system. Light or other radiation can generate free radicals, but is not widely used for
emulsion polymerization.
By far the most common thermal systems are peroxy compounds; ammonium,
sodium and potassium persulfate and a wide range of organic peroxides and hydroperoxides. The rate of decomposition of these materials is usually specified by the
half-life, defined as the time taken at a particular temperature for the concentration
of a solution of the material to reduce to one half of its initial value through thermal
decomposition. The three persulfates have a similar half-life and their effectiveness
in emulsion polymerization is therefore also similar. However, the lower water solubility of the potassium salt makes it less commonly used than the others. Persulfates
are generally used for polymerization in the temperature range 50100 C, and production of free radicals takes place in the aqueous phase of the emulsion. At higher
temperatures, decomposition is usually too fast to give efficient use of the free radicals due to radical recombination. At lower temperatures, persulfates can still be
used in conjunction with a reducing agent such as sodium bisulfite.
The organic peroxides and hydroperoxides cover a wide range of half-life, and can
provide an appropriate choice for most normal polymerization temperatures. The
2.2 Chemistry
Tab. 2-6
A range of thermally dissociating initiators (from manufacturers product literature).

Half-life (h)1
Substance
Dicyclohexyl peroxydicarbonate
Ammonium persulfate
Dilauryl peroxide
Dibenzoyl peroxide
t-Butyl peroxybenzoate
Dicumyl peroxide
Cumene hydroperoxide
t-Butyl hydroperoxide
40 C
50 C
70 C
18
4.1
192
50
0.27
8.4
3.2
14
90 C
0.55
0.29
1.2
70
110 C
0.13
6
23
570
130 C
150 C
0.7
2.3
100
520
0.26
20
70
Approximate values only. pH and the presence of other components can significantly influence
decomposition
differing solubilities in water also determine if the free radicals are produced in either the aqueous or the monomer phase. Table 2-6 lists some of the commonly used
thermally dissociating initiators, along with their half-life. Most commonly, the peroxides and hydroperoxides are used at lower temperatures, 050 C, as a part of a redox system.
Often persulfates are chosen in preference to the organic peroxides because of the
increase in colloidal stability that results from the sulfate end groups on the polymer
chains. On the negative side, these sulfate groups also increase the water sensitivity
of dried polymer films.
The thermal decomposition of persulfate produces both sulfate and hydroxyl radicals, according to the mechanism:
S2O82 2SO4
SO4 + H2O HSO4 + HO
2OH H2O + 12O2
It is generally accepted that the primary initiating species is the sulfate anion radical, and to the extent that termination is predominantly caused by another sulfate
initiated radical species, it is expected that most polymer chains would contain two
sulfur atoms. This is generally found to be the case.
An organic peroxide decomposes as follows:
ROOR 2RO
and the reduction of a hydroperoxide by iron(II):
ROOH + Fe2+ RO + HO + Fe3+
During the nucleation stage of emulsion polymerization, the concentration of initiator exerts an influence on the number of polymer particles formed. An initiated
particle grows very rapidly as polymer is formed. As the particle increases in surface
area, it adsorbs surfactant from solution thus reducing the possible number of micelles in the system. Therefore, the faster that initiation occurs, then the greater will
31
32
be the number of polymer particles formed before micellar surfactant is exhausted.

Because the thermal decomposition of the initiator is first order with respect to its
concentration, the higher the concentration, the greater will be the rate of radical
production and the shorter the initiation period. The number of polymer particles
formed is approximately proportional to the concentration of initiator to the power of
0.4. As discussed in Sect. 2.2.1, the overall rate of polymerization is proportional to
the number of polymer particles, and therefore the consequent rate of polymerization is also proportional to [Initiator]0.4. However, after completion of the nucleation
stage, subsequent changes in the initiator concentration (assuming a certain minimum) have little effect on the rate of polymerization. This is due to the fact that the
number of particles remains fairly constant, and the average number of radicals per
particle is dependent on the environment within the particle, not the rate of radical
production. The molecular weight of the polymer is however influenced by the initiator concentration, because, neglecting other influences, the time available for a
polymer chain to grow is dependent on the rate at which free radicals enter the particle. One entering radical initiates polymerization, the next normally terminates the
chain. The higher the concentration of initiator, the higher the rate of production of
radicals and the higher the rate of entry of radicals into a particle. Although this effect on molecular weight is significant, chain transfer agents often exerts a bigger influence.
2.2.6
Other Ingredients
The use of chain transfer agents in emulsion polymerization was briefly discussed in
Sect. 2.2.1. As stated, the most commonly used chain transfer agents are the mercaptans (thioalcohols) RSH, although a wide range of other compounds also exert a
modifying effect during polymerization, for example carbon tetrachloride, certain
disulfides, rosin acid salts, 4-vinylcyclohexene (butadiene dimer) amongst many others, which may also include impurities in other raw materials.
The effectiveness of a chain transfer agent is denoted by its transfer constant, ,
which is the ratio of rate of the chain transfer step to the propagation step:
Ks
RM(n)SH + R
RM(n) + RSH
Kp
RM(n) + M RM(n + 1)
Ks
=
Kp
It can be shown that, neglecting all other reactions of monomer and chain transfer
agent, that a plot of log [S] against log [M], where [S] and [M] are the concentrations
of modifier and monomer respectively, should be a straight line with slope . This
linear relationship is generally found to hold true in emulsion polymerization, but
the slope is often not equal to as determined from bulk polymerization. This is because the rate-determining step for mercaptan consumption can often be the diffusion of mercaptan through the aqueous phase into the reaction zone in the polymer
particle. In general, the fewer the number of carbon atoms in the alkyl group of the
2.2 Chemistry
mercaptan, the closer the apparent transfer constant in emulsion polymerization becomes to that measured in bulk (faster diffusion). This means that the shorter chain
mercaptans tend to disappear more quickly than the longer chains. Thus the short
chain modifiers tend to exert a greater modifying influence during the early stages of
a batch emulsion polymerization, whereas the longer chain alkyl groups tend to be
more effective toward the end of polymerization. C12 chains often show the best balance between these extremes, hence the very common use of n-dodecyl and t-dodecyl
mercaptans. Of course, the overall effect of the chain transfer agent can also be controlled by making injections at appropriate times during polymerization, or with
semi-batch reactions by having continuous (linear or non-linear) feeds of modifier.
Polymerizable cross-linking agents are often included in emulsion polymerization
recipes, either to form cross-links during the polymerization (increasing the gel in
the polymer, or increasing the so-called green strength) or to form cross-links subsequent to polymerization, by heat application or chemical means. As previously discussed, when a diene is one of the monomers in an emulsion polymerization, the
second double bond in the diene will lead to a considerable degree of cross-linking
during the polymer formation. In the absence of a diene, other monomers that are
commonly used to produce cross-links during the polymer formation are divinyl
benzene and a range if diacrylates and triacrylates, for example butanediol diacrylate
and trimethylolpropane triacrylate. These materials would normally be incorporated
at low levels, <0.1 weight percent of the monomer, so one can see that, on average,
the number of cross-links introduced would be less than one per thousand
monomer units.
To introduce heat sensitivity into the polymer (cross-linking which occurs after
polymerization, usually when a dried polymer film is heated), two commonly used
monomers are N-methylolacrylamide and N-methylolmethacrylamide. The structure
of N-methylolacrylamide is as follows:
CH2=CHC(O)NHCH2OH
Incorporation into the polymer backbone takes place through the vinyl double
bond. Cross-linking then takes place between two methylol groups.
|
CH2CHC(O)NHCH2NHC(O)CHCH2
Electrolytes, most often alkali metal phosphates or sulfates, are utilized in emulsion polymerization systems for a variety of reasons. When present in a micelleforming surfactant solution, electrolytes can increase the aggregation number of the
micelles (the number of soap molecules per micelle). Thus with increasing electrolyte concentration the number of micelles is reduced, and this is an additional
means of controlling the number of polymer particles formed. Electrolytes are also
used to reduce the viscosity of the polymer emulsion, especially during the polymerization process, an effect that is achieved through compression of the electric double
layer. Finally, electrolytes are often used as part of a buffer system to minimize pH
variation during polymerization. High concentrations of electrolytes will generally
cause de-stabilization and agglomeration of polymer particles.
33
34
It is common to include a chelating agent, normally a salt of ethylenediamine

tetraacetic acid (EDTA), in emulsion polymerization recipes. Use of this compound
to chelate metal ion impurities in the system, particularly calcium, magnesium and
iron, generally leads to lower coagulum levels in the final latex, and often gives more
consistent initiation of polymerization. It is fairly common practice in the manufacture of emulsion polymers at higher temperatures to use untreated (non-deionized)
water as the continuous media. The use of a chelating agent protects against the
hardness salts. In low temperature systems with redox initiators, a chelating agent
is often a part of the redox system, used to complex the iron component and prevent
precipitation.
2.3
Manufacturing Processes
2.3.1
Types of Process
Compared with many other types of chemical manufacture, the production of emulsion polymers is relatively simple in terms of the unit operations required. Typically
there is a reaction stage, where the polymer is made, a purification stage to remove
residual organic volatile components, some type of filtration or screening to remove
any coagulum from the latex and a final stage where post additions of other ingredients may be made along with final adjustment of latex properties such as pH and
solids content. Occasionally there may be a concentration of the latex to reduce the
water content, and for some processes there may be some purification of raw materials, or recovery and recycling of raw materials.
Industrial chemical processes are categorized as batch, semi-batch or continuous,
and the manufacture of emulsion polymers is carried out in all these process types.
The processes differ not only in equipment type and economics of operation but also
in the specific properties imparted to the polymer and the emulsion. In a batch
emulsion polymerization, all ingredients are added to a vessel, polymerization is initiated and the reaction proceeds to completion over a period of time. Thus, conditions in the reactor gradually change from monomer + water polymer + water,
passing through all intermediate ratios of monomer/polymer.
A continuous polymerization may be carried out in a continuous, stirred-tank reactor, where the reactants continuously enter a stirred vessel and the product continuously exits. Here the conditions in the reactor remain constant with time, the composition being equal to the exit composition. There may be only one CSTR, or multiple CSTRs in a chain, the product from one being the feed for the next in the chain.
The greater the number of CSTRs in a chain, the closer the properties approach
those from a batch reaction. A plug-flow continuous reactor is one in which the reacting mixture passes through the reactor without any forward or backward mixing,
as for example in a tubular reactor. In this type of system, at any given position in the
reactor, the composition is constant with time. Distance along the reactor is equiva-
2.3 Manufacturing Processes
lent to time in the batch reactor. Although emulsion polymerization in a continuous

tubular reactor has been the subject of much research in the past, this process is not
commonly used because of the poor degree of mixing, heavy fouling of the reactor
and the difficulties of cleaning.
In a semi-batch process, only a portion of the total ingredients is added to the reactor initially, polymerization is initiated and the remainder of the ingredients is
added over a period of time until the desired filling volume is reached. The material
is then discharged and the process repeated. In the semi-batch process, conditions in
the reactor change rapidly when the feeds start (monomer monomer + polymer),
remain relatively constant for the majority of the feed period, and change rapidly
again when the feed stops (monomer + polymer polymer). For safety reasons
(Sect. 2.3.4) semi-batch is the preferred manufacturing process.
Figure 2-8 shows the typical progression of the monomer/polymer composition
profile in these main process types and Fig. 2-9 is a diagrammatic representation of
the processes.
(A)
(B)
100
% Conversion
% Conversion
100
80
60
40
20
0
80
60
40
20
0
(C)
(D)
70
100
60
CSTR 5
50
CSTR 4
40
30
CSTR 3
20
CSTR 2
10
CSTR 1
% Conversion
% Conversion
Time
Time
80
60
40
20
0
Reactor number in chain
Distance along reactor
Variation of monomer/polymer in different processes expressed

as % conversion of added monomer: (A) batch; (B) semi-batch;
(C) chain of five CSTRs; (D) continuous plug flow.
Fig. 2-8
There are novel variations of these processes in use, as are combinations of the
processes. The reactor type and the process conditions exert large influences on the
resulting properties as discussed in Sect. 2.3.2.
The product from emulsion polymerization reactors usually contains a small
amount of non-reacted monomers, along with volatile impurities from many
sources. Such impurities may include a range of solvents originating from various
raw materials, dimers and co-dimers either present in monomers or formed during
the polymerization, alcohols from hydrolysis of vinyl esters, products formed from
35
36

Feed
Feed
Final Level
a)
b)
Initial Level
Product
Product
Product
c)
Feed
Feed
d)
Product
Types of process used for emulsion polymerization: (a) batch;
(b) semi-batch; (c) continuous stirred tank (chain of three); (d) continuous
plug flow (tubular).
Fig. 2-9
organic initiators, and a whole range of saturated and unsaturated organics coming
from the monomers. In many cases, polymerization is taken to a high degree of conversion in the reactors (>99 %), so that the residual monomers are often <1 %. However, it is normal to further polymerize this residual monomer, often using a redox
initiator system. Because of the low monomer concentration at this stage, the rate of
polymerization is relatively slow, and with reactor time normally being at a premium
this chemical stripping is carried out in separate, lower cost equipment. Of course
many of the organic impurities are either not polymerizable or cannot be polymerized under typical emulsion polymerization conditions. To remove these contaminants, physical separation techniques are often employed. Steam distillation is the
most widely used technique, either in batch strippers or in continuous processes
such as a column stripper. In some cases, solvent extraction, membrane separation
or adsorption processes may be used.
The production of styrene-butadiene rubber emulsions is one case where polymerization is deliberately stopped at a low conversion, typically 7080 %, in order to
limit the crosslinking reaction from the pendant vinyl groups in the butadiene units.
With such large amounts of residual monomer, economics force the recovery and recycling of both butadiene and styrene. After the polymerization stage, residual butadiene is flashed off under vacuum, compressed, cooled and returned to the reactor
feed, and styrene is steam stripped in a column stripper, condensed and also returned to the reactor.
Coagulum formed during the manufacture of emulsion polymers can cause problems with application processes, and although much progress has been made in the
industry to minimize these problems, (improved recipe design, better stabilization
systems, improved control of process parameters), there still exists the need to remove coagulum during various stages of the process. All types of filtration equipment are used in the industry, from simple filter bags and static screens through
wiped screens, band filters, vibrating screens, filter presses to quite complex selfcleaning filters of various types, both with and without the use of filter aids such as
diatomaceous earth. Centrifugation is also used, although with many lattices, the
density difference between polymer and the disperse medium is too small to make
this an efficient process.
Post additions to the latex product, and final adjustments to properties such as pH
and solids content are carried out usually in simple stirred tanks, although continuous in-line mixing may also be practiced.
2.3.2
Influence of Process Conditions on Polymer/Colloidal Properties
As shown in Sect. 2.3.1, the three main types of reaction process differ in the
monomer/polymer concentration profile throughout the reaction. Because many of
the chemical reactions occurring during emulsion polymerization, such as branching, crosslinking and propagation, are competitive and dependent on the relative
quantities of monomer and polymer at the reacting site, it can be seen that all of
these will be influenced by reactor type. Branching and crosslinking are favored at
high polymer concentrations. Therefore, given the same reaction temperature, a
batch process, which has the highest average monomer concentration through the
process, will give the least branched polymer with the lowest degree of crosslinking.
The opposite end of the scale is represented by a single CSTR operating at a high
conversion which will tend to give a highly branched and crosslinked polymer. Increasing the number of CSTRs in a chain will lead to a reduction in branching and
crosslinking. A semi-batch process can be operated at both ends of the scale. With
very fast feed rates, the system is monomer flooded and the product will be close in
properties to the batch reaction. Slow feed rates (monomer starved) lead to high
branching and crosslinking. In particular, in systems containing butadiene where
the pendant vinyl groups contribute strongly to crosslinking, the influence of
monomer/polymer ratio is highly significant. Crosslinking increases rapidly as con-
37
Relative X-linking
0.00045
0.0004
0.00035
Variation in
the relative degree of
crosslinking with percentage conversion
during the emulsion
polymerization of
styrene/butadiene
25:75 in a batch
system at 30 C.
(average number
of cross-links per
monomer unit in
polymer)
Fig. 2-10
0.0003
0.00025
0.0002
0.00015
0.0001
0.00005
0
0
20
40
60
80
100
% Conversion
version increases (Fig. 2-10) necessitating shortstopping of the polymerization at low
conversion when a polymer with high elongation is required.
Temperature similarly influences branching and crosslinking, both normally reducing with lower temperatures. Molecular weight tends to increase with reducing
temperature. In a semi-batch and a CSTR, the influence of temperature is enhanced
because reducing the temperature at a constant feed rate causes a reduction in polymerization rate and hence a reduction in the instantaneous conversion.
The number of particles in the polymerization system influences the rate of reaction; the larger the number (smaller final particle size) the faster the overall rate.
Therefore in a semi-batch reactor or a CSTR, for a given feed rate, the number of particles exerts an influence on instantaneous conversion and thus all of the properties
previously discussed under conversion. Figure 2-11 shows this influence.
This control over polymer properties by the number of particles in the system
makes it critical to control particle number, and has been one of the driving forces to100
% Instantaneous Conversion
38
90
80
70
60
50
40
30
20
10
0
0
Time in Hours
PD = 135 nm
PD = 155 nm
PD = 175 nm
Fig. 2-11 Influence of

number of particles on
the instantaneous conversion in a semi-batch
emulsion polymerization of styrene-butadiene 45:55 with a feed
time of 4.5 h at 85 C.
ward the use of seed polymer. The use of seed reduces the variability of the nucleation stage, making it less dependent on temperature, surfactant concentration, electrolyte concentration etc. Of course this is in turn dependent upon the seed itself being a consistent raw material.
2.3.3
Equipment Considerations
The reactors used for the manufacture of emulsion polymers are normally relatively
simple, agitated vessels, ranging in size from 5 m3 (less than this is normally considered to be pilot plant scale) to 200 m3, with the majority being in the range
15100 m3. Carbon steel, glass-lined construction used to be the standard (the glass
surface minimizing polymer deposition) for polymerization under acid or slightly alkaline conditions. For high pH systems (for example those based on the alkali metal
salts of fatty acids and using redox initiator systems) carbon steel reactors are the
standard. As emulsion stability has been improved over the years, and better cleaning techniques have been developed (high pressure water jets), it has become common to replace glass-lined reactors with either stainless steel or carbon steel with
stainless steel cladding. Typically, to avoid contamination from metal ions, all
pipework associated with feeds into and product from the reactor would be stainless
steel construction.
Pressure ratings of reactors range from atmospheric to >100 bar with temperature
of operation in the range 5200 C. (in certain special cases sub-zero temperatures
may be achieved through the use of anti-freeze agents in the emulsion). The most
common temperature range for emulsion polymerization is 60100 C.
To control the temperature of these highly exothermic reactions, reactors are fitted
with a variety of cooling systems. This may be a jacket around the reactor (annular,
dimpled, half-pipe); the reactor may be fitted with internal cooling coils or cooled
baffles; there may be supplemental cooling systems such as reflux condensers, or
heat exchangers of various types through which the reaction mixture is circulated.
For agitation, a wide variety of impeller types are in use; both axial and radial flow
turbines, propellers, paddles, anchor agitators and many other proprietary designs.
The choice of impeller is very much dependent on the properties of the emulsion
polymer being made (stability, viscosity etc.).
Latex may be transferred through subsequent parts of the process either using inert gas pressure or with a variety of low shear pumps. It is normal to neutralize the
latex after the reaction stage, thus greatly increasing stability. High-pressure equipment is not usually necessary downstream of the reactor, although some operations
will require full vacuum rating.
As discussed in Sect. 2.3.1, batch strippers, stripping columns, filtration equipment and mixing vessels are all in use to a varying extent downstream of the reaction
stage. Because of the tendency of emulsion polymers to cause deposits in the
process, the secret of successful operation is usually to keep equipment simple. Ease
of cleaning is paramount, and moving parts, particularly if high shear is imparted
to the latex, should be avoided where possible.
39
40
2.3.4
Safety Considerations
To carry out emulsion polymerization safely, the pressure which can develop under
a worst case scenario should always be less than the design pressure of the reactor.
As with any highly exothermic chemical reaction, if the generated heat is not removed from the system, the temperature (and in an enclosed system, the pressure)
will increase in an exponential manner. The pressure can rapidly exceed the design
pressure of the containing vessel, resulting in rupture of the vessel or its associated
piping if the system is not protected by appropriate relief devices. It has to be questioned whether or not relief devices are ever really appropriate in reality, although
the reactor may be protected, a potentially hazardous situation is being transferred
elsewhere (vent tanks, quench tanks, environment). The correct sizing of relief systems for emulsion polymerization reactors is also not a trivial exercise, in part because it is difficult to define a worst case scenario and in part because emulsion and
polymer properties at extreme reaction conditions are not well known. Very large relief devices are often indicated, which in turn means a large problem outside the reactor.
A major driving force for the change from batch to semi-batch polymerization
processes, despite the loss in some polymeric properties which often accompanies
this change, has been the inherently safer aspects of semi-batch, with smaller quantities of monomer in the reactor at any given time.
Thus, the major capacity limitation in the process can be seen to be a function of
the pressure rating of the reactor, the rate and efficiency of removing heat from the
system, and the safety systems which are in place to ensure that the maximum reactor working pressure can never be exceeded.
References
1 W. D. Harkins, J. Am. Chem. Soc. 1947,
69, 1428.
2 W. D. Harkins, J. Polym. Sci. 1950, 5,
217.
3 W. V. Smith, R. H. Ewart, J. Chem. Phys.
1948, 16, 592.
4 D. C. Blackley, Emulsion Polymerisation
Theory and Practice, Applied Science,
1975.
5 T. G. Fox, P. J. Flory, J. Appl. Phys.
1950, 21, 581.

6 M. J. Rosen, Surfactants and Interfacial
Phenomena, John Wiley and Sons,

1989.
7 The schematic diagram is a courtesy
of C. D. Anderson, M. S. El-Aasser,
Emulsion Polymers Institute, Lehigh
University, Bethlehem Pennsylvania.
Characterization of Aqueous Polymer Dispersions

Harm Wiese
3.1
Introduction
Aqueous polymer dispersions and the polymer films that form from them exhibit a
diverse and complex range of properties. Moreover, these systems possess a marked
heterogeneity at the mesoscopic level and their characterization is therefore a difficult task. In addition to determining the macroscopic properties of the dispersion
(Sect. 3.2.1), characterization requires investigating the polymer particles themselves
(Sect. 3.2.2), the residual volatile content (Sect. 3.2.3) and the aqueous phase
(Sect. 3.2.4). It is also important to understand the process of film formation
(Sect. 3.3.1) and to be able to describe the macroscopic and microscopic properties of
the film (Sects 3.3.2 and 3.3.3).
Given the large number of parameters and the numerous techniques employed to
measure them, this article can only hope to provide a broad overview of this vast subject area. For more detailed descriptions of the various measurement methods, the
reader is referred to the literature.
Beyond the general physical and chemical characterization of dispersions and
polymer films, a large number of application-specific tests exist. In this chapter,
space does not permit discussion of these tests nor of the wide variety of the formulations used in the different applications. Other areas which have had to be excluded
are the on-line and off-line methods of monitoring emulsion polymerization [1] and
techniques for determining the microbial contamination of polymer dispersions.
41
42
3 Characterization of Aqueous Polymer Dispersions
3.2
Polymer Dispersions
3.2.1
General Characterization of Dispersions

Solids content
In most of the applications the determination of the solids content is the first part of
any routine characterization of emulsion polymers, since it is the polymer and not
the water which is used in the final product.
Typically, the dispersion is dried to constant mass at a temperature of between 100
and 140 C (see, for example, ISO 1625) and the solids content is then expressed as
the percentage ratio of the dry matter to the total mass of the sample.
The dry matter comprises the polymer, emulsifiers and inorganic salts (formed by
the decomposition of the initiators and from neutralization). The volatile part includes the water and monomers which were not converted during the polymerization reaction. A comparison of the theoretical solids content (that is assuming complete monomer conversion) to the experimental value therefore provides a means of
assessing how far polymerization has proceeded to completion.
To accelerate the drying process, most modern laboratories make use of alternative drying techniques such as halogen lamps, microwaves and infrared radiators.
Because of a possible thermal decomposition of the polymer or emulsifiers however
the temperature of the sample must not be allowed to rise much above the temperature range specified above. Furthermore, the drying rate should not be too high since
this may cause skin formation on the surface of the sample. If the skin bursts material can be lost from the sample tray.
Coagulum and grit
In many applications polymer dispersions must only contain a very small fraction of
agglomerates with diameters greater than 1 m. Coarse components may be removed by filtration. Mesh sizes of between 45 and 180 m are typical. The filter
residue is known as the coagulum content or sieve residue.
A determination of sieve residue according to ISO 4576 may involve pre-diluting
the dispersion with water before filtering it through stainless steel filters having the
above mesh size. The residue is rinsed with water, dried and weighed. The amount
of residue is expressed as a fraction of the original dispersion mass. The type of filter
and the mesh size should be specified.
Fine agglomerates or large polymer particles which cannot be separated by filtration but are still visible in the wet or dry polymer film are known as grit. The grit is
undesirable in many applications, particularly in transparent coatings and must be
prevented during the polymerization process. To characterize the fraction of grit
present, the filtered dispersion is cast on to a glass plate using film applicators with
specified gap size (for example 45 or 125 m). When viewed with transmitted light,
grit particles can be detected by their refraction and diffraction effects. Normally, the
assessment is performed on the dry film. The number of grit particles per unit area
3.2 Polymer Dispersions
is counted or the grit pattern classified by comparison with standard samples. Possible sources of error in assessing grit content are wetting defects and occluded gas
bubbles.
pH, density and surface tension
pH is an important factor in both the stabilization and the formulation of polymer
dispersions. For example, dispersions that contain carboxylic acids are usually adjusted to a pH of between 7 and 9 in order to improve their stability and to increase
viscosity. pH measurements can be performed using a standard combination electrode (see ISO 976). Problems however often arise due to film formation on the glass
membrane.
The densities of most polymer dispersions are close to 1 g cm3 as the corresponding
polymers (with the exception of polyvinyl chloride and poly(vinylidene chloride))
have densities in the range 1.0 to 1.2 g cm3 [2]. Since the densities of the polymer
particles almost match the density of the aqueous phase, sedimentation is usually
only a problem in emulsion polymers if they contain very coarse particles. Density
measurements have been used in the past to follow the course of emulsion polymerization reactions, because the density of the monomer is usually lower than that of
the polymer (densitometry [1]). Densities can, for instance, be determined quite simply with a pycnometer (see ISO 2811). Very high precision density measurements
(5 106 g cm3) are possible with a vibrating-tube densimeter [3]. In this method,
the change in the resonant frequency of the tube, which depends on its total mass, is
measured when the dispersion is placed in it. It is essential that the sample is wholly free of gas bubbles.
The surface tension of a polymer dispersion is of major importance in the coating
of substrates. Good wetting of the substrate is achieved with a dispersion of low surface tension (Sect. 3.3.2). A general approach to obtain information on the wetting
properties of a dispersion is by measuring its surface tension in air, which is generally easy to determine experimentally. As a result of the emulsifiers used in emulsion
polymerization, the surface tensions of polymer dispersions generally lie some 20 to
40 units below that for water (73 mN m1).
Surface tension measurements can be made by the Du Nouy ring method (see ISO
1409), the hanging drop method or by using a stalagmometer [4]. In the latter two
techniques, the shape or volume of a drop of the dispersion as it emerges from a capillary is used to compute the surface tension. In the Du Nouy ring method, a thin
ring of platinum wire, suspended in the dispersion parallel to the surface, is withdrawn from the dispersion and the tensile force exerted by the liquid lamella that extends from the ring to the bulk liquid is measured just before it ruptures. As this
method requires relatively low dispersion viscosities (< 200 mPa s), it is often necessary to dilute the dispersion before measurement.
The ring method enables the static surface tension of the dispersion to be determined. When polymer dispersions are applied on large-scale coating machines, it is
also important how fast the surface tension of a freshly generated surface is able to
decrease. A device which permits this dynamic surface tension to be measured is the
maximum bubble pressure tensiometer [5]. In this method, gas bubbles are blown
43
44
through a capillary into the dispersion. The surface tension can be calculated on the
basis of the pressure changes during bubble formation. By varying the gas speed, the
dynamical processes during the growth of the surface can be accessed. It is worth
noting that the hanging drop and stalagmometer techniques are also dynamic methods, because the dispersion is continuously emerging from the capillary, albeit much
more slowly than the gas exiting the capillary in the maximum bubble pressure tensiometer.
Flow behavior
The flow behavior of a polymer dispersion or of its formulation is a central, and often
critical, processing parameter [6]. Paints, for example, must be easy to apply, should
form smooth surfaces, but should not sag when applied to a wall and should not
spatter during brush application. In contrast to conventional liquids, the rheological
properties of dispersions with a solids content above roughly 25 % are complex and
strongly dependent upon the forces applied, developing, in certain cases, a memory of these forces. This behavior is caused by the particle interactions that become
apparent when the solids content is high. Apart from solids content, particle size and
particle size distribution play a crucial role. Other factors affecting flow behavior are
the electrostatic charges of the polymer particles, their surface composition and water-soluble oligomers in the aqueous phase. In practice, particle charge has only a
relatively minor influence because the ionic strength of the aqueous phase is generally high enough (due to the presence of ions arising from the decomposition of the
initiator and from neutralization) to restrict to a few nanometers the range over
which the electrostatic forces are effective. Even relatively small amounts of watersoluble polymers have a pronounced influence on the flow properties of a dispersion
and this fact is used in practice to adjust the viscosity of the dispersion to the desired
level (thickeners). In contrast to polymer solutions, molecular weight and polymer
composition do not have a significant effect on the rheology of a polymer dispersion.
A simple crude assessment of flow behavior can be achieved on-site using socalled flow cups funnel-shaped vessels with specified orifices in their bases. The
measurement variable is the efflux time, that is the time taken for a known volume
of dispersion to exit the cup through the orifice. It is important to be aware of the fact
that a variety of cups are in use and that each type of cup produces a different efflux
time. The most common types are the ISO cups (complying with ISO 2431) and the
Ford cups used in the ASTM D 1200 test procedure.
The efflux time characterizes the low-shear flow behavior of a dispersion flowing
under its own weight. In many industrial applications, however, much greater shear
forces are applied (for example in coating machines) and these forces often have a
strong effect on the rheological properties of the dispersion (non-Newtonian behavior, see below). The effect of shear forces can be investigated by measuring a flow
curve with a rotational viscometer (Fig. 3-1 and ISO 3219). The dispersion is sheared
in a cup by an immersed rotating cylinder (spindle). In the measurement the velocity gradient (or shear rate) between the outer surface of the cylinder and the inner surface of the stationary cup is varied. The flow curve is the plot of the torque acting on
the cylinder (or the shear stress which can be derived from it) as a function of the
Rotational
viscometer
Flow curve
shear stress
shear
stress
shear
rate
shear rate D
Measuring a flow
curve using a rotational
viscometer.
Fig. 3-1
viscosity = / D
shear rate D. The (dynamic) viscosity is defined as the quotient of shear stress and
shear rate at every point along the flow curve. As both low viscous aqueous-like and
highly viscous dispersions are used, a measurement range of between one and
several thousand mPa s must be accessible. Because of the technical limitations of
the shear-force transducers, different cylinder/cup sizes are usually required in order to cover both low-viscosity to high-viscosity dispersions. Shear rates of up to
about 1000 s1 can be accessed with conventional rotational viscometers.
The Brookfield type of viscometer, in which one of a number of different spindle
types (RV, LV and so forth) is rotated in the sample dispersion, also enjoys widespread use for viscosity measurements (see ISO 2555 and 1652). The disadvantages
associated with this type of viscometer are that the shear rate is not well defined and
that the results of measurements made using different spindle types cannot be compared with one another.
Figure 3-2 presents a number of /D and /D curves which summarize the various phenomenological descriptions of how dispersion viscosity depends upon shear
rate or time. In many cases, one observes shear thinning (viscosity decreases with increasing shear rate) and thixotropic behavior (viscosity falls with time at a constant
shear rate). For this reason, the flow curve is recorded (as shown in Fig. 3-1) by measuring the shear stress both as a function of increasing shear rate and as a function of
decreasing shear rate. The hysteresis visible in Fig. 3-1 is typical of thixotropic dispersions.
Figure 3-3 shows a viscosity/shear rate dependence which is often observed for
polymer dispersions. In this log-log plot, an high initial plateau at low shear rates is
followed by a region of shear thinning which leads to a lower plateau at high shear
rates. Increasing the shear rate further induces a strong dilatancy and possibly also
coagulation. The shear thinning is assumed to be caused by the onset of ordering
within the dispersion as the polymer particles align themselves in parallel layers
(Fig. 3-3). The dilatancy is thought to be the result of the temporary formation of aggregates which can only pass by one another with difficulty.
45
46

Phenomenological
classification of the flow
behavior of polymer dispersions (, shear stress; D, shear
yield stress rate; , viscosity; t, time).
Shear rate dependence
Fig. 3-2
Newtonian
pseudoplastic,
shear thinning
dilatant,
shear thickng.
plastic
Time dependence (constant shear rate)
thixotropy
rheopexy
log (viscosity)
shear
thinning
dilatancy
log (shear rate)
statistical
distribution
Typical dependence
of the viscosity of a polymer dispersion on the shear rate.
Fig. 3-3
shear-induced
ordering
aggregation
When processing dispersions, a particular viscosity is often desired both at low

and at high shear rates, and these viscosities may be very different. A key objective in
the formulation and production of polymer dispersions is therefore to adjust the
shear-rate profile to meet the demands of the particular application. One way in
which this can be achieved is by the addition of polymeric thickeners, which influence the viscosity at low and at high shear rates differently depending upon their
structure and molecular weight.
Figure 3-4 shows schematically how the viscosity of a polymer dispersion varies as
a function of the volume fraction of the particles. The volume fraction is normalized to unity. In rheology it is more commonly used than the alternative solids
content of the dispersion. A characteristic steep increase in the viscosity is observed
as one approaches a maximum volume fraction m. Semi-empirical expressions

Dependence of viscosity on
the particle volume fraction.
Fig. 3-4
viscosity
shear rate:
low
high
volume
fraction
exist which provide more or less reasonable approximations of the experimental

curves. For the purposes of illustration the DoughertyKrieger equation is reproduced here:

= 1
0 m
2.5m
(3-1)
where 0 is the viscosity of the aqueous phase.

The theoretical upper limit for the maximum volume fraction m of monodisperse
spheres is 0.74, which is the value associated with hexagonal close packing. However, the steep rise in viscosity can occur at smaller volume fractions (often at around
0.55 to 0.6), depending upon the type of packing and the distance over which the
interparticle forces act. If the volume fraction is constant, decreasing particle size
results in a decrease in the distance between the particles and an increase in the
total particle surface area. This is the reason why dispersions containing fine
particles have higher viscosities than those containing coarser ones. Low viscosity at
high volume fractions can be achieved with a bimodal or broad size distribution
where the interstitial spaces between the larger particles are filled with the smaller
ones.
Machine processing exposes dispersions not only to shear but also to tensile
stresses (extensional flow). Because of the lack of commercially available test equipment, studies of the extensional flow of polymer dispersions are still in their infancy.
Little use is also made of viscoelastic techniques where the sample is subjected to
low-amplitude oscillatory shear and the amplitude and phase of the oscillating stress
is measured (usually as a function of the frequency of the oscillation).
Stability
The production, transport and processing of polymer dispersions expose these materials to significant degree of mechanical and thermal stress, which can lead to coagulation, sedimentation, phase separation or changes in viscosity. These changes are
generally due to instabilities of the polymer particles.
To avoid these problems, polymer dispersions are routinely tested for mechanical
and storage stability and, for certain applications, also subjected to freeze-thaw cycles.
After testing, any changes can be inspected visually or quantified using the methods
available for assessing the coagulum, the viscosity or the particle size distribution.
47
48
Mechanical stability: The dispersion is subjected to intensive, defined stirring (using a serrated stirring disk or rotor/stator units) as, for example in ISO 2006 where
the sample is agitated for 10 min at 14 000 rotations min1.
Storage stability: Accelerated testing is achieved by storing the dispersion at
enhanced temperature for a particular time (for example for 15 h at 80 C).
Freeze-thaw stability: This test provides information about the re-dispersibility of a
dispersion after having been frozen. The test involves subjecting the dispersion to
repeated freeze-thaw cycles (for example 16 h at 20 C followed by 8 h at + 23 C).
See, for example ISO 1147.
Stability with respect to additives: For many formulations, the stability of the dispersion with respect to various additives, such as electrolytes, solvents, fillers and pigments, must be tested. The additives are added either directly or, where necessary,
appropriately diluted, with any changes of the dispersion being assessed as described
above. Testing is often conducted on diluted dispersions to permit simple visual inspections to be carried out, though the conclusions that can be drawn from these
qualitative assessments are naturally limited.
Foaming behavior
Because of the presence of emulsifiers, polymer dispersions tend to foam. For many
applications (for example spray coating) foaming must be suppressed by the addition
of defoaming agents. The tendency of a dispersion to foam can be assessed by a
number of application oriented methods which can be used for relative measurements [7]. One common method uses a graduated cylinder whose base is sealed by a
porous glass frit through which gas can enter the cylinder. A known quantity of the
dispersion is placed on the frit, the gas flow initiated and the height of the foam within the cylinder is then recorded as a function of time. Good reproducibility requires
careful temperature control and thoroughly clean cylinders and frits. An alternative
approach is to measure the foam height after beating the dispersion within a cylinder with a perforated plate for a set time.
3.2.2
Characterization of Polymer Particles
This chapter restricts itself to a presentation of the methods used to characterize the
size and the surface of the polymer particles. Analysis of the polymer itself or the
particle morphology is usually performed on the polymer film or on the dried particles and is therefore treated later in Sect. 3.3.3.
Particle size
Polymer dispersions contain particles with diameters ranging from 10 to about
1500 nm. Typically, the particle size is between 100 and 250 nm. In the majority of
applications, particle size and particle size distribution are highly significant factors
that determine the properties of a polymer dispersion, such as its flow behavior or its
stability (Sect. 3.2.1). Measuring particle size is thus an important element when developing polymer dispersions and is also used in in-process control. A broad range of
methods are available for determining particle size [8] of which only light-scattering
and sedimentation techniques as well as modern fractionation methods will be discussed here. Electron microscopy is dealt with later in Sect. 3.3.3 which discusses the
characterization of particle and film morphology.
Light transmission
A distinctive feature of polymer dispersions is their turbidity. It is caused by light
scattering of the polymer particles due to the difference in the refractive indexes of
the polymer (typically 1.4 to 1.6 [2]) and water (1.33), and provides a simple way of
accessing the mean particle size in the dispersion. The link between the scattering
behavior of a dispersion of spherical particles and their diameter is provided by Mie
theory [9] and is shown in Fig. 3-5 for the relative transmission of white light through
various 0.01 %, w/w dispersions. Transmission increases as particle size falls or with
decreasing relative refractive index (refractive index of the polymer/refractive index
of water). If the relative refractive index is known, Fig. 3-5 can be used to determine
the mean average particle size from the observed relative light transmission. The
measurement can be performed within a matter of seconds using a simple arrangement of lamp, cell and photocell detector.
LT / %
100
80
Relative light transmission LT

of 0.01 % polymer dispersions as a
function of particle diameter for different relative refractive indexes, m.
LT = transmission through water/transmission through dispersion (2.5 cm cuvette, white light). m = refractive index
of the polymer/refractive index of water.
Fig. 3-5
60
m =1.10 (polyacrylate)
40
m =1.20
(polystyrene)
20
0
100
m =1.15
200
300
400
500
600
diameter / nm
For polydisperse dispersions, the measured light transmission is the inverse geometric mean of the relative transmissions LT1, LT2, of the respective mass fractions m1, m2, :
LT
= LT1 m 1 LT2 m 2
(3-2)
Laser light scattering

Of the many methods based on laser light scattering, dynamic light scattering
(DLS, also called quasielastic light scattering QELS or photon correlation spectroscopy PCS) has established itself as the most important technique of measuring
particle size in polymer dispersions [10]. The measurement (Fig. 3-6) involves directing a laser beam into a highly diluted sample of the dispersion and recording the
scattered light impinging on a photomultiplier at a particular angle.
49
50

laser
Dynamic light scattering.

Experimental set-up and intensity
fluctuations.
Fig. 3-6
sample
scattering angle
polarizer
analyzer
intensity
photomultiplier
time
The intensity of the scattered light reaching the detector is determined by the mutual interference of the light waves scattered from the individual particles in the dispersion. Because laser light is highly coherent, the scattered waves have a fixed phase
relationship to one another which is determined by the geometrical arrangement of
the scattering particles. The Brownian motion of the particles causes a statistical variation of the phase relationship in time, producing corresponding fluctuations in intensity at the detector (Fig. 3-6). The mean frequency of these fluctuations, which in
DLS is determined by autocorrelation of the scattering intensity, is proportional to
the diffusion coefficient of the particles. A hydrodynamic particle diameter d can
then be calculated from the measured diffusion coefficient, D, using the StokesEinstein equation:
D=
kT
3d
(3-3)
where k is Boltzmanns constant, T temperature, and the viscosity of the aqueous

phase. If the approximation of hard, non-interacting spheres is assumed, the hydrodynamic diameter is equal to the particle diameter.
The measurement, which takes only a few minutes to perform, can be used to determine particle diameters of between 5 nm and 5 m. In order to avoid complications due to multiple scattering of the laser light and due to particle interactions,
which influence diffusion, the measurements must be carried out on highly dilute
samples (105 to 102 %, w/w).
DLS is used as a routine means of determining particle size in monodisperse polymer dispersions. Typical systems employ a red helium-neon laser (wavelength:
633 nm) and a scattering angle of 90. However, the resolution achievable with such
systems when measuring polydisperse samples is generally quite low. As a rule of
thumb, the particle diameters of two fractions must differ by a factor of 3 or 4 if they
are to be clearly differentiated.
A further fact which complicates the analysis of polydisperse samples is that the
diffusion coefficients are weighted according to the scattering intensity. According to
Mie theory, the scattering intensity of light on particles whose diameter d is approximately equal to the wavelength of the light is a complex function of d, , the refractive indexes of the particles and the scattering angle. This fact considerably complicates the calculation of the exact mass fractions. For this reason, most equipment
manufacturers make use of simple approximate descriptions of the dependence of
scattering intensity on particle size. A more accurate approach is to measure the absolute scattering intensities and intensity fluctuations at a number of angles and
then to use Mie theory (assuming that the refractive indexes of the particles are
known) to convert the measured data to a particle size distribution [11].
Compared with DLS, static light scattering, in which the absolute intensity of the
scattered light is analyzed as a function of scattering angle, has become less relevant
as a method of determining polymer particle size. Static measurements are today
mainly used for characterizing dissolved macromolecules (with gyration radii
<100 nm) and for particles with a diameter greater than 1 m (Fraunhofer diffraction). The reader is referred to the literature for further details on these techniques [12, 13].
Centrifugation
Centrifugation methods allow a detailed and comprehensive characterization of
polymer dispersions. Figure 3-7 is a schematic view of an analytical ultracentrifuge
(AUC) equipped with two types of optical detection systems (schlieren optics and turbidity measurement at fixed radial position, turbidity optics) [14]. Particle size
determination with an AUC exploits the different sedimentation rates of the particles in the centrifugal field. According to Stokes law, the sedimentation time, ts, for
the path between the radial position of the meniscus, rm, and the position of the detection optics r (Fig. 3-7) in a centrifuge rotating at a constant angular velocity, , is
given by:
ts =
18 ln(r/rm )
(3-4)
( m )d 2 2
where is the viscosity of the aqueous phase, m the difference in density between the particles and the aqueous phase, and d is the particle diameter. Thus particle size determination requires the precise knowledge of the particle densities.
schlieren optics
turbidity optics
photomultiplier
video camera
schlieren
plate
Schematic diagram
of an analytical ultracentrifuge
( is the angular velocity of
the rotor).
Fig. 3-7
sample
cuvette
rm
r
lamp
laser
51
52
The measurement of the particle size distribution (PSD) is performed on dilute

samples (typical concentration: 0.05 to 2 %, w/w) in a so-called sedimentation velocity analysis using the turbidity optics (Fig. 3-7). At the start of the measurement the
dispersion is uniformly distributed throughout the cell and the detector registers an
attenuated laser beam. As soon as the first particle fraction has migrated under the
influence of the centrifugal field out of the optical path, the signal at the detector increases. Particle size can then be determined by measuring the time at which the signal begins to rise. By applying Mie scattering theory (knowledge of particle diameter
and refractive index required) the mass fraction of that particular particle fraction
can be computed from the increase in signal amplitude.
Measurements can be performed with high resolution in the diameter range between 20 and 2000 nm. Figure 3-8 illustrates the result of a sedimentation velocity
analysis on a mixture of ten polystyrene calibration latexes. Measurements on such
broadly distributed samples are usually performed with an exponentially increasing
rotation speed and require centrifuges capable of reaching 60 000 rotations min1
(Eq. 3-4); a measurement typically lasts 1 h. Machines designed to allow simultaneous determinations with eight sample cells per rotor are described in the literature [14].
Particle size
distribution (differential and cumulative)
of a mixture of ten
polystyrene calibration
latexes (sedimentation
velocity analysis).
Fig. 3-8
By carrying out the sedimentation velocity analysis not only in H2O but also in
D2O and in a 1:1 H2O:D2O mixture (H2O/D2O analysis), both the PSD and information on the density (and thus chemical uniformity) of the individual particle fractions
may be obtained.
Apart from the sedimentation velocity analysis, the AUC may also be used to perform a so-called density gradient analysis. In a density gradient analysis, a water-soluble substance of high density (CsCl or the iodinated sugar metrizamide) is added to
the sample so that in the liquid phase a radial density gradient is established at equilibrium in the centrifugal field. The various particle fractions migrate along the gradient to the point having their own density, thus allowing the densities as in the
H2O/D2O analysis to be determined. I this case the schlieren optics (Fig. 3-7),
which detect changes in the refractive index along the radial axis, is used for the
analysis. In contrast to the turbidity optics, a photo of the entire cell is taken once
equilibrium has been established. Normally between 10 and 20 h are needed to
achieve equilibrium.
The advantage of using the schlieren optics is that in addition to the particle fractions also dissolved macromolecules can be studied with respect to chemical composition and molecular weight. Like the polymer particles, the macromolecules migrate
along the density gradient to their isodensity point. However, the small size of the
macromolecules means that the bands are diffusion broadened. If the scaling law
that relates the diffusion coefficient to the molecular weight is known, the latter can
be calculated.
The considerable amount of information obtainable by AUC analyses must be
viewed in the light of the considerable technical expense and effort needed to run
such a machine. At present, only a few laboratories have access to this technology.
Disc centrifuges are a cost-effective alternative (rotation speeds of up to 15 000 rotations min1).
Because of the lower rotation speeds in a disc centrifuge a different analysis technique has to be employed. The cell is first filled with a spin fluid and then a sample
layer is injected on top of the fluid while the disc is rotating. By this means the particle fractions migrate past the detection optics layer by layer according to their differing sedimentation velocities. Unfortunately, it is often difficult to achieve a uniform
injection layer in practice (because of disruptions of the sample flow front). For this
reason, and also because of the low density difference between the polymer particles
and the aqueous phase, disc centrifuge sedimentometry is not widely used for the
characterization of polymer dispersions.
Modern fractionation methods
In recent years a number of new fractionation techniques, such as capillary hydrodynamic fractionation (CHDF) [15] and field field-flow fractionation (F-FFF) [16],
have established themselves as reliable alternatives to centrifugation in PSD analysis. Only CHDF will be discussed here. The technique involves injecting a small
amount of the sample into an aqueous eluent containing an emulsifying agent. The
eluent is pumped through a glass capillary tubing (inner diameter 710 m) and in
so doing adopts a laminar flow profile (Fig. 3-9). The larger the particles, the less able
they are to approach the capillary wall during thermal Brownian motion. Large particles are therefore, on average, flowing in faster stream lines than smaller ones and
are transported more rapidly through the capillary. The particle fractions are detected using a UV-detector. Complications due to specific interactions between the particles themselves or between the particles and the wall are eliminated by using a particular type and amount of emulsifier and working at low ionic strength.
When the apparatus has been calibrated with particles of known size, the PSD of a
sample can be determined from its elution curve. As is the case for AUC, calculating
the mass fractions requires application of Mie scattering theory, but this is not implemented in CHDF equipment currently available on the market. The manufacturers content themselves with a relative conversion based on the extinction coefficients
53
54
glass capillary
parabolic
flow field
Capillary
hydrodynamic
fractionation (CHDF):
the principle.
Fig. 3-9
inaccessible regions
(shown for two
different particle sizes)
particle
of polystyrene calibration latexes. Typically, CHDF is able to measure particle diameters in the range 10 to 400 nm. By using capillaries with a larger inner diameter, the
range can be extended to include particles about 1 m in diameter, but the resolution
achievable at the lower end of the particle size range is then reduced. A measurement takes about 10 minutes to complete.
Particle surface
The surface characterization of a polymer particle involves investigating the adsorption of ions and amphiphilic molecules (emulsifiers, oligomers), determining the
number of covalently bonded functional groups and acquiring information on the
structure of the interfacial layer (swollen state or hairy layers). Presently this task
can not be solved satisfactorily. The main methods used are titrimetric analyses on
purified dispersions, soap titration and electrokinetics.
Titrimetric methods
Titrimetric analysis of polymer dispersions is mainly used to quantitatively determine acidic and basic groups covalently bonded to the particle surface (from initiators or comonomers). Before titration the dispersion has to be cleaned thoroughly,
that is all traces of amphiphilic and ionic components have to be removed. The recommended purification technique employs a combination of anionic and cationic
ion-exchange resin beads [17]. The beads have to be thoroughly purified themselves
before use.
After purification, the dispersion is titrated potentiometrically to determine the
quantity of residual, that is covalently bonded, acid or base groups [17]. When titrating for acids, the different pKa values enable distinction of sulfuric/sulfonic acid and
carboxylic acid. Fundamental questions that arise in connection with this method
are (1) whether all of the bonded acid groups can be neutralized because of the high
resulting charge density, and (2) to what extent the particle surface reorganizes during neutralization. The increasing hydrophilicity might, for instance, cause particle
swelling and a migration of acid groups from the particle interior to the surface.
Soap titration
Soap titration is employed to determine the emulsifier coverage of the polymer
particles in the dispersion. Emulsifier coverage is defined as the percentage of the
particles total occupiable surface area that is covered by emulsifier. In soap titration
the surface tension of the dispersion is measured, for example using the Du Nuoy
ring method [4], as a function of the emulsifier added (Fig. 3-10). The emulsifier
molecules distribute themselves between the particle surfaces, the aqueous phase
and the dispersion/air interface where the surface tension is measured. As a rule the
equilibrium lies well over in favor of adsorption on the particle surface, so that if the
surfaces are not fully covered, only a few of the added emulsifier molecules are
found at the dispersion/air interface where, as a consequence, relatively high surface
tension values are recorded. As more and more emulsifier is added, gradually decreases (Fig. 3-10). When the surface of the particles is completely covered, the excess emulsifiers must be taken up by the aqueous phase, leading eventually to the
formation of micelles. From this point on the aqueous phase can accommodate large
amounts of emulsifier and remains essentially constant. The sharp change in the
gradient of the curve shown in Fig. 3-10 determines the critical micelle concentration (CMC) of the particular emulsifier in the dispersion under test.
The soap titration is usually carried out at a series of solids contents (for example,
2.5, 5, 7.5 and 10 %, w/w) in order to eliminate the amount of emulsifier required for
micelle formation. Plotting the resulting CMC values against the solids content produces a straight line whose slope is inversely proportional to the emulsifier coverage
(Maron plot, see [18, 19]). If the size of the particles is known, the effective molecular surface area of the emulsifier occupied on the particle can be calculated. Studies
have shown that the emulsifier molecular surface area is determined not only by the
type of polymer, but also by the way in which comonomers and initiator residues are
incorporated into the particle surface.
air
emulsifier
polymer
particle
model
dispersion
100% coverage of
particle surface
micelle
formation
surface
tension
Fig. 3-10 Soap titration. Determination of

the emulsifier coverage
of the polymer particles.
cmc
log(emulsifier conc.)
55
56
The soap titration technique is strictly only applicable for dispersions which contain one type of emulsifier. However, many polymer dispersions are stabilized by a
combination of emulsifiers, often both ionic and non-ionic types. One approach in
such cases is to perform the study with the emulsifier mixture, though there is the
problem of exchange processes occurring on the particle surfaces if one of the emulsifiers is preferentially adsorbed. The results may also be affected by adsorbed amphiphilic oligomers generated during the emulsion polymerization.
Electrokinetics
Electrokinetic measurements [20] are used to access the electrophoretic mobility
e of the polymer particles and thereby to get information on their charges. Because
of the relatively small particle size of 100 to 250 nm, the measurement technique
used for polymer dispersions is laser Doppler electrophoresis. Sample preparation
and experimental set-up correspond to those of a dynamic light scattering experiment (Sect. 3.2.2, Fig. 3-6). The only difference is a pair of electrodes immersed in
the sample between which the particles are moved backwards and forwards by an alternating voltage.
The electrophoretic mobility, e, is related to the zeta potential, , which is defined
as the electric potential at the surface of shear of the particles and is therefore a
measure of their total charge. Unfortunately, the electrophoretic mobility of dispersion particles does not depend solely on the zeta potential, but also in a complex way
on particle size and on the ionic strength and viscosity of the aqueous phase [21]. It is
only at the limits of very high and very low ionic strength that can be directly computed from the measured e values (HelmholtzSmoluchowski or Hckel approximations).
These complex dependencies and some experimental difficulties (for example,
due to electro-osmotic convection) are the reason why electrokinetic measurements
are still of only minor importance in the characterization of polymer dispersions. On
the other hand, the technique provides a simple means by which the adsorption of
amphiphilic components (emulsifiers, protective colloids and so forth) on the particle surfaces can be followed at least qualitatively.
3.2.3
Residual Volatiles
The increased attention paid to ecological and environmental issues in recent years
has lead to a growing significance of residual volatile determination in polymer dispersions. Depending upon the production process, polymer dispersions may contain
small quantities of residual monomers, monomer impurities, substances formed by
the decomposition of the initiator or from chemical reactions between the various
components in the reaction mixture. The European Union has defined such substances as volatiles, if they have a boiling point below 250 C.
The determination of the residual volatiles is usually performed by capillary column gas chromatography [22]. Different sampling techniques are described. In the
headspace technique (see ISO 13741-2) a diluted dispersion sample is mixed with an
internal standard and a polymerization inhibitor. The sample is then heated in a

sealed vial (for example at 90 C for 1 h) and, after equilibration, a small part of the
headspace vapors is introduced into the chromatography column. In the direct liquid
injection method (see ISO 13741-1) a diluted dispersion sample is mixed with an internal standard and directly injected on to the hot insert liner (temperature
150200 C) of the chromatograph causing the dispersion to vaporize instantly. In
both techniques the column (typically coated with a 1 m thick layer of polydimethylsiloxane, PDMS) is initially thermostatted at 50 C causing the injected
volatiles to condense at the entrance part of the column. The temperature of the column is then raised linearly to 250 C and the component substances are fractionated
by the column in the order of their volatility and detected for example by a flame ionization detector (FID). Careful calibration is necessary in order to assign elution time
and signal height to the type and amount of the components. With this technique,
the typical residual volatiles of polymer dispersions can be quantitatively determined
in a range between 10 and approximately 10,000 ppm (measurement duration about
45 minutes).
3.2.4
Aqueous Phase Analysis
In common practice the aqueous phase, or serum, of a polymer dispersion is only investigated for its pH (Sect. 3.2.1). On the other hand, the aqueous phase contains a
host of substances which play an important role in many applications. These substances include: (a) emulsifiers, (b) initiator residues, (c) electrolytes from the neutralization process or from initiator decomposition (for example sodium sulfate from
sodium peroxodisulfate), (d) unreacted water-soluble monomers such as acrylic acid
or vinyl sulfonic acid, and (e) water-soluble oligomers formed from this kind of
monomers.
To analyze the aqueous phase for any of these substances, it must first be separated from the polymer particles. Both flocculation and membrane filtration techniques
can be used for this purpose and they are described in more detail below. The detection of the substances listed above can then be performed with the usual array of analytical methods used for characterizing aqueous media. For the determination of
emulsifiers, electrolytes and water-soluble monomers, ion chromatography (IC) and
high-performance liquid chromatography (HPLC) are particularly suitable. The techniques of choice for characterizing oligomers are gel permeation chromatography
(GPC) and capillary electrophoresis (CE). As these analytical techniques are not specific to colloidal chemistry, they will not be described further here and the reader
should consult the literature for more information.
Serum separation techniques
Flocculation techniques
The dispersion is for instance flocculated by the addition of acids or salts (typically
containing polyvalent ions). Examples of salts of this type are aluminum sulfate or
57
58
the combination of K4Fe(CN)6 and ZnSO4 (Carrez precipitation). Subjecting the dispersion to freeze-thaw cycles also often proves successful. A further possibility is
centrifugation. If the centrifugal forces are high enough, the dispersion flocculates at
the base of the cell allowing the aqueous phase to be subsequently drawn off. In the
case of well-stabilized dispersions, high-performance centrifuges are required. Two
disadvantages of the flocculation methods should be mentioned. First, the flocculated polymer particles can release considerable amounts of emulsifier into the aqueous phase. Secondly, centrifugation may cause components in the aqueous phase to
be flocculated along with the polymer particles.
Membrane filtration techniques
In this case, the polymer particles are separated from the aqueous phase by a
membrane through which the particles cannot permeate. Suitable membranes include dialysis tubes (molecular weight cut-off: 10 00015 000 g mol1) or, for example, Nucleopore membranes, which are available with pore diameters from 15 nm to
several micrometers.
In dialysis the dispersion is placed in a well-sealed tube and immersed for several
days in water, which should be changed regularly. Before being analyzed, the
dialysate usually has to be concentrated. Changing the water and concentrating the
dialysate can both be carried out easily if the dialysis tube is placed inside a Soxhlet
apparatus.
In the diafiltration method [23], which uses the Nucleopore membranes, the dispersion is filtered under pressure through the membrane. Like the dialysis method,
diafiltration can be used not only to separate the aqueous phase, but also to purify a
polymer dispersion, that is to separate all the water-soluble components. When used
for the latter purpose, the dispersion is continuously rinsed with water during the diafiltration process. Filter cake formation is prevented by adopting a cross-flow filtration arrangement in which, for example, a stirrer is used to create a convective current parallel to the surface of the membrane.
3.3
Polymer Films
In the typical applications such as paints, adhesives, textiles and non-wovens the dispersions or their formulations are subjected to a drying process. The properties of
the dispersion itself are for this reason only of relevance during processing. It is the
properties of the polymer film that are of importance to the end product, and these
properties are essentially determined by the polymer itself. Characterizing the properties of the polymer films is thus a subject of central relevance to the typical dispersion applications.
In the description of methods presented in this chapter, the focus is on pure polymer films. However, these methods are equally applicable to characterizing formulated films such as paints.
3.3 Polymer Films
3.3.1
Film Formation
In the drying stage at the end of water evaporation the particles adopt a hexagonal
close-packed geometry. Good subsequent film formation requires a high level of
polymer particle deformability and the rapid interdiffusion of polymer chains between the particles. Emulsion polymers therefore possess a so-called minimum film
formation temperature (MFT), below which no compact film can be formed. The determination of the MFT is discussed below.
Immediately after its formation, the properties of the polymer film are still mainly
determined by the particulate structure of the dispersion. The interstitial regions will
still house the water-soluble components (salts, emulsifiers, oligomers and so forth)
and multiphase particles, for example, will initially give films with micro domains.
The phases formed directly after drying are not in thermodynamic equilibrium with
one another. Changes in these micro domains can occur gradually with time, or more
rapidly if subjected to higher temperatures. An example of such changes is the tendency of the water-soluble components to group together or to migrate to the surface
of the film. In multiphase films, the micro domains can merge to form macro domains.
The quality of a polymer film is therefore influenced not only by the properties of
the constituent polymer, but also by the conditions under which the dispersion is
dried. To achieve reproducible results when characterizing polymer films, it is necessary to control such parameters as wet film thickness, drying temperature, air humidity, air convection currents, and drying and storage times. Rapid drying, in particular, can cause a skin to form on the surface of dispersion, thus hindering the controlled drying of the dispersion below. If low-volatility substances, such as certain
film-forming agents, are present, thorough drying of the film is essential if the measurement results are to be meaningful.
To create a film with a defined (dry film) thickness of up to about 200 m, the dispersion is usually cast on to the substrate using either a drawdown film applicator or
a roller applicator. Suitable substrates are glass, polyethylene, polyethylene terephthalate or teflon. Films with thicknesses in the millimeter range, such as are used for
mechanical strength testing, can be formed by pouring the dispersion into flexible
polyethylene or silicone rubber trays, which facilitate the removal of the film after
drying.
Minimum film formation temperature (MFFT)
The minimum film formation temperature is determined according to ISO 2115 by
spreading the dispersion at defined layer thickness (for example at 200 m wet) on a
plate along which a linear temperature gradient is established (for example from 0 to
40 C). Commercial equipment usually has shallow channels engraved in the plate
which facilitate the spreading of the dispersion. The drying has to be performed in a
controlled atmospheric environment. Once completely dry, the film is visually inspected for the presence of cracks and cloudiness. The MFFT is the lowest temperature at which a homogeneous and crack-free film forms. The MFFT is either displayed by built-in temperature sensors or can be determined using a surface temper-
59
60
ature probe. The method also enables the so-called white-point temperature to be
determined. This is the temperature below which a cloudy film forms and above
which a clear, transparent film results. The white-point temperature always lies a few
degrees below the MFFT.
As an aqueous dispersion can only dry above 0 C, the MFFT and white-point temperature are only defined above this value. The control of the polymer layer thickness
is crucial for the measurements. Mechanical stress may develop during film formation (particularly when crosslinking is involved) which leads to crack formation
above a certain layer thickness. A further point which should be considered is that
very short drying times are often used in dispersion processing, for example on coating machines. In this case, the MFFT may well lie above the value determined
according to ISO 2115. The discrepancy is caused by kinetic limitations in water
evaporation and polymer interdiffusion [24].
The main factors determining the MFFT of an emulsion polymer are the composition, molecular weight and crosslinking density of the main copolymer [24]. However, particle size and the water-soluble substances such as auxiliary monomers or
emulsifiers also play an important role. The effect of these substances is to retard the
rate at which water leaves the interstitial region. As long as the water is present the
mobility of the polymer chains is increased and interdiffusion thus favored. The
MFFT of a dispersion can therefore be lowered by inclusion of auxiliary monomers.
In the case of multiphase polymer particles, the MFFT is strongly dependent upon
morphology. An example of this type of system are the core-shell particles with
copolymers of differing glass temperature discussed below.
3.3.2
Macroscopic Characterization of Polymer Films

Thermal characterization
Thermal characterization of an emulsion polymer essentially means the measurement of the glass transition temperature Tg, that is the temperature above which the
hard, glass-like polymer film becomes viscous or rubber-like. Polymers whose Tg lies
well above room temperature are designated as hard, those with a Tg much lower
than room temperature as soft. Normally Tg is measured by differential scanning
calorimetry (DSC [25]). In this technique, the difference between the heat absorbed
per unit time by the polymer film to that absorbed by a thermally inert reference material is recorded during a linear temperature ramp. The sample and the reference
are placed on a sensor plate of defined thermal resistance R, and the temperature difference T between the sample and the reference is then recorded over the temperature ramp. Usually, the heat flow difference, which is the negative quotient of T and
R, is plotted as a function of temperature (Fig. 3-11).
Figure 3-11 is a schematic representation of a DSC measurement in which a glass
transition and a melting process are shown. A glass transition is not a second-order
transition between two defined equilibrium states. It therefore occurs over a relatively wide temperature range and depends upon the rate of temperature change. For
this reason a number of different definitions of the glass transition temperature can
3.3 Polymer Films
melting process
heat flow
difference
Hs
increasing
endothermicity
Fig. 3-11 DSC. Investigation

of glass transitions and melting
processes in polymer films
(, heating rate; Tg, glass
transition temperature;
Cp, heat capacity difference
of the polymer in the temperature regions below and above
Tg; Tonset and Tpeak, different
definitions of the melting
point; Hs, enthalpy of
melting).
glass transition
Tpeak
Cp
Tonset
Tg
temperature
be found in the literature. The Tg shown in Fig. 3-11 is that of the so-called midpoint definition. The ISO 11357-1 standard specifies a heating and cooling rate of
between 0.5 and 20 K min1 and recommends the repeat heating of the sample (that
is heat/cool/heat). This repeat heating helps to eliminate any influence of the thermal history and the drying process, for example due to the presence of residual water. Tg should always be determined during the second heating ramp. The investigated temperature range, in the case of soft adhesives, should start at 110 C and, in
the case of hard coatings, should extend to 150 C.
Melting processes are uncommon in the emulsion polymers described in this
book. Exceptions are the melting and crystallization phenomena observed with ethylene oxide chains when highly ethoxylated emulsifiers or protective colloids are employed in the polymerization process.
The glass transition temperature of an emulsion polymer is the temperature above
which the polymer chains become mobile and it is therefore directly related to the
minimum film formation temperature MFFT. In contrast to Tg, which is essentially
determined by the main copolymer, the MFFT is influenced by the drying process.
If, for instance, water is able to solubilize part of the copolymer during the coalescence of the particles at the end of the drying stage, the MFFT can be lowered significantly. This phenomenon, which is known as Tg/MFFT splitting, is typical of vinyl
acetate emulsion polymers but also observed for other polymer types when large
amounts of hydrophilic monomers are used in the polymerization process.
Tg/MFFT splitting is important for all applications in which a hard film with a low
MFFT is required.
Tg values of several important homopolymers are listed in reference [2]. The values
were determined on samples of non-crosslinked emulsion polymers. In crosslinked
polymers, Tg is shifted to higher temperatures as a result of the restricted chain mobility. A number of approximations for calculating the Tg of copolymers have been
proposed in the literature [26]. The GordonTaylor equation usually produces reliable results:
61
62
Tg =
Tg(1)m 1 + Tg( 2)m 2

m 1 + m 2
(3-5)
Here m1 and m2 are the mass fractions of the monomers 1 and 2 and is defined
as (2)/(1), with the difference in the coefficient of expansion of the molten
and glass states of the respective homopolymer. If is not known, the Fox equation
can be used to provide a simple estimate:
1 m1 m 2
=
+
Tg Tg(1) Tg( 2)
(3-6)
For statistical copolymers, the width of the glass transition corresponds approximately to that of the homopolymers. The transition broadens with increasing
inhomogeneity of the monomer distribution within and between the polymer
chains.
Beyond enabling the glass transition temperature to be measured, differential
scanning calorimetry also provides a simple means of investigating polymer compatibility and phase separation in polymer films. If a film contains two phases, this
shows up as two glass transition regions in the DSC scan. The relative fraction of the
phases can be determined by the ratio of the measured heat capacities. If, on the other hand, the constituent polymers are wholly compatible, only one glass transition is
recorded and this lies between those of the individual components. In a similar way,
the compatibility of the polymer to low molecular weight substances such as plasticizers can be examined.
Mechanical characterization
The mechanical characterization of a polymer film is performed on a free film. This
requires drying of the dispersion on a substrate of low surface energy (such as Teflon
or silicone rubber) from which it can be lifted without applying strong mechanical
forces. Great care is required when preparing such free films as defects or deformations caused by mechanical stress have a detrimental effect on the reproducibility of
the measurements. Mechanical characterization is typically performed by recording
the stress-strain curve up until film rupture takes place (large deformations) or by
dynamic mechanical analysis within the elastic limit (small deformations).
Stress-strain measurements
A stress-strain measurement on a free polymer film is performed as a uniaxial tensile test. The film (typical geometry: 250 m thick, 30 mm long and 510 mm wide)
is loaded into a tensile testing machine and the stress (force per unit area) recorded
as a function of tensile strain (elongation over original length) at a constant drawing
speed (typically 10100 mm min1) until the test sample ruptures [27]. Figure 3-12
shows a typical form of a stress-strain diagram measured for a polymer film. At
small levels of deformation, the stress-strain curve is linear and the film behaves
elastically. The gradient of the curve in this region is called the elastic modulus (or
Youngs modulus) of the material under test. Other parameters available from this
test are the tensile strength and the elongation at break. The integral under the curve
3.3 Polymer Films

Fig. 3-12 Typical stress-strain
curve for a polymer film.
stress
tensile strength
work of fracture
elongation
at break
strain
to failure represents the energy per unit volume required to rupture the sample
(work of fracture or toughness).
The stress-strain behavior shown in Fig. 3-12 is typical of the elastomeric response
of a polymer film. Curves of this type are found in crosslinked films above the glass
transition and in non-crosslinked films in the so-called entanglement region (see
dynamic mechanical analysis below). Hard, highly crosslinked films below their
glass transition temperature are characterized by their relatively small elongation at
break and their high tensile strength. These materials show essentially elastic behavior up until rupture. On the other hand, non-crosslinked films (in the vicinity of
Tg) are elastic at small elongations and start to deform plastically above a critical value. This phenomenon is known as necking. In this case, the tensile stress passes
through a maximum after which it remains relatively constant over a certain deformation range (before rising again shortly before rupture).
Stress-strain measurements are also a useful tool for studying film formation in
polymer films. Such an investigation, in which the process of polymer chain interdiffusion in n-butyl methacrylate films was followed by monitoring the films work of
fracture, has been reported elsewhere [28].
Dynamic mechanical analysis
In dynamic mechanical analysis (DMA [27]) of a polymer film, a sample with the
same dimensions as in the tensile stress-strain analysis described above is slightly
pre-tensioned and then subjected to a low-amplitude and low-frequency sinusoidal
deformation (typically 0.1 % and 1 Hz respectively). As the measurement is performed below the materials elastic limit, the stress follows the strain in a sinusoidal
manner. The amplitude ratio and the phase difference between the stress and strain
oscillations enables the dynamic elastic modulus E* to be calculated:
E* = E + iE
(3-7)
where E is the so-called storage modulus, E the loss modulus and i = (1). E is a
measure of the (recoverable) energy stored in the film during deformation and E is
the (irrecoverable) energy that is dissipated in the film as heat.
In conventional DMA, the storage and loss moduli are recorded as a function of
the oscillation frequency. Of more widespread application are DMA measurements
63
64

Dynamic mechanical
analysis. Storage (E) and loss
(E) moduli as a function of
temperature for a polymer film
of poly(2-ethylhexyl methacrylate).
Fig. 3-13
in which E and E are measured at a constant frequency over a temperature range.

As a result of the time-temperature superposition principle, the temperature scan
provides the same information as the frequency scan. Figure 3-13 shows a typical
DMA measurement (temperature scan) on a non-crosslinked polymer film.
The storage and loss moduli can be seen to vary over several orders of magnitude
across the temperature range. A high storage modulus is measured in the glassy
state. It decreases rapidly in the glass transition region as the film softens. The loss
modulus passes through a maximum at the beginning of the glass transition region.
This maximum can be used as an alternative definition of the glass transition temperature of the sample (compare with Sect. 3.3.2).
After passing through the glass transition region, the moduli decrease more weakly with temperature as a result of polymer chain entanglement and crosslinking
within the film. In the case of non-crosslinked polymers, a further increase in temperature causes the film to undergo plastic flow.
For non-crosslinked polymers, the entanglement region is only observed above a
critical molecular weight (typically between 2000 and 10 000 g mol1). This molecular weight corresponds to the polymer chain length above which physical chain entanglement (temporary crosslinking) can occur (entanglement molecular weight).
For crosslinked polymer films, the storage and loss moduli measured above the
glass transition region remain relatively constant or exhibit a slightly positive temperature dependence (crosslinking plateau). E assumes significantly lower values
than E. According to the theory of rubber-elasticity, the storage and loss moduli in
this region have the following values:
E = 3RT/Mc; E = 0
(3-8)
where is the film density, R the gas constant, T the temperature and Mc the average
molecular weight between two crosslinking sites. Equation (3-8) shows that in this
ideal case the storage modulus of a crosslinked film increases linearly with temperature and provides a direct means of accessing the crosslinking density of the polymer ( = /Mc).
3.3 Polymer Films
When analyzing multiphase samples, it may be possible to detect several glass

transitions in a DMA measurement as was the case in the thermal characterization
of multiphase polymer films described above. DMA is also able to provide information on the effects of plasticizers, resins and fillers on the polymer film.
In the case of soft films which tend to flow it is easier to measure the dynamic
shear modulus G* = G + iG than the elastic modulus E*.
The advantage is that the film is placed between two plates rather than being
clamped at its ends. G* is measured by exerting a small sinusoidal torsional displacement of one of the plates. The information content of the shear moduli curves
corresponds to that of the elastic moduli ones.
Optical characterization
The transparency, gloss and color of a film are important in many applications. The
complete optical characterization of a polymer film would require measuring the optical response of the film as a function of wavelength, angles of incidence and detection (relative to the surface normal), film thickness and type of substrate. Despite the
fact that a multitude of optical techniques are available for such measurements (UVvisible spectroscopy, ellipsometry, laser scattering and so forth), in most applications
simple techniques using white light are employed [29].
Film opacity is usually measured by the transmission of white light through a free
film. The back-scattering power is determined using an integrating sphere photometer, that is diffuse illumination and detection of the scattered light at 0 to the film
surface normal. Measurements of film gloss are performed by recording the intensity of light reflected at a specified angle to the normal (usually 20, 60 or 85). In colormeasuring instruments, wavelength-dependent measurements are conducted at
known angles of incidence and detection and the results then converted to color values. It is important to realize that when investigating films that are not wholly
opaque to the wavelength concerned, the results will be influenced by film thickness
and by the choice of substrate (color, transparency and so forth). For this reason, optical measurements on polymer films are often performed using black foils as substrate (for example pigment blackened PVC).
Behavior with respect to liquids
In a multitude of applications, polymer films get in contact with water or organic
solvents. These liquids can wet, swell, permeate or even dissolve the film. To characterize these processes (with the exception of wetting) simple gravimetric methods
are normally used.
Wetting
If a series of liquids with increasing surface tension L are brought into contact
with a polymer film, complete wetting will occur below a critical surface tension C
and partial wetting (that is droplet formation) will be observed above this value (see
Fig. 3-14). The critical surface tension C is a characteristic of the polymer film and a
measure of its surface energy. Films with a high C are easy to wet, those with a low
C value can only be wetted with difficulty.
65
66

Determination of
the critical surface energy C
of polymer films using the
Zisman method ( is the
contact angle).
Fig. 3-14
Wetting is quantified by measuring the contact angle, which is the angle subtended by the drop at the point of contact to the film. A contact angle of 0 reflects complete wetting. In contrast, a value of 180 represents complete non-wetting (see
Fig. 3-14). The contact angle is measured either by image analysis (sessile drop
method) or by using a Wilhelmy balance [4, 30].
In the Wilhelmy balance method, the polymer film is suspended vertically from
the balance and then lowered slowly until it is in contact with the liquid. If the surface tension at the liquid-air interface is known, the contact angle can be calculated
from the difference in sample weight when in and out of contact with the liquid.
The Wilhelmy method can also be used to investigate dynamic wetting processes
by recording the formation of the liquid lamella in time or by immersing and withdrawing the polymer film into and from the liquid at constant rate. Time-dependent
measurements are also useful for examining cases in which liquid is taken up after
the polymer film has been wetted or, conversely, in which the liquid dissolves film
components such as emulsifiers.
In addition to their use in determining the critical surface energy C, contact angle
measurements can also provide information on the polarity of the film surface. In
this case the measurements are conducted with a series of liquids of different polarity (for example isopropanol-water mixtures). For evaluating the data a number
of procedures have been published (see for example the Good-Girifalco-Fowkes
method [30, 31]).
Swelling, dissolution and permeation
The usual means of characterizing swelling and dissolution processes involves
storing weighed films in the solvent of interest (for example water or tetrahydrofuran). After a defined period of immersion (for example 24 h), the film is removed
3.3 Polymer Films
from the liquid, liquid adhering to the surface of the film is removed and the sample
is weighed in its wet and dry state.
The percentage increase of the wet film relative to its initial weight prior to immersion is known as the solvent or water uptake. The weight loss of the dried film
compared to the initial sample weight specifies the extraction loss and is due to the
partial dissolution (leaching) of film components in the liquid. Soluble and insoluble
film parts are frequently referred to as the sol and gel fractions. Measurements conducted for different storage periods provide information on the kinetics of the sorption and dissolution processes. The speed with which the wet film dries may also be
of significance for certain applications. Further parameters of interest are the volume changes that accompany the swelling and the subsequent drying.
Interparticle crosslinking (that is crosslinking after film formation) reduces the
swelling and dissolution of the polymer film strongly. Quantifying the solvent uptake and extraction loss is therefore a simple means for characterizing this type of
crosslinking. In a crosslinked film, the mean molecular weight Mc between two
crosslinking sites can be calculated from by the degree of swelling in a particular solvent using the Flory-Huggins equation [32]:
Mc =
VS (Q 5/ 3 Q / 2)
0.5
(3-9)
where Q is the swelling ratio by volume, is the polymer density, VS the molar volume of the solvent and the Flory-Huggins interaction parameter for the polymersolvent pair (see also Eq. 3-8).
Sorption and dissolution measurements on polymer films in various solvents are
also the basis for determining the solubility parameters of a polymer [33], which are
a measure of its solvent compatibility. In many applications, what is sought is the
greatest possible compatibility or incompatibility between a polymer film and a particular solvent. In the case of a crosslinked polymer film, the greater the swelling the
better the compatibility. In the case of a non-crosslinked polymer film, the greatest
level of compatibility is achieved at the maximum solution viscosity.
Many of the methods used for the characterization of the emulsion polymer
macromolecules (see Sect. 3.3.3) require the polymer film to be dissolved in a solvent. Full dissolution is hindered if a gel fraction is present. The gel fraction is the result not only of covalent crosslinking between polymer chains, but also of the physical entanglement of the chains in these high-molecular-weight emulsion polymers.
The gel fraction is often higher in polymer films which have been subjected to longer
drying times as the chain segments then have the opportunity for greater interdiffusion.
Swelling particularly due to the uptake of water often creates opacity within the
film (whitening) which is undesirable in many applications. This phenomenon is
caused by refractive index inhomogeneities created in the film when water penetrates the interstitial regions between the particles. Characterization of film whitening can be done with conventional techniques as discussed above.
The permeation of a polymer film by a liquid can be investigated by filling the liquid into a container whose base is made of the polymer film under test. The loss of
67
68
liquid is then recorded gravimetrically as a function of time. Such measurements are

only reproducible if pore-free films can be produced. Films can be tested for the absence of pores by examining their gas tightness.
Gas permeation
The permeability of polymer films to vapors can be measured gravimetrically in analogy to liquid permeability (above), with the difference that the film now acts as the lid
rather than the base of a container partially filled with the liquid forming the vapor.
If, rather than being filled with a liquid, the container is filled with a material which
acts as a strong absorber for a particular gas (for example sodium dihydrogen phosphate for water vapor or sodium hydroxide for carbon dioxide), gas permeation into
the container can also be monitored. As an alternative to these gravimetric methods,
conventional gas analytical techniques may be used to examine permeability, for instance by monitoring the pressure drop across the film or by the specific determination of a gas component that permeates the film. As in the liquid permeation studies,
the film samples examined must be free of pores.
3.3.3
Microscopic Characterization of Polymers
Macromolecules
Most of the methods used for the microscopic characterization of emulsion polymers in terms of their macromolecular composition, molecular weight and
crosslinking require the removal of water. For this reason the investigations are performed on the dry polymer film or on freeze-dried samples. The methods employed
are the standard techniques of polymer characterization [3436].
Some of the measurements are performed on solutions of the polymer in organic
solvents such as tetrahydrofuran or dimethylformamide. Because of their high molecular weight and their partial crosslinking, complete dissolution of an emulsion
polymer is often difficult (see Sect. 3.3.2), and the information that can be provided
by these methods is in such cases rather limited.
Chemical composition
The chemical composition of an emulsion polymer sample can for instance be determined by Fourier transform infrared (FTIR) spectroscopy [37]. The measurement
is performed on a polymer film. Quantitative analysis involves comparison of the
spectra obtained with those of standard calibration substances.
An alternative or complementary method is pyrolysis gas chromatography. In this
technique the polymer is rapidly heated causing depolymerization or decomposition
and the products are separated and detected gas chromatographically [34].
Polymer composition can also be determined by 1H and 13C NMR [38] on dilute
samples of the polymer in an organic solvent. NMR analysis also enables end group
analysis and to a limited extent monomer sequence studies (for example in terms of
triad distributions).
3.3 Polymer Films
In recent years there has been increased interest in using gradient HPLC techniques, such as gradient polymer elution chromatography (GPEC [39]), for determining the compositional distribution of copolymers. The solubility gradient is created by mixing a solvent in which the polymer dissolves well with one in which it
does not dissolve (the so-called non-solvent). The copolymer is dissolved in the good
solvent and then injected into the LC column with the non-solvent as eluent, with the
result that the copolymer precipitates at the entrance of the column. During gradient
elution, the amount of the good solvent in the eluent is gradually raised which leads
to the re-dissolution and fractionation of the copolymer.
Molecular weight
The determination of the molecular weight of the polymer is also carried out in organic solution. A simple method is to measure the intrinsic viscosity [] of the solution [34]. The measurement is normally made using a capillary viscometer and involves recording the solution viscosity as a function of polymer concentration c and
then extrapolating the data to zero concentration (see ISO 1628-1). The dependence
of the intrinsic viscosity and the molecular weight, M, is given by the Mark-Houwink
equation:
1 ( c ) 0
(3-10)
[ ] = lim
= AM
c 0 c
0
where c is the polymer concentration, 0 the solvent viscosity and A and are quantities which are constant at specified temperature for the solvent-polymer pair. Normally, the c 0 extrapolation is too involved for routine measurements. In such cases viscosity is only measured at one particular (low) concentration and used as a relative measure for the molecular weight of the investigated polymer.
The Mark-Houwink equation (Eq. 3-10) assumes that the polymer in solution is
present in the form of random statistical coils. For a given molecular weight, branching and crosslinking in the macromolecule lead to a lower viscosity. In doubtful cases, alternative methods of absolute molecular weight characterization (static light
scattering, density gradient analysis in an analytical ultracentrifuge, membrane osmometry, end-group analysis, and so forth) should be used for comparison purposes [3436]. A modern alternative is that of matrix-assisted laser desorption ionization
mass spectrometry (MALDI MS [40]). In this technique the polymers are embedded
in a matrix made of a strong UV absorber which enables the unfragmented ionization of the macromolecules by a UV laser pulse. Absolute molecular weight determination is achieved in this mass spectrometer by time-of-flight measurement.
Because emulsion polymers are prepared by a radical polymerization process, the
molecular weight distribution (MWD) is generally quite broad. MWD is usually characterized by gel permeation chromatography (GPC, also referred to as SEC, size exclusion chromatography). GPC fractionates a polymer solution according to coil size
by passing it through a micro-porous gel with a defined pore size distribution [34]. In
addition to simple UV and refractive index detectors, other techniques such as FTIR
spectrometry and light scattering are now used to characterize the individual fractions as they elute from the column. The latter two detectors enable both the chemi-
69
70
cal composition and the molecular weight of the individual polymer fractions to be
accessed directly.
Crosslinking
Internally crosslinked polymer particles (micro-gels) can be characterized by comparing hydrodynamic volumes and molecular weight. High molecular weights coupled with small hydrodynamic volumes indicate extensive crosslinking. The hydrodynamic volume is best accessed by viscosity measurements or dynamic light scattering, while molecular weight can be determined by the density gradient analysis in
an analytical ultracentrifuge or by static light scattering.
Micro-gel fractions are a common feature of emulsion polymers because of intraparticle crosslinking. On the other hand, interparticle crosslinking, which occurs after film formation, significantly reduces the solubility of the polymer film. In this latter case, crosslinking is characterized by performing swelling experiments in organic solvents.
Film and particle morphology
Polymer particles can be produced in a number of morphologies. Figure 3-15 shows
examples of structures that have been observed.
Fig. 3-15
Morphologies of polymer particles.
The morphology of the film, directly after its formation, will be determined by the
structure of the particles, but a significant restructuring of the phases can occur as a
function of time (leading for example to larger domains). The major technique used
to characterize particle and film morphology is transmission electron microscopy
(TEM), which is described below.
Other techniques are small angle X-ray and neutron scattering (SAXS [41] and
SANS [42]), atomic force microscopy (AFM, [43, 44]) and NMR spin-diffusion and
spin-relaxation techniques [45]. However these methods are not in widespread use
and their ability to characterize the composition, size, shape and superstructure of
the domains is somewhat limited. The reader is referred to the literature for further
details.
Transmission electron microscopy
In transmission electron microscopy [46] the dry sample has to be transferred into
ultrahigh vacuum and is illuminated by a high-energy beam of electrons (for example 100 keV). In an ideal case, a lateral resolution of around 1 nm is achievable.
Since sample preparation is rather involved, TEM is not a routine technique. In order to examine individual particles, they have to be placed separately on a suitable
3.3 Polymer Films
substrate under conditions which prevent film formation (that means high dilution
of the sample and drying below the minimum film formation temperature). For the
TEM inspection of a polymer film a thin section containing only one particle layer is
required (typical thickness <100 nm). The thin-cut can only be done at a temperature
below the glass transition temperature of the polymer. Sometimes it is also possible
to directly deposit a particle monolayer on a substrate by drying the dispersion at the
right dilution.
Transmission electron micrographs directly show the size and shape of the individual polymer particles. However, to draw any reliable conclusions on the distribution of particle size or shape the laborious counting of a large number of particles is
required (>1000!).
A fundamental problem of using electron microscopy to analyze polymer samples
is their low electron density, which causes low contrast in the images. Improved contrast can be achieved by staining the polymer with heavy-metal compounds such as
RuO4, OsO4 or uranyl acetate. These compounds are incorporated into the polymer
network directly or via a suitable coupling agent.
Staining agents which exhibit high selectivity for certain polymers also form the
basis of morphology studies. For example, polystyrene and polybutadiene can be selectively stained with RuO4. Acrylates, on the other hand, require treatment with hydrazine and OsO4. A core-shell particle with a polystyrene core and an acrylate shell
can thus be characterized by staining the core with RuO4. In the same way a possible
phase restructuring taking place in the film of these particles can be studied.
An alternative to the above preparation methods, albeit a rather involved one, is
the freeze-fracture technique, in which the dispersion is shock frozen by being
poured into liquid nitrogen. The freezing process has to be fast enough to avoid crystallization of the water phase. The sample is then cryo-transferred to the electron microscope where it is fractured. The fracture surfaces can then be imaged using, for
example, replica techniques.
Acknowledgments
I wish to thank Dr J. Lamprecht, Dr W. Mchtle, Dr A. Zosel, Dr H. Nissler,
Dr R. Baumstark, H.-J. Heiter, and S. Krause for their assistance in the preparation
of the manuscript.
71
72
References
1 W.-D. Hergeth in: Polymeric Dispersions:
4
5
6
7
8
10
11
12
13
14
15
16
Principles and Applications, J. M. Asua

(ed.), Kluwer Academic Publishers,
The Netherlands, 1997, pp. 267288.
E. Penzel in: Ullmann's Encyclopedia of
Industrial Chemistry, Vol. 21, Verlag
Chemie, Weinheim, 1992, pp. 157178.
R. S. Davis, W. F. Koch in: Physical Methods of Chemistry, Vol. VI: Determination of
Thermodynamic Properties, B. W.
Rossiter, R. C. Baetzold (eds), Wiley,
New York, 1992, pp. 5962.
A. W. Adamson, Physical Chemistry of
Surfaces, Wiley, New York, 1990.
V. B. Fainerman, R. Miller, P. Joos,
Colloid Polym. Sci. 272, 731 (1994).
E. J. Schaller in: Emulsion Polymerization
and Emulsion Polymers, P. A. Lovell,
M. S. El-Aasser (eds), Wiley, New York,
1997, pp. 437466.
J. J. Bikerman, Foams, Springer, Berlin,
1973.
E. A. Collins in: Emulsion Polymerization
and Emulsion Polymers, P. A. Lovell,
M. S. El-Aasser (eds), Wiley, New York,
1997, pp. 385436.
C. Bohren, D. Huffman, Absorption and
Scattering of Light by Small Particles,
Wiley, New York, 1983.
W. Brown (ed.), Dynamic Light
Scattering, Oxford University Press,
Oxford, 1992.
C. Wu, K. Unterforsthuber, D. Lilge,
E. Lddecke, D. Horn, Part. Part. Syst.
Charact. 145149 (1994).
P. Kratochvil, Classical Light Scattering
from Polymer Solutions, Elsevier, Amsterdam, 1987.
H. G. Barth, Modern Methods of ParticleSize Analysis, Wiley, New York, 1984.
W. Mchtle in: Analytical Ultracentrifugation in Biochemistry and Polymer Science,
S. E. Harding, A. J. Rowe, J. C. Horton
(eds), Royal Society of Chemistry,
Cambridge, 1992, pp. 147175.
J. G. DosRamos, C. A. Silebi, J. Colloid
Interface Sci. 135, 165 (1990).
A. M. Botana, S. K. Ratanathanawongs,
J. C. Giddings, J. Microcolumn Sep. 7, 395
(1995).
17 J. W. Vanderhoff, H. J. Van den Hul,
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
R. J. M. Tausk, J. T. G. Overbeek in:

Clean Surfaces, G. Goldfinger (ed.),
Marcel Dekker, New York, 1970.
S. H. Maron, M. E. Elder, I. N. Ulevitch, J. Colloid Sci. 9, 89 (1954).
J. G. Brodnyan, G. L. Brown, J. Colloid.
Sci., 15, 76 (1960).
R. J. Hunter, Zeta Potential in Colloid
Science, Academic Press, London, 1981.
R. J. Hunter, Foundations of Colloid
Science, Vol. II, Clarendon Press,
Oxford, 1989, Chapter 13.
Gas Chromatography, J. P. Baugh (ed.),
Oxford University Press, Oxford, 1993.
S. Ahmed, M. S. El-Aasser, G. H.
Pauli, G. W. Poehlein, J. W. Vanderhoff, J. Colloid Interface Sci. 73, 388
(1980).
P. M. Lesko, P. R. Sperry in Emulsion
Polymerization and Emulsion Polymers,
P. A. Lovell, M. S. El-Aasser (eds),
Wiley, New York, 1997, pp. 619655.
V. B. F. Mathot (ed.), Calorimetry and
Thermal Analysis of Polymers, Hanser,
Munich, 1994.
H. F. Mark, N. M. Bikales, C. G. Overberger, G. Menges, J. I. Kroschwitz
(eds) Encyclopedia of Polymer Science
and Engineering, Vol. 7, Wiley, New
York, 1987, p. 539.
I. M. Ward, Mechanical Properties of
Solid Polymers, Wiley, New York, 1983.
A. Zosel, G. Ley, Macromolecules 26,
2222 (1993).
J. V. Koleske (ed.), Paint and Coating
Testing Manual, ASTM manual series,
MNL 17, ASTM, Philadelphia, 1995,
Chapters 4042.
P. C. Hiemenz, Principles of Colloid
and Surface Science, Marcel Dekker,
New York, 1986, Chapter 6.
W. D. Bascom, Adv. Polym. Sci. 85, 89
(1988).
P. J. Flory, Principles of Polymer
Chemistry, Cornell University Press,
Ithaca, 1953.
A. F. M. Barton, CRC Handbook of
Solubility Parameters and Other
Cohesion Parameters, CRC Press,
Boca Raton, 1983.
References
34 C. Booth, C. Price (eds), Comprehensive
35
36
37
38
39
Polymer Science, Vol. 1, Polymer Characterization, Pergamon Press, Oxford,

1989.
B. J. Hunt, M. I. James (eds), Polymer
Characterization, Blackie, London, 1993.
E. Schrder, G. Mller, K.-F. Arndt,
Polymer Characterization, Hanser,
Munich, 1988.
D. O. Hummel, Atlas of Polymer and
Plastics Analysis, Vol. 1, Polymer:
Structures and Spectra, Verlag Chemie,
Weinheim 1978.
J. L. Koenig, Spectroscopy of Polymers,
ACS Professional Reference Book,
American Chemical Society, Washington, 1992.
G. Glckner, Gradient HPLC of Copolymers and Chromatographic Cross-Fractionation, Springer, Berlin, 1991.
40 H. S. Creel, Trends Polym Sci. 1, 336
(1993).
41 R. Grunder, G. Urban, M. Ballauff,
Colloid Polym. Sci. 271, 563 (1993).

42 R. H. Ottewill in: Polymeric Dispersions:
43
44
45
46
Principles and Applications, J. M. Asua

(ed.), Kluwer Academic Publishers,
The Netherlands, 1997, pp. 229242.
J. Didier, Y. Wang, J. Lang, O. Leung,
M. C. Goh, M. A. Winnik, J. Polym. Sci:
Part B: Polym. Phys. 33, 1123 (1995).
S. Akari, D. Horn, W. Schrepp, Adv.
Mater. 7, 549 (1995).
K. Landfester, C. Boeffel, M. Lambla,
H. W. Spiess, Macromolecules 29, 5972
(1996).
L. C. Sawyer, D. T. Grubb, Polymer
Microscopy, Chapman and Hall,
London, 1987.
73
Applications in the Paper Industry

Jrgen Schmidt-Thmmes, Elmar Schwarzenbach, and Do Ik Lee
4.1
Introduction
In 1998, the world demand for emulsion polymers (dry) was 7.4 million metric tons
and is forecasted to increase to 8.8 million metric tons in 2003 with an annual
growth rate of 3.6 % [1]. Of this 1998 world demand, about 35 % and 32 % were consumed in North America and Western Europe, respectively, while about 23 % was
for paper and paperboard coatings. If the world-wide uses of emulsion polymers for
both paper and paperboard coatings and paints and coatings are combined, they will
account for about half of the world consumption of emulsion polymers. For this reason, the industry for paper and paperboard coatings is a core market for emulsion
polymers, along with the industry for paints and coatings. The world demand for
emulsion polymers in 1998 is shown by market and region in Fig. 4-1, while Fig. 4-2
shows the demand forecast in 2003 [1].
Other Markets
(18%)
Paints & Coatings
(26%)
Carpet Backing
(11%)
Adhesives Paper & Paperboard
(22%)
(23%)
By market
Other Regions
(21%)
North America
(35%)
Japan
(12%)
Western Europe
(32%)
By region
The 1998 World Emulsion Polymer Demand:

7.4 Million Metric Tons
Fig. 4-1
The 1998 world demand for emulsion polymers by market and region.
75
76
4 Applications in the Paper Industry
Other Markets
(17%)
Paints & Coatings
(26%)
Carpet Backing
(10%)
Adhesives Paper & Paperboard
(23%)
(24%)
By market
Other Regions
North America
(24%)
(34%)
Japan
(11%)
Western Europe
(31%)
By region
The 2003 World Emulsion Polymer Demand Forecast:

8.8 Million Metric Tons
The 2003 world demand forecast for emulsion polymers by market
and region.
Fig. 4-2
This chapter will cover the applications of emulsion polymers in the paper industry, especially in surface sizing and paper coating. Since information on the breakdown in the uses of emulsion polymers for surface sizing and paper coating is not
readily available in the world markets, it is hoped that information available on the
Western Europe market would provide some perspectives on their relative uses of
emulsion polymers. Table 4-1 shows the amounts of emulsion polymers used for
these applications in Western Europe: 3 % and 97 %, respectively [2].
Tab. 4-1 The Western European market for emulsion polymers in the
paper industry [2].
Market segment
Amount of polymer dispersions in metric tons

and percent (1997)
Surface sizing
Paper coating
Total
35 000 ( ~3 %)
1 150 000 (~97 %)
1 185 000
4.2
The Paper Industry

4.2.1
History
The precursors of paper were papyrus and parchment, which were used for writing
as early as 3000 BC in Egypt. In China, strips of bamboo or wood were used for writing and drawing before the discovery of paper. The invention of paper has been attributed to Tsai Lun in AD 105, who produced a uniform writing-material paper
from felted plant fibers [3]. The original paper was made in China from rags, bark
4.2 The Paper Industry
fiber, and bamboo. The plants were crushed in mortars and water was added to create a homogeneous fiber pulp. By dipping a hand wire screen into the suspension, a
thin layer of the pulp was removed and then dried. Even today, these are still the fundamental steps in the papermaking process. The art of papermaking finally reached
Central Asia by AD 751 and Baghdad by 793, and by the 14th century there were
paper mills in several parts of Europe [4]. Later, it landed in the New Continent.
With the invention of the printing press by J. Gutenberg in the middle of the
fifteenth century, paper assumed a previously unimagined importance and there
was a massive increase in the demand for paper. As a result of further discoveries,
increasing levels of trade and for other reasons, the level of paper consumption continued to rise. Numerous raw materials were used for paper manufacture and there
were rapid developments in industrial papermaking with the first papermaking machine being built in 1799. Nicholas-Louis Robert constructed the first papermaking
machine. Using a moving screen belt, paper was made one sheet at a time by dipping a frame or mold with a screen bottom into a vat of pulp. A few years later, the
brothers Henry and Sealy Fourdrinier improved Roberts machine, and in 1809 John
Dickinson invented the first cylinder machine [4].
4.2.2
The Paper Industry Today
In 1998, the world production of paper and paperboard excluding newsprint and tissue totaled approximately 240 million metric tons and is expected to grow to approximately 290 million metric tons in 2003 with an annual growth rate of 4 % [1].
The main raw material used to make paper is wood. Both softwoods (long fiber)
and quick-growing hardwoods (short fiber) are processed.
The intermediate stage between the raw materials and the finished paper is socalled half stuff (pulp). Typically, this is:
Cellulose from which lignin, resins, and incrustations have been removed by the
refining process to leave high-grade cellulose fiber that is particularly well suited to
paper manufacture.
Mechanical pulp, which is produced from wood that has been ground or refined
by mechanical means. This type of pulp is less well suited for paper manufacture,
as the incrustations are still present to a large extent and the properties of the pulp
are determined by fiber bunches and fragments inevitably present.
Paper made of pure cellulose is designated as wood-free paper, whereas that
made from mechanical wood is called wood-containing paper.
In an effort to protect wood resources, large amounts of recycled papers are also
used in todays papermaking industry. Modern technology combined with appropriate process chemicals enables this secondary raw material to be used not only for paperboard, but also for high-quality paper.
The proportion of the chemical additives used as fillers in both paper and coatings
is about 3 %, a surprisingly small amount compared to the other constituents such
as recycled paper, cellulose, and pigments. Of this 3 %, synthetic additives comprise
only about one third so that overall synthetic additives make up only about 1 % of the
77
78
Chemical additives
Chemical pulp
43%
3%
1.0%
Synthetic
chemical
additives
0.5%
Alum
1.5%
Starch
8%
35%
11%
Waste paper
Mechanical pulp
Pigment/Filler
The proportion of chemical additives relative to the total global

raw material demand of the paper industry in 1996.
Fig. 4-3
total content (Fig. 4-3). The two most important groups of the synthetic additives are
the synthetic binders (50 %) and the sizing agents (25 %), as shown in Fig. 4-4. While
synthetic binders are composed of emulsion polymers, sizing agents can be
monomeric or polymeric. In the latter case, they are in the form of polymer dispersions.
Additives relevant to paper
properties
Additives relevant to
manufacturing process
(Functional chemicals)
(Process chemicals)
Synthetic binders
50%
(Paper
coating)
1%
1%
1%
Biocides
Defoamers,
deaerators
Dispersants,
cleaners
8%
3%
6%
Sizing agents 25%
Wet strength resins
Bleaching chemicals
Dyes, OBA
Fig. 4-4
5%
Retention drainage
aids, curing agents,
flocculants,etc.
8%
Process chemicals used in the papermaking.
The pulp is prepared for the paper machine in an upstream unit. In this unit, the
wood is ground, washed, and sorted, and then fiber concentration and consistency
are adjusted to the desired levels.
The paper machine itself is a single continuous production line with a length that
today may exceed 200 m and comprises the following main sections: headbox, wire
section, pressing section, drying section, and finishing section.
4.3 Surface Sizing
In the headbox, the pulp suspension is spread across the entire width of the web
and passed onto the wire mesh at the correct speed. The sheet is formed as the water
drains from the mesh and the fibers are fixed into their final orientation while still in
the wet mat stage. In the pressing section, water is driven out of the wet mat by applying pressure to the web. The web enters the pressing section with a dry content of
about 20 % which increases to 4050 % as the web leaves this section of the machine.
On passing through the drying section, the web is dried to a final moisture content
that is in equilibrium with the ambient air. The drying section is often equipped with
additional devices which improve the surface properties of the paper or board. Examples of such devices are the size press, the machine calendering cylinder, various
types of calenders, and coating equipment. The paper or board web is wound onto rolls
in the finishing section which also contains roll handling and wrapping equipment.
The size of todays paper production lines is enormous. The state-of-the-art papermaking and finishing machines are up to 10 m wide in web widths and up to
2000 m min1 (120 km h1) in production speeds. A wide range of production and
finishing processes guarantees that even the most demanding quality requirements
can be met.
The largest part of the papers produced today is for printing, also known as graphic arts, i.e. for printing paper and board. The requirements that these materials must
meet include:
high degree of uniformity and smoothness
good optical properties of which brightness and gloss are the most important
high opacity and high strength
In short, the physical characteristics of the paper or board must ensure both good
processability and good printability.
To meet these demands, the following two processing stages are incorporated into
the drying section of the papermaking line:
surface sizing
paper coating
The use of emulsion polymers in the paper industry is essentially restricted to
these two processes which are described in more detail in the following sections.
4.3
Surface Sizing
Surface sizing means a pigment-free application of hydrophobicizing substances,

the surface sizing agents, in combination with starch. The application will be on-line
to the paper machine by either a size press or a film press. In relation to the paper
mass usually 3 to 5 % (w/w) of starch and 0.1 to 0.25 % (w/w) of sizing agents, each
calculated as solid, will be applied. So in a size press formulation starch clearly dominates with more than 95 % of the solids content. Starch enhances the strength of the
paper, the surface sizing agent hydrophobicizes the paper sheet, thereby reducing
the absorbency of the paper. Thus, the penetration and spreading of print colors are
controlled and the loss of strength in the wet state is reduced.
79
80
An alternative to surface sizing is internal sizing, the addition of a sizing agent to

the wet end before the formation of the paper sheet. In this process step, however,
exclusively low molecular weight sizing agents like rosin acids or alkyl ketene dimers
(AKD) are applied.
For surface sizing, mostly polymeric sizing agents are used. The most important
product classes are acrylic copolymer dispersions stabilized by protective colloids.
The particles of the sizing agent consist of a hydrophobic polymer core and a hydrophilic shell formed out of the protective colloid (Fig. 4-5).
Charged hydrophilic
protective colloid
+
+
+
+
+
+
+
Hydrophobic core
+
+
+
+
+
+
Charged hydrophilic
protective colloid
70 - 200 nm
Fig. 4-5
Structure of a polymer-based sizing agent.
The composition of the polymeric core influences hydrophobicity, glass transition

temperature, viscous flow, and binding strength of the polymer. The hydrophilic
shell is highly swollen in water and normally carries either an anionic or cationic
charge. It renders stability to the dispersions during storage and against the high
shear stress during application. It also plays an important role in the interaction between starch and sizing agent. The hydrophobic effect of surface sizing stems from
the formation of a stable coherent film at the paper surface providing a halftone-like
screen (raster) formed from well defined hydrophobic barriers and areas of hydrophilic character (Fig. 4-6). Polymer particles sitting at the interphase between
starch film and fiber surface support the fixation of the starch film to the fiber. Polymer particles in the interior improve the wet strength and delay the dissolution of
starch and the flow of aqueous media within the starch layer. Polymer particles at the
surface reduce the wettability of the surface. Only dispersions stabilized by protective
colloids are able to form such a coherent hydrophilic/hydrophobic raster. The protective colloid tightly fixed to the polymer core acts as a compatibilizer between
starch and hydrophobic polymer core, preventing a rupture of the film during drying
and shrinking of the starch.
4.4 Paper Coating

Starch
Polymer protective colloid
Polymer core
Hydrophilic
Hydrophobic
Fiber
Fig. 4-6
Formation of a starch-polymer film.
The hydrophilic/hydrophobic balance of the surface can be individually controlled

by:
the ratio between starch and hydrophobic polymer
properties of the starch-like film formation, swelling, and water uptake
hydrophobicity, average particle size, and viscous flow of the polymer particles
Also, in special paper applications like photocopy and ink jet papers, the addition
of polymer dispersions to surface sizing formulations can lead to positive effects.
The interaction between hydrophobic toner and polymer particle enhances the toner
adhesion in case of photocopy papers. This proves to be very helpful in cases where
the process conditions in the copier are insufficient to guarantee complete melting
of the toner on the paper surface.
Applied to ink jet papers, a hydrophilic/hydrophobic raster on the paper surface
results in a highly accurate fixation of the dye right to the spot at the paper surface.
Whereas the hydrophilic areas allow a fast dewatering of the printing ink, mostly to
the interior of the paper sheet, the hydrophobic points prevent a spreading parallel to
the paper surface. Additional modification of the starch/polymer film by cationic
groups results in an additional fixation of the anionic dyes by ionic interaction.
Thereby, color density and outline sharpness can be further improved.
4.4
Paper Coating
Paper coating is the most important surface finishing process for paper in terms of
both the amount of paper that is coated and the quantity of emulsion polymers consumed in the coating process. The method involves coating the surface of the paper
with a water-based pigmented coating color. The emulsion polymer used in the coating color formulation binds the individual pigment particles together and helps the
entire pigment layer to adhere to the surface of the paper. Furthermore, emulsion
polymers are also added to improve the processability and/or runnability of the coating color. Coating is typically applied onto paper and board for printing or packaging
81
82
applications. Other specialty kinds of paper that undergo coating are labels, wallpaper, and non-printed silicone papers which act as the backing sheets for self-adhesive
labels.
Coating paper or board increases the homogeneity of the surface and considerably
improves its optical characteristics such as gloss, smoothness, brightness, and opacity. The properties of the pulp severely limit the surface homogeneity achievable with
uncoated papers. The surface of an uncoated paper will contain fibers which are approximately 13 mm (10003000 m) long and approximately 10 m thick. If this paper is printed by the halftone process using a 50 lines/cm screen, the dots (200 m)
are smaller than the dimensions of the fiber. The fibers are thus the limiting factor
dictating image definition. In contrast, the pigments used in the coating color can be
easily ground to a particle size of less than 1 m. While the surface of an uncoated
paper comprises numerous individual fibers of varying degrees of hardness, the
surface of a coated paper is, by contrast, uniform and homogeneous in structure.
Figures 4-7 and 4-8 demonstrate clearly the differences in the quality of offset and
rotogravure printing on coated and uncoated paper surfaces, respectively.
Uncoated grade,
supercalendered
Coated grade,
supercalendered
Fig. 4-7
Effect of coated paper on offset printing.
For the reasons given above, coated paper exhibits more uniform ink receptivity
and better holdout than uncoated papers. Coating also produces a much smoother
paper surface that is particularly a significant factor when printing individual dots,
especially when using a rotogravure process (Fig. 4-9).
Low basis-weight papers require a high degree of opacity if show-through (i.e.,
when the printing on one side of the paper can be seen from the other side) is to be
prevented. The opacity of an uncoated paper is determined by the cellulose fibers
and any fillers it contains. While fillers are naturally better than cellulose in increasing opacity, they are unable to provide the opacity levels attainable by coating. The
crucial factor determining opacity is the volume of the coating, since this determines
4.4 Paper Coating
Coated
gravure
paper
Uncoated
gravure
paper
Fig. 4-8
Effect of coated paper on rotogravure printing.
typical dotsize
critical area for
missing dots
Result of printing paper of insufficient smoothness by the

rotogravure printing process.
Fig. 4-9
the area of the pigmentair interface (within the coating layer) at which the scattering of incident light occurs.
83
84
Gloss is a critical property when assessing the quality of printing. Calendering is

only able to improve the gloss of an uncoated paper surface to a limited extent. The
gloss of a coated paper surface can be varied over a wide range, either by purely mechanical means (calendering), by the coating process itself, or by controlled addition
of gloss-imparting pigments. In this way, a full range of coated papers from highgloss to semi-gloss to matte are easily obtained.
The degree of brightness can be controlled by selecting appropriate pigments, but
can also be adjusted by the use of optical brighteners or toning dyes or both. The
brightness of a coated paper also depends strongly on that of the base paper. If the
base paper is of low brightness (e.g., unbleached), opacifying pigments such as titanium dioxide (TiO2) and special techniques such as double or triple coating are used.
4.4.1
Coating Techniques
A number of different coating machines exist for applying the coating color onto the
base paper. Figures 4-10ac illustrate the common coating methods, along with the
range of coating weights that can be achieved, the required level of solid content, and
the viscosity of the coating colors.
Stiff blades are more commonly used in North America, while bent blades are
more widely used in Europe.
It is apparent that the various coating methods place different demands on the
rheological properties of the coating color. These requirements must be taken into
account when formulating a coating color for a particular application.
The major components of a coating color are:
inorganic pigments to cover the surface of the base paper
co-binder and thickener for controlling the processing properties
binder (water-soluble or disperse systems or a combination of the two)
4.4 Paper Coating
Fig. 4-10 Coating equipment. (A) Stiff blade, bent blade, and roll blade;
(B) Air-knife; (C) Pre-metered size press.
Quantitatively, pigments are the principal constituent of any coating color, binders
being used in relatively small amounts. For every 100 parts pigment, there are typically about 520 parts binder and 0.13 parts of other additives. Coating color compositions common in both North America and Europe for sheet-fed offset and rotogravure printing processes are listed in Tab. 4-2.
The quantities given here always refer to the amount of active ingredient required.
A more detailed description of the constituents of a coating color is presented in
Sects 4.4.24.4.4.
Once coated, the paper is smoothed as part of the calendering process. Calendering involves subjecting the paper surfaces to high temperatures and pressures in or-
85
86

Tab. 4-2 Typical coating color compositions for sheet-fed offset and rotogravure printing processes in both North America and Europe.
Sheet-fed offset
Rotogravure
North American formulation

75 parts fine kaolin clay
25 parts fine ground calcium carbonate
12 parts emulsion polymer
3 parts starch
0.5 parts calcium stearate
North American formulation

85 parts delaminated clay
15 parts talc
2 parts starch
European formulation
80 parts fine ground calcium carbonate
20 parts fine kaolin clay (high gloss clay)
0.5 parts co-binder
0.5 parts curing agent
0.5 parts optical brightener
European formulation
50 parts talc
50 parts kaolin clay (coarse or high aspect ratio)
5 parts rotogravure sole binder
der to create a smooth, glossy surface. A distinction is made between soft-nip calendered and supercalendered papers. In the soft-nip calender process, the number of
nips is kept low, and higher temperatures and lower pressures are used, compared to
the supercalender process. The advantages of the soft-nip calendering are that it can
be performed on-line, i.e., immediately after the coating process and that the bulk
of the paper does not decrease as much as in supercalendering. By varying temperature and pressure in a controlled manner, a very broad range of gloss levels can be
achieved. In the supercalender, the number of nips used to smooth the paper is
greater, with typically twelve rolls in a supercalender stack. The smoothest and
glossiest paper surfaces are achieved by supercalendering.
4.4.2
Pigments used in Coating Colors
The main constituents of a coating color formulation are the inorganic pigments,
which serve to cover the surface of the base paper and thus to improve its optical
properties.
Coating pigments must therefore satisfy the following requirements:
high purity
high brightness and opacity
high refractive index
good dispersibility and desirable rheological properties
amount of binder required should be low
The most important pigments are:
kaolin clay (often referred to simply as china clay)
calcium carbonate, natural or precipitated
titanium dioxide
4.4 Paper Coating
Nearly in all cases, not one but a combination of several pigments is used in coating color formulations. Kaolin clay and calcium carbonate are the most commonly
used pigments. There are a great number of different types in each of the two pigment groups: the calcium carbonate grades being distinguished mainly by particle
size, while the plate-like kaolin clays are classified according to their so-called aspect
ratio (ratio of surface diameter to thickness) and particle size.
In the recent years, the use of ground calcium carbonate pigments in North America has been steadily increased so that the differences in coating color formulations
between North America and Europe are being narrowed.
The pigments used in the preparation of coating colors are prepared as slurries.
These are aqueous dispersions which by using dispersing agents such as tetrasodium pyrophosphate or sodium polyacrylate can have a solid pigment content of
greater than 70 %.
The different pigments require different amounts of binder in order to ensure adequate adhesion of the coating to the surface of the paper and sufficient binding between the pigment particles. For this reason, it is important to keep the specified
binder-to-pigment ratios when formulating coating colors. The following table
(Tab. 4-3) lists the amount of binder required by various pigments to achieve a given
level of binding strength (pick strength) for sheet-fed offset printing paper.
Tab. 4-3 Amount of binder in coating colors as a function
of pigment type.
Pigment
Kaolin clay
Ground calcium carbonate
Precipitated calcium carbonate
Titanium dioxide
Binder demand (%)

Paper
Board
12
11
15
14
14
12
18
16
More binder is needed when coating board to ensure good glueability in folded
cardboard boxes.
4.4.3
Co-binders and Thickeners used in Coating Colors
Pumping, transfer, re-circulation, and, most particularly, the actual coating method
require certain rheological properties of the coating colors. Low-shear and highshear viscosities (shear rates of 10 to >106 s1) and water retention values are highly
important parameters. For example, in roll coating applications, the thixotropic behavior of the coating color is particularly important, whereas Newtonian or structurally viscous (i.e. pseudoplastic or shear-thinning) flow at high shear rates is important for all blade coating techniques. Coating colors are characterized by their viscosity, solid content, immobilization point, and water retention capacity.
87
88
To adjust these properties to the required level, co-binders and thickeners are
added to coating color formulations. If possible, these additives should be chosen to
have a positive influence on the gloss, smoothness, printability, brightness, binding
strength, and glueability of the paper, and they should certainly not have a detrimental effect on any of these properties. Typical amounts are 0.13 parts of co-binder or
thickener to 100 parts pigment and approximately 12 parts binder. In addition to the
emulsion polymers described in greater detail below, other substances are used as
co-binders and thickeners. These include natural products such as starch and synthetic water-soluble polymers such as polyvinyl alcohol and carboxymethylcellulose.
The chemical composition and the behaviors of co-binders and thickeners with respect to pH are shown in Fig. 4-11.
Dispersion
Solution
pH < 7
pH > 7
Hydrophobic
polymer chains
in form of
small balls
(dispersion particles)
- COOH
Alkali
- COO
- COO
- COOH
Anionic charges
repel each other,
polymer chains
stretch and
dissolve
Alkali
MAIN MONOMERS
CH2=CH-COOH
Acrylic acid
CH2=C(CH3)-COOH
Methacrylic acid
CH2=CH-COO-R
Acrylic acid esters
Acrylonitrile
CH2=CH-CN
CH2=CH-O-CO-CH3
Vinyl acetate
Fig. 4-11
Chemical structure of synthetic co-binders.
In contrast to the emulsion polymers used as binders, those employed as cobinders and thickeners contain large fractions of hydrophilic (typically carboxyl-rich)
monomers. This high degree of hydrophilicity means that the particulate nature of
the dispersion is lost when the acidic dispersion (pH < 7) is added to the alkaline environment of the coating color formulation (pH > 7). The resulting structures, which
range from massively swollen polymer networks to polymer chains dissolved in the
aqueous phase, influence the rheology of the coating color in a complex manner and
are still not fully understood.
Apart from the increase in the viscosity of the aqueous phase due to the dissolved
polymer molecules, which are present as stiff chains at the pH of the coating color
4.4 Paper Coating
formulation, polymer bridges also form between the pigment particles (Fig. 4-12).
These structures, which are strongly dependent on the state of shear in the coating
color, result in a rise in its low-shear viscosity. If, in addition, one succeeds in incorporating hydrophobic side chains into the polymer, the resulting associative interaction between the dissolved chains enables the low-shear viscosity to be increased still
further.
Dispersion
+ Alkali (pH>7)
Solution
Carboxylate
groups with
anionic charges
Functional
groups with
high polarity
Additional
hydrophobic
side chains
Anionic
charges repel
each other
Adsorption
on pigment
surfaces
Associative
interactions
between polymers
Extended
polymer chains
in the aqueous phase
Polymer bridges
between
pigment particles
Additional
network structures
(micelles)
Viscosity
in the
aqueous phase
High viscosity at
low shear
Very high
viscosity at
low shear
Latex particles
Extended polymer chains
Bridges between pigments
Associative thickening
Fig. 4-12 Thickening mechanisms with

various types of alkali-soluble co-binders and
thickeners. (A) Alkali solubilization and thick-
ening behaviors of various acrylate copolymers;

(B) Various thickening mechanisms of synthetic co-binders and thickeners.
89
90
All effects induced by the co-binder and thickener in the coating color are very
strongly dependent on the shape, charge distribution, and size of the pigments used
as well as on the solid content of the formulation. Choosing the right thickener or cobinder for a coating color which is to be formulated for use in a particular type of
coating machine is a complex task that requires good product knowledge and a considerable degree of practical experience.
4.4.4
Binders used in Coating Colors
Both natural and synthetic binders are used in the paper coating. Binders from natural sources are used in the form of aqueous solutions and include:
starch
soy protein
cellulose derivatives such as carboxymethylcellulose (CMC).
Synthetic binders, which are prepared as aqueous polymer dispersions, are:
styrene and butadiene
styrene and butyl acrylate
poly(vinyl acetate)
acrylates
vinyl ester and acrylic ester
ethylene and vinyl ester
These synthetic binders commonly known as latexes are mostly modified with
functional monomers such as vinyl acids, amides, acrylonitrile, etc. to improve the
colloidal and rheological properties of coating color formulations and the printing
and/or packaging properties of coated papers and paperboards.
As a water-soluble substance, polyvinyl alcohol represents a special case among
synthetic binders.
When the coating of paper began more than one hundred years ago, animal glues
and gelatin were used as binders. Partly because of their high price, these materials
are no longer used today except in a few specialty applications (e.g., gelatin in the
manufacture of photopaper). The natural products of more lasting significance were
starch (from potatoes, corn, and rice) and casein (from milk). Both are binders
which, like the synthetic sole binders, combine the characteristics of binder and cobinder. However, unlike the synthetic products, starch and casein cannot be added
directly to the pigments, but must first be pre-processed. Table 4-4 presents a general comparison of natural and synthetic binders.
The most important natural binder still in use today is starch, though it is now frequently used in combination with synthetic binders. Corn starch is more common in
the USA, whereas potato starch is more prevalent in Europe. Native starch containing two fractions of amylose (linear chain) and amylopectin (branched chain) is not
suitable for coating paper and board because the amylose fraction tends to undergo
retrogradation and the viscosity of coating colors made with native starch is too
high [5]. For these reasons, only treated (i.e., depolymerized) or chemically modified
starches are used. Most paper mills carry out their own starch preparations in-house.
4.4 Paper Coating

Tab. 4-4
Comparison of natural binders including polyvinyl alcohol with synthetic binders.

Natural binders and
polyvinyl alcohol
Synthetic binders
Sold as
Quality consistency
Dissolution/digestion needed
Concentration in aqueous form
Viscosity in aqueous form
Film properties
Solid (powder)
Good to poor
Yes
Maximum 1020 %
High
Very hard and brittle
Tendency to foam
Bacterial decay
Water retention
Binding strength (pick strength)
Water resistance
Casein yes; starch no

Yes
High
Medium high
Poor
Dispersion
Very good
No
50 %
Low
Variable, ranging from soft
to hard, thermoplastic, elastic
Yes
No
Practically none
High-very high
Very good
The properties of the starch depend on how it is treated or modified. The best results
are achieved by ethylation. However, the most economical method of modification is
enzymatic degradation to prepare enzyme-converted starches. Also, oxidized starches are widely used in North America. Table 4-5 compares the advantages and disadvantages of using starch as a binder.
Tab. 4-5
Evaluation of starch as a binder.
Advantages
Disadvantages
Low-price binder
Improves runnability, particularly
well-suited for roll coating (thixotropic
coating colors can be prepared)
Coating colors with a high solid content
can be prepared
Low binding strength compared to synthetic binders

Highly soluble in water, low wet-pick strength
Not compatible with satin white
Risk of non-uniform printing in an offset printing
Variable quality of commercial products
Liable to rot
In addition to starch, another natural binder still used in North America is soy protein. It is mainly used for recycled board coatings.
Emulsion polymers were first used successfully as coating color binders in the
nineteen forties. The advantages and disadvantages of these synthetic binders are
summarized in Tab. 4-6.
The binder in a coating color formulation must be capable not only of binding the
pigment particles together, but also of securing them at the coating surface and of
anchoring them to the base paper. The pigment particles at the coating surface must
be held sufficiently tightly so that the coated paper can be smoothed in calendering
and subsequently printed. The mechanical stress experienced by the surface of the
paper depends very much on the printing process used and on the tack of the chosen
91
92

Tab. 4-6
Advantages and disadvantages of emulsion polymers as binders.
Advantages
Disadvantages
Binder properties can be optimized

to meet requirements of printing process
High transportation costs (50 % water)
Does not affect coating color viscosity,

high levels of solid content possible
Freeze-sensitive
Water resistance of coating is higher than

that achieved with natural binders
No acceptor sites for optical brighteners
Better gloss and smoothness attainable

Simple to use:
no digestion needed
feed can be controlled via a flow meter
printing ink. The amount of binder added to the coating color formulation must
therefore be chosen appropriately. Special papers are an exception to this rule because in these materials the binder not only determines the papers printability, but also
performs other functions such as controlling its oil- or water-resistance. Table 4-7
provides a rough guide to the amounts of binder required for the various types of
printing process.
Tab. 4-7
The dependence of binder quantity on printing process.
Printing process
Amount of binder per 100 parts of pigment
Letterpress printing
Sheet-fed offset process
Web offset process
Flexographic printing
Rotogravure process
815 parts
1020 parts
1018 parts
1018 parts
410 parts
The amount of binder in coating colors used to coat board that is to be printed
by rotogravure, flexography, or the sheet-fed offset process is usually somewhat
greater than in coating color formulations for paper. More binder is needed for
coated board in order to meet such additional requirements as folding strength and
glueability.
Using too much binder not only increases the price of a coating color unnecessarily, but also can be detrimental to quality. Large amounts of binder can cause the
porosity of the coating to decrease so much that the printing ink does not transfer
properly to the surface or, in extreme cases, is repelled by the surface. Drying times
increase considerably as a result, causing set-off in the stack (i.e., the transfer of wet
ink from a newly printed sheet to the reverse side of the following sheet).
The binder accounts for approximately 15 to 40 % of the total cost of a coating color, depending on the printing process used.
4.4 Paper Coating
In addition to the amount of binder used, which is a dominant factor determining

the binding strength, the type of binder is also of crucial significance in determining
the properties that influence the appearance and classification of paper and board.
These important properties are:
pick resistance (dry pick strength, IGT method, Pruefbau)
water resistance or wet pick resistance (wet pick strength, IGT method, Pruefbau)
gloss (specular reflection intensity)
brightness (reflection of visible light = 475 nm)
opacity (hiding opposite to transparency)
smoothness (Parker Surface Roughness Test, etc.)
porosity
compressibility (rotogravure)
stiffness (more important for light-weight papers)
drying/setting of printing inks
mottling (uneven uptake of ink)
water absorption capacity (the capacity of the paper to absorb water, thus permitting the transfer of inks to moist surfaces)
ink absorption capacity (the capacity of the paper to absorb ink and to prevent ink
being transferred from the freshly printed areas to the rubber blanket of the following printing station)
blistering in web offset process (blister-free printing)
glueability of board and packaging paper
In Sect. 4.4.5, the most important methods of testing coated papers will be described.
The extent to which a coated paper needs to fulfil the various requirements listed
above depends on the printing process to be used. The most exacting requirements
on binder strength must be met by paper grades to be printed by the sheet-fed offset
process. Because an aqueous fountain solution is used in the offset process, the wet
pick strength (i.e. the binding strength of the moist paper) is crucially important. As
the sheet-fed offset process is principally used to create high-quality prints, the demands made on optical parameters (brightness, gloss) and on printability (ink absorption, absence of mottling) are particularly stringent.
As the printing inks used in a web offset press have less tack than those used in
the sheet-fed offset process, the requirements on the binding strength for paper
printed by the web offset process are not so high. However, the paper must exhibit
high resistance to blistering. Once printed, the paper in a web offset press passes
through a drier in order that the printing ink solvents and any residual water within
the base paper can evaporate. If the porosity of the coating is too low, the water vapor
can become trapped causing blistering and detachment of the coating layer.
The rotogravure process uses inks with a very low viscosity. It therefore has the
lowest requirements in terms of the pick strength of the paper. To guarantee the
even and error-free transfer of the printing inks (i.e. low number of missing dots)
from the rotogravure cells to the paper, requires paper which is both smooth and
compressible.
93
94
When choosing or developing a suitable binder for one of the various printing
processes, one generally focuses on those four parameters whose effect on binder
properties is sufficiently well known. These are:
nature of the constituent monomers
glass transition temperature
particle size and particle size distribution
molecular structure of polymers
As mentioned at the beginning of this section, the binders used in coating color
formulations are based on combinations of different monomers. The most common
combinations are styrene with butadiene or acrylic esters and vinyl acetate combined
with ethylene or acrylic esters. An important difference between styrene-butadiene
binders and styrene-acrylic ester binders is the tendency of the binder to yellow under
the influence of UV radiation or heat. Products containing a butadiene-based binder
are considerably more susceptible to yellowing due to the much greater fraction of
double bonds in the polymer. Acrylic ester copolymers are significantly less prone to
thermal or UV-induced yellowing (as shown clearly in Figs 4-13 and 4-14) and these
are the copolymers of choice for the production of high-quality, long-life prints.
Generally speaking, binders based on polyvinyl acetate or on styrene-acrylate produce a more porous coating than do binders based on a butadiene copolymer.
The glass transition temperature of a polymer is determined by the amounts of its
different monomer constituents. Paper used in offset printing contains binders
whose glass transition temperature lies between 0 C and 30 C. The high smoothness and compressibility required for paper grades used in the rotogravure printing
process are achieved by using binders with a much lower glass transition temperature (<0 C). Figure 4-15 shows the typical dependence of dry and wet pick strength,
stiffness, gloss, porosity, and evenness of offset printing on the glass transition temperature.
Fig. 4-13 Thermal yellowing as a function of the chemical composition of

the binder.
4.4 Paper Coating
Brightness Loss
14
After 8 hours of UV exposure
12
10
8
6
4
2
0
Base paper
Chemical Basis
Styrene/Acrylate
Chemical Basis
Styrene/Butadiene/Acrylate
Chemical Basis
Styrene/Butadiene
Fig. 4-14 UV-induced yellowing as a function of the chemical composition

of the binder.
- wet pick
- paper gloss
- porosity
Goal
Fig. 4-15 Dependence

of paper properties on
the glass transition
temperature of the
binder.
Goal
- dry pick
- print gloss
- printability
Glass transition temperature (Tg)
Particle size and particle size distribution are influenced by the choice and
amounts of emulsifiers and protective colloids that a polymer dispersion contains.
These components are added to stabilize the dispersion thus making it both processable (i.e., enabling it to be conveyed, metered, filtered, etc.) and storable. Variations
in the emulsion polymerization process also have a major effect on the size and size
distribution of the polymer particles. Typically, binders used in the paper coating
process have particle sizes of between 100 and 300nm. Figures 4-16 and 4-17 demonstrate that both the viscosity of the coating color and the wet pick strength of the
coated paper are strongly dependent on particle size.
In contrast to the other possible monomer components, butadiene possesses two
double bonds both of which can act as polymerization sites. Binders based on a
styrene-butadiene combination therefore have a more cross-linked and branched
polymer structure. The extent of cross-linking affects the dry and wet pick strength,
the print gloss and the degree of blistering, which is a highly significant parameter in
95
96
Viscosity, mPas
1200
1000
800
600
400
200
0
50
100
150
200
250
300
350
Particle size (D), nm

Fig. 4-16
Dependence of the viscosity of binder dispersions on particle size.
Wet pick strength

100
50
Wet pick strength of paper

and board coatings improves
with decreasing particle size
0
100
150
200
250
Particle size (D), nm

Fig. 4-17 Dependence of the wet pick strength of binder dispersions
on particle size.
web offset printing. Unfortunately, binding strength and blister resistance tend to
oppose one another and cannot therefore be optimized by the choice of binders
alone (Fig. 4-18).
A very similar dependence is observed with the styrene-acrylate binders (Fig. 4-19).
In this case, binding strength and blister resistance show a mutually opposed dependence on the relative molecular weight of the polymers.
The polymer structure, and thus the desired balance between binding strength
and blister resistance, can be controlled in the two classes of binders by careful
adjustment of the polymerization conditions and by the addition of a so-called chain
transfer agent. Additional information on paper coating can also be found elsewhere [614].
4.4 Paper Coating
Blister resistance
Pick strength
Pick strength
Blister
resistance
Low
% Gel content
High
Fig. 4-18 Relationship between blister resistance and binding strength

for styrene-butadiene binders.
Blister resistance
Fig. 4-19 Relationship

between blister
resistance and binding
strength for styreneacrylate binders.
Dry pick strength
Molecular weight of Styrene/Acrylate copolymers
4.4.5
Test Methods
In this section, the most important methods of testing coated papers will be described. The printability and the final print quality can often be successfully predicted on the basis of these relatively simple tests.
Coating strength tests
The strength required for a paper surface is to a large part determined by the tack of
the ink used in the printing process. Whether or not the paper is dampened prior to
printing is also of considerable importance, particularly in the offset process. The following tests simulate the stresses experienced by the paper surface during the printing process, in particular ink splitting during the offset process (Fig. 4-20).
97
98

Fig. 4-20. Ink splitting
in offset printing.
blanket
printing ink
ink splitting
paper or board
Cylinder
Wet pick test

This is a test to determine the water resistance of a coated paper. After wetting the
test strip at constant speed and uniform pressure to create a precisely defined moisture content, the strip is printed with the testing ink while moving at constant or
increasing speed through the press.
Using a hole template to define ten separate measuring dots (representing
precisely defined strip speeds), the color density of each of the ten dots is measured
using a densitometer and then expressed relative to the full tone of the printed surface. When plotted as a function of printing speed, the color density values are a
measure of the water resistance of the paper strip.
When the paper strip is printed at constant speed, the measuring dots used to
determine color density are chosen randomly.
Dry pick test
This test determines the tensile strength of the coating strip when subjected to ink
splitting during the printing process:
The test strip is printed at a precisely defined plate pressure while being accelerated through the printing zone. The location of the first picking point and the position
at which picking is visible right across the test strip are determined by inspection and
analyzed quantitatively with the aid of a computer program.
However, since in practice, the paper passes through not one but several printing
presses (48 in the offset process), a further test can be performed to examine the
effects of this sequential stressing of the paper surface. This is the so-called offset
test.
4.4 Paper Coating
Offset test
This test simulates repeated ink splitting caused by contact between the printed area
and the rubber blanket during the printing process.
Ink is transferred to the test strip from a plate at an exactly specified plate pressure
and a constant known printing speed. The printed region is subsequently reprinted
five times at 10-s intervals using the same plate but without re-inking. The number
of passes at which the first signs of picking become apparent is recorded. In North
America, Paper-Ink Stability Test (P&I Test) is widely used [15]. The test measures
the rate of ink setting by calculating the slope of the ink splitting force as a function
of the number of impressions taken at a given time interval. Also, this test measures
the number of passes-to-fail. In general, the faster the rate of ink setting, the lower
the number of passes-to-fail. Therefore, for press runnability, the rate of ink setting
and the number of passes-to-fail must be balanced.
Printability tests
Mottle test
This test determines the evenness of the printing.
Ink is transferred to the test strip from an inked plate at an exactly specified plate
pressure and a defined constant speed, and subsequently split three times by an offset rubber blanket-covered cylinder. If the coating on the paper is unevenly distributed, the printed image may appear cloudy as a result. The inhomogeneity of the
printed image is either ranked visually or with a mottle tester (which measures fluctuations in color density).
Measurement of ink gloss
A test strip is printed using a precisely defined plate pressure and constant printing
speed. Once the test strip is dried, the ink gloss is measured using a gloss meter.
Ink set-off test
This test measures the speed at which the oils in the printing ink penetrate the coating of the paper during the drying (setting) process: A test strip is printed from an
inked plate applied at a precisely defined pressure and a constant printing speed. A
blank counter strip is pressed against the original strip once every 15 s during the duration of the test (900 s). The counter strip will pick up some of the non-dried printing ink from the original strip. The color density of any ink transferred to the counter strip is measured using a densitometer. The Paper-Ink Stability Test mentioned
as an offset test can provide information on ink set-off in terms of the ink setting
rate [15].
Rotogravure test
This test determines the suitability of paper or board for printing by the rotogravure
printing process: To perform this test, a gravure cylinder and blade must be added to
a standard IGT tester. The gravure cylinder is inked and the excess ink removed
from the non-printing areas by the blade. Printing is carried out at a constant speed
99
100
and a defined force exerted by the impression cylinder. Each test strip is examined to
determine the length at which 20 missing dots have occurred. This particular test
method is known as Helio test.
4.5
Concluding Remarks
Science and technology in the fields of paper surface sizing and paper coating have
been significantly advanced over the past two decades and will be continued to move
forward to meet the needs in the paper industry. There are many challenges
confronting the paper industry. Some of the challenges are conservation of raw
materials, especially trees as fiber source, by improving the current basis weight
vs. stiffness relationship as well as by using recycled and secondary fibers more
effectively, environmentally friendly papermaking, coating, and finishing processes,
better quality coated paper and paperboard products at lower costs, etc. These
challenges will require us to continuously innovate in papermaking, coating, and
finishing. It will be interesting to see how well the paper industry can succeed in the
21st century.
Acknowledgments
One of the co-authors (DIL) would like to thank his two other co-authors (JS-T and
ES) for letting him contribute to this chapter. This chapter has been based on
an English translation of the Paper Industry portion of Chapter 5 Anwendung in der
Papier- and Graphischen Industrie, by Jrgen Schmidt-Thmmes, Elmar Schwarzenbach, and Berhard Prantl in Polymerdispersionen, Dieter Distler (ed.), Wiley-VCH,
1998.
101
References
1 P. A. Ita, World Emulsion Polymers,
2
3
The Freedonia Group, September, 1999.

BASF Corporation.
G. D. McGinnis, F. Shafizadeh, Cellulose and Hemicellulose, Chapter 1 in:
Pulp and Paper: Chemistry and Chemical
Technology, 3rd edn, Vol. I, J. P. Casey
(ed.), John Wiley and Sons, 1980,
pp. 138.
Paper, The New Encyclopaedia Britannica,
Vol. 9, Encyclopaedia Britannica, 1987,
p. 126.
R. L. Kearney, H. W. Maurer (ed.), Starch
and Starch Products in Paper Coating,
Tappi Press, 1990.
L. Gttsching, Papier in unserer Welt,
Econ Verlag, Dsseldorf, Vienna,
New York, 1990.
T. W. R Dean, The Essential Guide to
Aqueous Coating of Paper and Board, Pita,
Lancashire, UK, 1997.
8 G. L. Booth, Coating Equipment and
Processes, Lockwood, New York, 1970.

9 R.W. Hagemeyer, Tappi Monograph
Series, 1976, 38.

10 A. R. Sinclair, Tappi Monograph Series,
1975, 37.
11 E. J. Heiser, F. Kaulakis, Tappi Mono-
graph Series, 1975, 37, 2263.

12 T. F. Walsh, L. A. Gaspar, Tappi Mono-
graph Series, 1975, 37, 98119.

13 J. J. Latimer, H. S. De Groot, Tappi
Monograph Series, 1975, 37, 120136.

14 R. C. Jezerec, G. P. Cogan, Tappi
Monograph Series, 1975, 37, 6469.

15 N. P. Sandreuter, Tappi Coating Confer-
ence Proc., 211, 1994.
Applications for Printing Inks

Barna Szabo
5.1
Introduction
The major printing processes used worldwide are: lithographic, gravure, flexographic, screen, letterpress and digital. Flexography is the only printing process that consumes significant quantities of water based (aqueous) ink. Less than 23 000 tons per
year of water based ink are used for gravure printing in the US and less than
14 000 tons in Japan; water based gravure volumes are negligible in Europe and Latin
America. Solvent based ink is used mostly for printing gravure, although it is readily
adaptable to aqueous ink. Oil- and solvent-based ink systems are used in the lithographic and letterpress processes. Lithography is the largest volume printing
process. Letterpress is one of the smallest. Both water and solvent based inks are used
in screen and digital printing; these consume comparatively small volumes of ink.
In the United States, approximately two-thirds of flexographic ink is water based;
one-third is solvent based in an estimated flexographic ink market of 200 000 tons.
The major volume of water based flexo ink consumed in the United States is for
printing corrugated containers. The total US ink market for all six printing processes listed above is estimated at over 1.1 million tons for year 2000 or approximately
4.5 billion $US.
In Europe, approximately two-fifths of flexographic ink is water based; threefifths is solvent based in an estimated flexographic ink market of 180 000 tons. The
total European ink market for all six printing processes is estimated at over 0.9 million tons for year 2000 or approximately 4.4 billion $US.
In Latin America less than one-third of flexographic ink is water; greater than twothirds solvent based in an estimated flexographic ink market of 34 000 tons. The total
Latin American ink market for all printing processes is over 125 000 tons for year
2000 or approximately 750 million $US.
The flexo ink market in Japan is very small. Approximately one-half of flexographic ink consumed is water based; one-half solvent in an estimated flexographic ink
market of 27 000 tons. The total Japanese ink market for all six printing processes is
over 400 000 tons for year 2000 or approximately 1.5 billion $US.
103
104
5 Applications for Printing Inks
The aqueous ink market in 2000 is summarized in Tab. 5-1.

Tab. 5-1
The aqueous ink market in 2000.
US
Europe
Latin America
Japan
Flexo ink
Solvent-based
Water-based
Total flexo ink

103 tons, estimated
Water and solvent
Total printing ink

103 tons, estimated
2/3
2/5
<1/3
1/2
200
180
34
27
1100
910
125
400
1/3
3/5
>2/3
1/2
Emulsion polymers are used in flexographic and gravure ink for printing flexible
packages, paperboard cartons, corrugated boxes, multi-wall bags, newspapers, and
other flexible substrates (films) and paper products. Styrene acrylic based emulsion
polymers are most commonly used in printing ink applications. Cost is a key factor
in ink raw material suitability for most ink systems. The level of styrene monomer
used in ink grade emulsion polymers is maximized due to film hardness requirements of paper and paperboard materials and its low price.
Prior to the mid 1970s, rosin fumarates (i.e. sodium and amine rosin salts) were
the main resins used in aqueous ink. Aqueous rosin based resin solutions provide
the performance properties similar to use of rosin phenolic and rosin maleic pentaerythritol esters in a lithographic printing ink. Rosin based resins have been used
in printing ink since the early days of letterpress printing. They are low cost, give inherently good pigment dispersion properties, and are easily modified to vary viscosity and hardness. When aqueous flexo and gravure printing began displacing solvent
based systems, a wider range in properties than possible with rosin became important.
Emulsion polymers provide a wide range in properties and low viscosity. Flexo and
gravure inks are referred to as fluid inks because of their low viscosity. Molecular
weight, Tg (glass transition temperature), and particle size distribution are key properties that are varied to meet specific ink requirements.
Pigment dispersion stability, room temperature film formation, and ink re-solubility are important properties to consider in the design of emulsion polymers for
printing ink. A support resin (Sect. 5.2.2) is used in most ink grade emulsions to
maintain these properties. The support resin is a low to medium molecular weight
styrene acrylic or other water soluble resin. It comprises up to 60 % solids content of
the emulsion and replaces up to 90 % of surfactant stabilizers.
5.1.1
Flexographic Ink
A flexo ink is a low viscosity (fluid ink) suitable for transfer from an ink fountain via
anilox roll to the plate cylinder and substrate. It dries by evaporation of the solvent
(water). Most presses are equipped with air circulating dryers. A flexo ink is comprised of low boiling point solvents for low temperature evaporation and fast drying.
5.1 Introduction
Fig. 5-1
Flexographic press [1].
The composition and solvency is limited to prevent swelling of rubber or photopolymer-based rolls. Water, alcohols, minimal concentrations of acetates (i.e. ethyl,
isopropyl alcohol), and minor levels of aliphatics such as heptane are mostly used.
Acetates and aliphatics are used to solubilize polyurethane and polyamide resins
used in solvent based laminating ink. Only aqueous ink is discussed in this chapter.
A diagram of a flexographic press is given in Fig. 5-1.
A flexographic printing press consists of:
An ink fountain roll (rubber). The fountain roll rotates in a reservoir of ink and
transfers a large volume of ink to the anilox roll.
An Anilox ink metering roll (chrome plated or ceramic coated). The anilox is
engraved with cells (of inverted pyramid shapes) varying in density (size) between
80 to 1000 cells per linear inch (2.5 cm). The anilox supplies a precise volume of
ink to the raised surface (print image) of the printing plate. A reverse angle doctor
blade is used to wipe excess ink.
A printing plate cylinder (steel). A photopolymer printing plate is attached to the
plate cylinder. The printing plates raised surface replicating the image contacts
the substrate to transfer ink.
An impression cylinder (smooth and polished chrome). A smooth polished chrome
cylinder that holds the substrate in contact with the printing plate.
105
106
5.1.2
Gravure Ink
A gravure ink is a low viscosity (fluid ink) with rheological characteristics suitable for
transfer out of small cells of an engraved cylinder to the substrate. A gravure ink is
comprised of low boiling point solvents for low temperature evaporation and fast
drying. Gravure utilizes various environmentally compliant solvents as required by
specific printing applications. Only water based ink is discussed in this chapter. A
diagram of a gravure press is given in Fig. 5-2.
Fig. 5-2
Gravure press [2].
A gravure printing press consists of:

A gravure print cylinder (chrome). The gravure cylinder is engraved with cells of
varying sizes replicating the print image. The cylinder rotates through the ink
fountain. Ink fills the cells. An excess is wiped by a doctor blade. Ink is transferred
directly from cylinder to substrate.
An impression cylinder. The impression cylinder is a rubber coated cylinder that
keeps the substrate in contact with the print cylinder. Its function is to control ink
transfer. The ink is drawn out of the cells of the print cylinder by means of impression pressure and capillary action. An ESA (electrostatic assist) mechanism is
sometimes used to assist in the capillary action. Ink rheology, electron charge and
surface energy are key variables that effect transfer.
5.2
Ink Composition
An aqueous flexo or gravure printing ink is composed of polymer, pigment, solvent,

wax, surfactant, crosslinker, and additives. The polymer (resin) functions as the
vehicle for carrying the pigment. It is also a key component for achieving printing
5.2 Ink Composition
performance properties. The polymer is the material or compound for dispersing a

pigment and preventing its re-agglomeration. It provides adhesion to the substrate.
The branched network of the polymer provides hold-out on porous substrates. The
smooth surface provides gloss for desirable visual effects. Oxidized or crosslinked
polymer structures provide resistance to chemicals that contact printed packages.
It provides resistance to scuffing or rubbing. It provides resistance to environmental
conditions such as: heat and temperature, freezethaw, ozone, light, oxidation, moisture, etc. The polymer provides viscosity and rheology characteristics necessary for
transfer of ink from press to substrate.
The pigment provides the color. Organic pigments are used in most cases for
lightfastness and transparency. Colorfastness and lightfastness is important to maintain desirable visual effects of printed materials. An average consumer would not
purchase a food item (i.e. box of cereal) with faded or shifted colors. This effect
would convey a message about its lack of freshness. Water (solvent) is used to solubilize the resin or polymer. Water is used mainly in flexo and gravure printing
processes. Other solvents such as ethyl-isopropyl alcohol, ethyl-isopropyl acetate,
toluene, and heptane are also used in flexo and gravure ink, but only aqueous flexo
and gravure inks are discussed in this chapter.
Illustrated in Tab. 5-2 is a generic formulation for an aqueous flexographic or
gravure ink. A printing ink formula is frequently modified to meet exact color reproduction specifications and/or a customers changing performance requirement.
Tab. 5-2
Generic aqueous flexo or gravure ink formulation.
Aqueous flexographic ink

Component
Pigment dispersion (Sect. 5.2.1)
Emulsion vehicle (Sect. 5.2.2)

Solution vehicle (Sect. 5.2.3)
Amine neutralizer
Wax emulsion compound
Wax powder
Surfactant
Crosslinking additive
Silica additive
Corrosion inhibitor
Defoamer
Other additives
Total
Amount
(%, w/w)
Gravure ink
Component
Amount
(%, w/w)
Dispersion varnish
Organic pigment
Total
5570
3045
100
3550
2535
1020
0.51.5
25
02
11.5
02
25
01
01
0.250.5
100
Most commercially manufactured printing inks are made from intermediates

such as: pigment dispersion (Sect. 5.2.1), emulsion vehicle (Sect. 5.2.2), solution vehicle(Sect. 5.2.3), and wax emulsion compound (Sect. 5.2.4). Using intermediates
minimizes the number of raw materials handled at the ink manufacturing or blend-
107
108
ing site. It facilitates the production of ink in blending plants with minimal equipment and at locations close to the customer and/or printer. Producing ink from intermediates offers flexibility in modifying formulas to meet color reproduction specifications and changing customer application requirements.
5.2.1
Pigment Dispersion
The pigment dispersion is made from dry pigment (which is surface treated) dispersed in an aqueous polymer solution. High speed mixers are used to disperse a
pigment from a dried form or an aqueous slurry. The most common polymers used
to disperse pigments are: low to mid-molecular weight styrene acrylics, SMA
(styrene maleic anhydride), or rosin fumarate ester resins. The degree of stabilization of a pigment dispersion (which relates directly to color strength development),
ink viscosity stability, transparency and pH drift are controlled by use of polymers
such as those containing salt groups and hydroxyl functionality. Table 5-3 illustrates
the physical properties of polymers used for dispersing pigments.
Tab. 5-3
Solution polymers used for pigment dispersions.
Styrene acrylic I
Styrene acrylic II
SMA ester
Rosin fumarate ester
Softening
point (C)
Glass transition
temp., Tg (C)
Mw (g mol1)
Acid number
(mg KOH g1)
140170
NA
NA
125145
70125
15 20
45110
80 90
12000 18000
30000 35000
50000150000
2000 10000
210240
65 70
165285
115200
The stabilization of organic pigment dispersions is achieved by use of polymeric

anionic surfactants that provide strong adsorption on the polar surface of the pigment and hydroxyl groups for interaction with the aqueous phase. Non-polar intermediate sections of a polymeric anion add adsorbed layer thickness [3].
A typical organic pigment particle size ranges between 0.02 to 100 m (aggregate
size). The particle size distribution of particles in a pigment dispersion are typically
0.5 to 1.5 m. Most emulsion polymers used in printing ink vary between 20 nm to
200 nm. Because of a pigments relatively large particle size and its wide range in particle size distribution, the smaller emulsion polymer particles are not suitable for
forming stable dispersions of organic pigment particles and agglomerates. They do
not have sufficient mobility to wet the surface area.
Pigments used in aqueous flexo and gravure ink are supplied as a presscake, in dry
form, or as chips. A presscake is a high solids dispersion of pigment in water. A
presscake is dried by various drying processes to yield pigment agglomerates in a
large range of particle sizes, between 0.02 to 100 m. Chips are a dry form of dispersed pigment particles in a polymer.
Most pigments used in pigment dispersions for printing ink are surface treated
with a resin or polymer compatible with the pigment surface chemistry. The poly-
5.2 Ink Composition
mer is added as a dissolved aqueous solution during the pigment striking step. It
adheres to the pigment surface via physical and/or chemical attraction. Surface treated pigments are known as resinated pigments. A pigment is surface treated or
resinated as part of the pigment manufacturing process. A resinated pigment minimizes agglomeration, contributes to increased color value and improves the efficiency of the dispersion process. An explanation about the type of resins and polymers used for surface treatment of pigment is a separate segment of ink-pigment
technology that is not covered in this chapter.
It is important that resins or polymers used in the surface treatment of pigment,
are compatible and do not react with the resins and polymers used in the pigment
dispersion. Furthermore, they must be compatible with the emulsion and solution
vehicles of the ink. Incompatibility between these components may cause: pigment
re-agglomeration (resulting in a loss of color strength), increased low shear viscosity
(known as thixotropy) leading to a change in ink rheology, and poor printability
(e.g. variable ink transfer) performance.
In addition there are various hybrid resins in use to disperse a pigment. They are
used to achieve specific ink application properties not obtainable by the conventional resins and polymers discussed above. For example, a glycerol ester of fumarated
rosin is further esterified with a styrene-allyl alcohol as taught in Westvaco Chemical
Corporations patent Rosin-Based Grind Resins for Aqueous Printing Ink. This
type of resin has high softening point and gives relatively stable low viscosity ink [4].
A fumarated rosin polyamine condensation resin is explained in a second Westvaco
patent Modified Rosin Resins for Waterbased Inks. The condensation reaction
product of polyamines with certain rosin-based polycarboxylic acids results in an efficient pigment dispersion resin and gives a stable viscosity over a wide range in pH,
between 8.5 to 10.5 [5]. These resins and others not discussed provide alternatives for
dispersing pigments.
5.2.2
Emulsion Vehicle
The emulsion vehicle provides the workhorse performance characteristics of an

ink (i.e. adhesion, gloss, low viscosity, printability, re-solubility in water, heat, and
chemical resistance at low cost). Most printing ink emulsion vehicles are polymer
dispersions composed of styrene acrylics, terpolymers of styrene--methylstyrene
and other acrylate monomers (i.e., ethyl acrylate, methyl methacrylate, butyl acrylate,
2-ethylhexyl acrylate, methacrylic acid, acrylic acid, 2 hydroxyethyl acrylate, amino
acrylate). Higher levels of styrene give higher Tg. Higher levels of butyl and 2-ethylhexyl acrylate give lower Tg, thus more flexible polymers. Compared to other polymers (i.e. polyurethanes) styrene acrylics do not give good alkali resistance, chemical
resistance, or adhesion to films and lamination ink (cohesive) bond strength.
Emulsion vehicles are prepared by emulsion polymerization in water in the presence of surfactant stabilizers. Viscosity is not dependent on molecular weight but
only on solids content and particle size distribution. As a result, high molecular
weights (>200 000 g mol1) are achievable at low viscosity. Emulsions with small par-
109
110
ticle sizes impart properties similar to solution resins with advantages of: low viscosity, near Newtonian rheology, pH stability, low polarity, and insolubility after drying
for immediate water resistance.
Most printing ink emulsions are resin supported. Printing ink emulsion polymers contain a support resin to reduce MFFT (minimum film forming temperature), and insure film coalescence. A support resin also decreases the need for surfactants. A support resin provides ink re-wettability, improves compatibility with pigment dispersions, and improves ink transfer and printability. Support resins are typically styrene acrylic polymers with acid functionality that are amine neutralized.
A rosin fumarate ester can be used as a support resin for ink grade emulsions.
According to Westvacos US Patent 5 216 064 [6], a fumarated rosin ester offers advantages such: as improved gloss, absence of residual glycol used in processing a
styrene acrylic, and higher resin solids. A higher solids emulsion gives faster drying.
Rosin based support resins are lower cost. Westvacos US Patent 5 656 679 teaches
that a rosin fumarate reacted with an alkanolamine containing at least one secondary
amine and one hydroxyl group is used as a support resin for ink grade emulsions for
providing improved adhesion to films [7].
Polyurethanes are known to give excellent chemical and product resistance properties but increase cost. A water soluble polyurethane is made by adding acid modified monomer to the polymer backbone, the polymer is neutralized with amine, then
used as a support resin in ink grade styrene acrylic emulsions. Polyurethane supported styrene acrylic emulsion polymers may be used to balance the high cost of
polyurethanes and provide improved chemical resistance [8].
Emulsion polymers are supplied in bulk quantities at solids levels between 45
and 60 %. They are produced by emulsion polymer manufacturers such as: SC
Johnson Polymer, Rohm & Haas, Avecia, Air Products, Westvaco, B.F. Goodrich and
others.
Outlined in Tab. 5-4 are: applications, emulsion characteristics, and physical properties of the styrene acrylic emulsion vehicles used in flexo and gravure ink. An
emulsion vehicle comprises 25 to 35 % of the total ink formula. The table is sorted by
increasing Tg.
For printing inks that require specific properties not obtainable by conventional
styrene acrylic emulsions, an aqueous dispersion of an acid functional polyurethaneepoxy acrylate hybrid (self crosslinking for improved chemical resistance) [9] patented by Air Products and Chemicals, Inc. or a self crosslinking styrene acrylic emulsion which reacts upon evaporation of water [10] patented by Akzo Nobel Resins BV,
may be used. The Air Products novel dispersion contains a quaternary ammonium
polyurethane acrylic hybrid carboxylate salt and pendant acrylate epoxide that selfcrosslink upon evaporation of water and ammonia. Akzos novel polymer contains a
diacetone acrylamide reactive monomer and a bishydrazide. The crosslinking reaction between ketone groups and a bishydrazide proceeds rapidly at room temperature, after evaporation of water from the ink.
4852
4550
4550
2540
2025
4749
S.C.
(%)
8.28.7
7.98.5
8.59.5
6.07.9
7.98.3
8.28.4
pH
150 500
150 500
150 500
452500
25006000
700 900
Viscosity
(mPa s)
>200000
>200000
>200000
~100000
70000100000
>200000
Mw
(g mol1)
40 55
40 55
40 55
125 50
120130
35 50
A.N.
(mg KOH g1)
95105
95105
40 48
30 35
10 35
30 to 1
Tg
(C)
P.S., number average particle size distribution in nanometer; S.C., solids content; A.N., acid number; MFFT, minimum film forming temperature
180220
55 65
Folding carton
Flexo news
40 50
160180
Direct print corrugated
Cup, plate, multi-wall bag, gift wrap
65 75
120140
Pre-print corrugated
P.S.
(nm)
Surface print
Application
Tab. 5-4 Typical styrene acrylic emulsion vehicles used in flexo and gravure
printing inks sorted by increasing Tg.
>60
>60
>45
<24
<24
< 7
MFFT
(C)
5.2 Ink Composition

111
112
5.2.3
Solution Vehicle
Solution vehicles consist of water soluble polymers not manufactured by emulsion

polymerization. The solution vehicle is an alkali soluble polymer in aqueous solution
or a blend of polymers with combined properties into a single waterborne varnish.
Soluble polymers are made by free radical polymerization in a processing solvent or
as addition or condensation products with heat reaching temperatures up to 265 C.
Solution vehicles are mixtures of soluble resins unlike emulsion polymers. A solution vehicle is used to increase adhesion to film and improve ink printability or transfer to meet specific performance requirements. The solution vehicle provides pigment dispersion stabilization, transparency, low film forming temperature, gloss
and re-solubility. An alkali soluble resin is a carboxylic acid functional polymer neutralized (solubilized) with ammonia, amine or sodium hydroxide. The acid numbers
are generally above 100. Ammonia or volatile amines are used in most aqueous inks
except for news print inks. After evaporation of the amine, the resin becomes insoluble and resistant to water spray or other water contact. The ink is re-solubilized with
alkaline water for the clean-up cycle. For news print ink, the polymers are solubilized
with sodium hydroxide to maintain re-solubility (open time) of the ink on the press.
News print ink pressman prefer unlimited open time and fewer clean-up cycles. Water resistance is not required since ink penetrates the news print paper fibers.
The key solution polymers (resins) used in printing ink are styrene or rosin based.
Styrene--methylstyrene monomer and acid functional co-monomers (i.e. acrylic or
methacrylic acid) comprise the bulk of styrene acrylic solution vehicles used in printing ink. Rosin acid reacted with fumaric acid gives a tri-functional adduct. The
adduct is partially esterified with polyols such as pentaerythritol, glycerin, diethylene glycol, etc. to achieve a range of acidity, viscosity, Tg and molecular weight.
The viscosity of aqueous polymer solutions is strongly dependant on molecular
weight. High performance characteristics such as rub resistance and heat resistance
are compromised since low ink viscosity is required for flexo and gravure fluid ink
printing. The volatile amines used to neutralize acid functionality results in pH
shifts, unstable viscosity, reduced pigment dispersion stability, and poor alkali resistance.
Water soluble styrene acrylics are processed via free radical polymerization in glycol ether solvents. The solvent is stripped by conventional or proprietary processes.
Rosin based resins are processed molten at high temperatures up to 265 C. These
materials are flaked or pelletized and packaged in bags or bulk storage for further
conversion.
There are various hybrid polymers and co-polymers in use to achieve specific ink
application properties not obtainable by conventional resins and polymers. Water
soluble fatty acid epoxy esters provide improved heat resistance. For example, an
aqueous fatty acid-acrylic acid epoxy ester patented by Reichold Chemical, which
crosslinks via heat and auto-oxidation is used to provide water and heat resistance [11].
Typical solution polymers are listed in Tab. 5-5.
5.2 Ink Composition

Tab. 5-5
Typical solution polymers.
Surface print
Folding carton
Alternative folding carton
Multi-wall bags and
gift wrap
Milk carton
Cup and plate
Towel and tissue
Resin/Polymer
Softening
point (C)
Tg
(C)
Styrene acrylic resin
145
73
4500 7500 108213
Rosin fumarate
ester resin
125145
8090
200010000 115200
Fatty acid (Castor oil)/ >125

acrylic epoxy ester
Styrene acrylic
Water and amine
neutralizer
>100
75100
Mw
(g mol1)
Acid
number
3000040000 5060
600010000 200230
5.2.4
Waterborne Wax Emulsions and Powders
Both natural and synthetic waxes are used in ink. Waxes provide increased block,
rub, scuff and/or water resistance. Waterborne wax emulsions are produced in a
range of particle sizes between 35 to 175 nm (number average particle size distribution) by Michelman, Shamrock Wax, and others. Polyethylene and Fischer-Tropsch
emulsions improve the rub and scuff resistance of an ink. Carnauba paraffin and
polypropylene emulsions are used to prevent blocking and improve water resistance
of an ink.
Certain waxes are micro-pulverized to yield particle sizes smaller than a dispersed
pigment particle. A micro-pulverized wax is stirred into ink as a powder. Recycled
PTFE (Teflon) is supplied in small particle powder form.
5.2.5
Ink Additives
An amine neutralizer is added to solubilize resins containing carboxylic acid functionality. The amine reacts with the resin carboxylic acid to form a water soluble salt.
Volatile amines such as dimethylaminoethanol (DMAE), morpholine or ammonia
are used to insure that a printed product becomes water resistant upon drying or
evaporation of the amine. The type of amine used is selected based on press speed,
pH requirement and evaporation rate and press drying capacity. Sodium hydroxide
is commonly used in news print ink to maintain re-solubility (open time) of the ink
on the press.
A crosslinking compound is added to provide covalent branching to a polymer for
enhanced printed film tensile strength and chemical resistance characteristics. Com-
113
114
pounds such as zinc ammonium complexes or zinc oxide react with available carboxylic acid functionality. Self crosslinking emulsion polymers may be used as explained in Sect. 5.2.2.
A surfactant is added to reduce the surface tension to give increased ink spreading
and substrate wetting particularly when printing untreated or partially treated films.
The surface tension of water is approximately 72 dynes cm1 whereas a polyethylene
film is approximately 3040 dynes cm1 after surface treatment. Surfactants increase
the foaming tendency of an ink. Therefore levels of surfactant and defoamer are
carefully balanced.
A defoamer is added to reduce foaming. A fine particle size silica powder is added
to increase the viscosity and modify print film slip or abrasion properties.
A corrosion inhibitor is added to prevent corrosion of press parts made of steel.
5.3
Physical Properties and Test Methods
Viscosity, pH and color strength are the main properties that relate to press performance and print quality. Viscosity is critical for satisfactory ink transfer or printability. A gravure ink has slightly lower viscosity than a flexo ink. The pH is controlled since it effects viscosity, viscosity stability and compatibility with other components. The viscosity changes with change in pH, but is readily adjusted by adding
amine or water.
Color accuracy (ink color strength) is important for achieving satisfactory print color and to maximize profitability. The color strength of a pigment dispersion intermediate is carefully controlled to narrow tolerances. Therefore, color adjustments in
the ink manufacturing step are minimized.
5.3.1
Typical Properties
The typical properties or specifications of aqueous flexo and gravure ink are:
Viscosity, Zahn efflux cup (ref. ASTM D4212-99) @ 25 C:
Flexo ink shipping viscosity, Zahn #3
2530 s
Gravure ink shipping viscosity, Zahn #3
2125 s
Flexo ink printing viscosity, Zahn #3
1822 s
Gravure ink printing viscosity, Zahn #2
1822 s
Zahn #3
810 s
pH
9.09.5
Color accuracy (ASTM D2244-93)
<2.0 Delta E* (CIELAB total color
difference) versus standard
Fineness of grind, (ASTM D1316-93)
<2.0
Residue (ref. ASTM F311-97)
<15 mg per 100 g ink
5.3 Physical Properties and Test Methods
5.3.2
Application Tests
Application specific pass/fail tests are specified to guarantee that an ink shipment
gives satisfactory performance. The application properties are measured relative to a
standard sample. The results are reported as pass or fail versus the standard. The following application tests are performed on aqueous flexo and gravure ink:
Abrasion resistance, dry/wet rub resistance, Sutherland Rub Tester
Adhesion at surface tension of 3844 dynes cm1, Scotch 610 Tape Test
Block resistance
COF (coefficient of friction), ink to ink, static at 26.6 slide angle
COF (coefficient of friction), ink to ink, kinetic at 19.3 slide angle
Crinkle resistance at room temperature or that of ice water
Drying with a 1 millimicron or 2 mil fineness of grind gauge
Freeze-thaw resistance, two cycles
Heat resistance, 98 C
Milk carton wet rub
Product resistance acid, fertilizer, limestone, wood oil
Re-wetting
Rub test metal corrugator
Surface tension of film
Viscosity, Zahn efflux cup
Water resistance, 24 h, immersion at 25 C
5.3.3
Test Method Abstracts
Abrasion resistance Sutherland Rub Tester: A test strip (18.8 cm) is rubbed by a
four pound test block with a 15 cm 7.5 cm strip affixed. The test is run either:
ink-to-ink or unprinted paper-to-ink, 20 to 40 rub cycles according to specifications.
A subjective comparison is made to a photograph standard or control sample that is
tested subsequently. This test method simulates scuffing that may occur during
in-line filling, handling or transporting of a package. Wax emulsions or micro-pulverized powders are added to adjust the abrasion resistance properties of an ink.
For heated abrasion resistance, the four pound test block is held in an oven for
twenty minutes at a temperature specified. The test simulates scuffing that may occur
on hot filling lines or under high friction conditions.
For wet-rub resistance (approximately twelve drops) water is applied to a 18.8 cm
test strip with a pipette. Un-printed paper is used to test paper or board substrates. A
swatch of cotton material is used to test film substrates.
The test simulates rubbing of a package by cotton clothing.
Adhesion/Scotch 610 Tape Test: A 2.5 cm wide 3-M 610 tape is attached to the ink
and pulled off at an angle of 180 degrees. Ink removal of greater than 10 % is a failure. This test is performed to flag unusual problems associated with poorly treated
films or ink composition errors
115
116
Block resistance wet/dry ink to ink and ink to substrate: The exposure time,
pressure, and temperature are specified by the end use requirement (i.e. 3 min at
1034 bar, 50 C for surface print ink (5.4) The ink surfaces resistance to heat and
pressure is subjectively measured. Ink properties that effect blocking results are:
hardness, adhesion, cohesion, and slip. The polymer glass transition temperature (Tg), molecular weight, and surface compatibility effect the block resistance
test.
Coefficient of friction measurement, TMI slip and friction tester: The peak angle
(static) and average force (kinetic) are measured. An emulsion polymer with low
glass transition temperature is required for high slide angles.
Crinkle resistance test at room temperature or at the temperature of ice water: The
print is immersed in ice water for one hour (re-ice water crinkle). Two surfaces of
ink are rubbed ink to ink for 10 cycles. Perform a subjective comparison between a
test sample and a standard.
Drying test with a 1.0 mil (25 m) or 2.0 mil (50 m) fineness of grind gauge: Drying time is measured subjectively by finger tapping and a stopwatch. A polymers
glass transition temperature, MFFT and emulsion particle size distribution effect
drying.
Freezethaw test: A sample of ink is placed in a freezer at 15 C for 4 h. Changes
in viscosity, homogeneity, and seeding tendency are observed.
Heat resistance test at 100 C Sentinel heat seal tester: Set-up a Sentinel heat
sealer according to heat pressure and time interval specified. A one by three inch
(2.5 cm 7.5 cm) print sample is folded ink surface-to-ink surface and placed between the sealer bars. The heat sealer is operated. After the sample has been
cooled, the sheets are separated and a subjective comparison is made for cling, ink
transfer and picking. The polymer glass transition temperature (Tg), molecular
weight, and surface compatibility affect heat resistance.
Milk carton wet rub test: A test print is immersed in milk at 1 to 7 C for 24 h. A
rub resistance test is performed using a Sutherland rub tester (see abrasion resistance). Specific polymers (Sect. 5.6.1) are used to give resistance to milk.
Product resistance and/or chemical resistance acid, fertilizer, limestone, wood
oil, etc : Three drops of an appropriate chemical solution is applied using a
3-mL pipette. After a specified time interval, a cotton swab is rubbed through
the drop over the print surface with moderate pressure. A comparison is made for
discoloration, ink removal, or blistering. A polymer composition, branching structure and crosslinking density have the largest effect on chemical resistance of an
ink.
Re-wetting test: A #4 Meyer bar drawdown is allowed to dry for 20 min at RT
(room temperature). A drop of water is placed on the ink surface and subsequently wiped with a cloth. A subjective comparison is made versus a standard sample.
Solution polymers are neutralized with volatile amines (Sect. 5.2.3) to prevent resolubilization after the ink print dries.
Rub test metal corrugator: For pre-print liner board, this test simulates the effects of a corrugator. The extent of scuffing/marring is subjectively compared to a
photographed standard. The emulsion polymers soft segment, glass transition
5.4 Inks for Flexible Substrates (Films)
temperature (Tg), and molecular weight have the largest effect on the rub resistance properties of an ink.
Surface tension of film: Accudyne level pens or solutions are used to estimate the
surface tension of treated films. A targeted range of 3842 dynes cm1 is specified
for most printing applications. The surface tension of most aqueous styrene
acrylic based pigmented inks are greater than 3842 dynes cm1.
Viscosity, Zahn efflux cup (ref. ASTM D4212-99), seconds: A Zahn efflux cup is a
fast and effective instrument for measuring viscosity of flexo and gravure ink. Viscosity is an important property for maintaining printability. For a flexo press, consistency of ink flow into the pan or well of the doctor blade system, ink-transfer to
the anilox roller, and release of ink from anilox roller are largely effected by ink
viscosity. On a gravure press the release of a consistent volume of ink out of the
cylinder cell is effected by viscosity. Viscosity changes due to pH drift or evaporation of solvent (water) should be corrected immediately.
Water resistance, 24 h, immersion at 25 C: A Crinkle test is performed. Two surfaces of ink are rubbed ink-to-ink for 10 cycles. A subjective comparison is made
between a test sample and a standard.
5.4
Inks for Flexible Substrates (Films)
The ink used for printing flexible substrates (films) contains a soft film forming
emulsion polymer based on styrene and co-monomers such as butyl acrylate, and
2-ethylhexyl acrylate. Solvent based inks have continued use in high performance
printing applications such as packages requiring lamination bonds (i.e. candy wrappers, potato chip bags). Flexo and gravure printing companies have invested in solvent incinerators to remain compliant with environmental regulations. Examples of
materials used for flexible packaging films are:
LDPE
Low density polyethylene (i.e. fruit and vegetable produce bags)
MDPE
Medium density polyethylene (i.e. department store merchandize bags)
HDPE
High density polyethylene (i.e. grocery item bags)
LLDPE
Linear low density polyethylene
(i.e. department store merchandize bags)
PP
Polypropylene (i.e. salt, fertilizer bags)
PP-EVA
Ethylene vinyl acetate modified polypropylene
OPP
Oriented polypropylene
PP-NO
Non-oriented polypropylene
PP-AC
Acrylic coated polypropylene
PP-PVDC Poly(vinylidene chloride)-coated polypropylene
PET
Polyethylene terephthalate
PVDC
Poly(vinylidene chloride) (Saran)
117
118
5.4.1
Surface Print Film
Surface print inks are designed for printing on polyethylene substrates used in utility bags, department store merchandize bags, grocery bags, and general purpose surface film applications. The films are surface treated via corona discharge increasing
to a surface tension of 3841 dynes cm1 before printing. A corona discharge induces
ions and free radicals to oxidize the surface of a film to form polar functionality. This
change in surface chemistry and roughness increases surface energy and improves
wetting of ink on film. A surface print ink is composed of a soft film forming styrene
acrylic emulsion vehicle to provide adhesion. A solution vehicle composed of low
molecular weight styrene acrylic resin is added to adjust printability. Typical properties of the emulsion polymers and solution resins used in ink for surface print films
are listed in Tabs 5-3 and 5-4.
5.4.2
Lawn and Garden Bags
Lawn and garden bag inks are designed for printing on polyethylene or polypropylene substrates used in fertilizer, salt, mulch, potting soil, manure, feeds and wood
bark bags. Lawn and garden bags require resistance to: weak acids, bases, fertilizers,
limestone dust, wood oils (i.e. cedar, pine), etc.
A typical Lawn and garden bag ink has a similar composition to surface inks. A
crosslinking compound (i.e. zinc oxide, carbodiimide, polyfunctional aziridine) adds
covalent branching, increases modulus and enhanced print film adhesion and resistance to chemicals.
As an alternative, a self crosslinking styrene acrylic emulsion which reacts upon
evaporation of water may be used according to the Akzo Nobel Resins paper presented at the 44th NPIRI Technical Conference [10].
5.5
Inks for Paper Board Substrates

5.5.1
Folding Cartons
Folding carton inks are designed for printing on paper board (or boxboard) substrates used in: fast food carry out packages, pastry cartons, cereal boxes, mail containers, auto parts boxes, beverage carriers, milk and juice cartons, and other packages. Folding cartons are made from solid bleached kraft or solid bleached sulfate
(SBS), unbleached kraft, solid unbleached sulfate (SUS), clay coated unbleached
kraft, recycled paperboard, and coated paperboard.
For beverage carriers, one substrate type is used consistently in most of the US
market. Many beverage carriers are over-coated with a clear protective coating layer.
5.5 Inks for Paper Board Substrates
A folding carton ink is composed of a hard non-film forming styrene acrylic emulsion vehicle and a styrene acrylic solution vehicle. As an alternative, a film forming
styrene acrylic emulsion vehicle and rosin fumarate ester solution vehicle are used.
A plasticizer (i.e. propylene glycol) and solvent (i.e. n-propyl alcohol) are added to
folding carton ink to improve printability and insure coalescence at room temperature.
5.5.2
Direct Print Corrugated Packages
Direct print corrugated inks are designed for printing on standard kraft paper board
substrates. Corrugated board is manufactured by laminating flat sheets of paper to a
corrugated inner layer to give an increased stiffness-to-weight ratio [12].
Direct print corrugated ink is made from styrene acrylic colloids. Colloids are polymers produced by emulsion polymerization followed by neutralization of available
carboxyl functionality. Colloids have molecular weights in the range of 25 000
100 000 g mol1. They are used in low cost ink systems for printing on porous substrates such as corrugated paper board. Colloids are also supplied in solid form for
dissolving in water by neutralization with an amine. This results in uncoiling of the
colloidal particle to form a colloid solution. Colloid solutions give a high viscosity.
They are supplied at low solids concentrations typically between 20 % to 40 %.
A direct print corrugated ink is composed of a styrene acrylic emulsion colloid vehicle and a rosin fumarate ester and/or styrene acrylic solution vehicle. As an alternative, a mixture of colloid solution with a film forming emulsion provides the overall corrugated ink properties.
Direct print corrugated ink specifications:
Residue
<15 mg per 100 g ink
1.071.11/8.99.3
Density (g cm3/lbs gal1)
Dry rub
100 rubs/1.8 kg (4 lb) weight
Grind, NPIRI
<2
5.5.3
Pre-print Corrugated Packages
Pre-print corrugated inks are designed for printing on standard kraft, bleached kraft,
mottled kraft, clay coated, and SBS coated paper board substrates. Many producers of
corrugated packages have installed flexo presses for pre-printing linerboard before
making the corrugated board. Printing on a smoother surface gives improved print
quality. These inks must withstand heat (175200 C), pressure, and marring/scuffing conditions of the subsequent paperboard corrugating process. Most pre-print
packages are coated with a clear, high gloss, heat resistant, and scuff resistant coating. The coating adds resistance properties and gloss.
A pre-print corrugated ink is composed of a styrene acrylic emulsion colloid vehicle and a rosin fumarate ester resin and/or styrene acrylic resin solution vehicle. The
physical properties of emulsions and resins used in pre-print corrugated ink are listed in Tabs 5.4 and 5.5 for.
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Plasticizers (i.e. propylene glycol) and coalescing solvents (i.e. glycol ether) are
added to maintain satisfactory printability and satisfactory MFFT (minimum film
formation temperature).
5.6
Inks for Poly-coated Board
Inks for polymer coated paper board are designed for printing on polyethylene coated SBS (solid bleached sulfate) paper board substrates used in milk cartons, ice
cream cartons, beverage cups, and paper plates.
A typical ink for coated board is composed of an epoxy ester based pigment dispersion, styrene acrylic emulsion vehicle, and an epoxy ester solution vehicle. The
epoxy resin commonly used is an ester of drying or semi-drying fatty acid and acrylic
acid (Sect 5.2.3). The system undergoes oxidation to give moisture and alkali resistance [11]. Alternative polymers that may be used in inks for coated board are: aziridine (ethylene imine) crosslinking styrene acrylic or a VAE (vinyl acetate ethylene)
self crosslinking emulsion polymer.
5.6.1
Milk Cartons
Milk carton ink must have resistance to alkaline detergent based chain lubricants. A
fatty acid acrylic epoxy ester [11] is the key resin used in this type of ink. Special pigment dispersions are used based on the same epoxy ester since conventional styrene
acrylic based pigment dispersions are not stable in epoxy ester based systems.
5.6.2
Cup and Plate
Cup and plate inks must have tolerance for hot wax coatings and resistance to hot
and cold fluids. They should meet the requirements for general purpose paper plate
use. A hard non-film forming styrene acrylic emulsion combined with hot-air drying
(by oxidation) fatty acid-acrylic epoxy ester [11] provide the resistance requirements.
5.7
Inks for Paper Products
A typical ink used for printing multiple wall bags, gift wrap, and envelopes are composed of a hard non-film forming styrene acrylic emulsion combined with a solution
vehicle comprising a rosin fumarate ester to balance printability and coalescence. A
polymer with high molecular weight and Tg fast drying via fast: resin-solvent (water)
separation, penetration of paper and brightness of color via holdout of pigment
particles on the paper surface.
5.7 Inks for Paper Products
5.7.1
Multiple Wall Bags
Inks for Multiple Wall bags are designed for printing on kraft: brown, or bleached,
mottled (compressed thin layers of bleached pulp on top of brown pulp), clay coated,
and uncoated paper substrates. Flexographic printing is the most used process for
multi-wall bags.
Multi-wall and other paper bags are made of one or more walls of paper glued together and treated to provide moisture resistance. Heavy duty bags used as shipping
sacks have three or more plies. Bags used for packaging consumer products (i.e. pet
food, sugar, flower) have two plies. The paper used in bags for packaging consumer
products has been upgraded in recent years to bleached kraft and clay coated.
5.7.2
Gift Wrap and Envelopes
Gift wrap is used for seasonal gifts, retail wrapping, liquor boxes, candy and other
products. The substrates used are 90 % paper and 10 % foil [12].
Inks for Gift Wrap are composed of a hard non-film-forming styrene acrylic emulsion combined with a solution vehicle to adjust printability and balance coalescence.
Gravure is the most used process for printing gift wrap.
Envelope ink is made from the same mix of polymers as gift wrap ink.
5.7.3
Newspapers
Newspapers were originally printed by the letterpress printing process. Low cost
black ink was mostly used. A letterpress black ink is composed of carbon black dispersed in high boiling point aliphatic petroleum solvent (ink oil). By 1995 the majority of newspapers converted to the offset lithographic printing process. Offset news
ink is composed of carbon black or organic pigments dispersed in high boiling point
aliphatic petroleum solvent based vehicles. The vehicles are resin solutions in ink oil
and/or vegetable oils (i.e. soybean oil). During the 1980s the remaining letterpress
printers began to switch to the flexographic process and water based ink. Aqueous
flexo news ink is based on higher cost emulsion polymers than typical petroleum hydrocarbon resin based offset inks. Therefore it was necessary to target certain newspaper market segments with higher value products. Flexographic newspaper printing introduced brighter colors to comics and advertising, and overall increased color
coverage per newspaper. A flexographic news ink contains a high molecular weight,
styrene acrylic emulsion with high Tg (glass transition temperature) to provide fast
drying.
A typical flexographic news ink is composed of a hard semi-film-forming styrene
acrylic emulsion vehicle.
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5.7.4
Towel and Tissue
The same styrene acrylic emulsions used for sizing tissue paper to provide wet
strength are used in the ink. The colorants used are mostly dyes or pigments that are
not dermatological irritants. The resin should give a waterproof bond and be low
cost. The components of a towel and tissue ink are re-pulpable for ease in recovery of
waste and/or off-grade material to achieve satisfactory economies of paper towel tissue converting.
References
1 Western Michigan University Web Site:
http://www.wmich.edu/ppse/flexo/,
Flexographic Process
Western Michigan University Web Site:
http://www.wmich.edu/ppse/gravure/,
Gravure Process,
Wicks, Z. W. Jr., Jones, F. N., Pappas,
S.P., Dispersions in Aqueous Media, in:
Organic Coatings, Science and Technology,
2nd edn, Wiley-Interscience, 1999,
Chapter 20.3, p. 395.
Schilling, P. Westvaco Corporation,
US Patent: 5,208,319, Rosin-Based
Grind Resins for Aqueous Printing Ink.
Zuraw, P. J., Westvaco Corporation ,
US Patent: 5,166,245, Modified Rosin
Resins for Waterbased Inks, 1992.
Rivera, M. A.; Zuraw, P. J., Westvaco
Corporation, US Patent: 5,216,064,
Rosin-Based Resin-Fortified Emulsion
Polymers
Hutter, G. F., Westvaco Corporation,
US Patent: 5,656,679, Rosin Ester-Amide
Support Resins for Acrylic Latexes.
8 Biggerstaff, J. A., Reuther, P. C., Jack-
10
11
12
son, K., Westvaco Chemical Division,

A Comparison of Water-borne Chemical
Resistant Technologies and the Variables
that Affect their Performance, 43rd
NPIRI Technical Conference, September 1517, 1999.
Tien, C., Mao, C., Snyder, J. M., Beck,
A., Air Products and Chemicals, Inc.,
US Patent 5,977,215, Low Temperature
Self-Crosslinking, Aqueous Dispersions of UrethaneVinyl Polymers for
Coating Applications.
de Krom, A., Mulder, H., Mestach, D.,
Akzo Nobel Resins BV, Self-Crosslinking Acrylic Dispersions Outperform Conventional Solventborne Liquid Inks, 44th
NPIRI Technical Conference, October
1820, 2000.
Meeske, C. J., Van der Tuin, E. H.,
Racey, M. J., Reichold Chemicals, US
Patent 4,166,054, Water Dispersible
Epoxy resin Copolymers and Methods
of Making Same, 1979.
Eldred, R. N., Ph.D., Package Printing,
Jelmar Publishing, 1993.
Applications for Decorative and Protective Coatings

Brough Richey and Mary Burch
6.1
Introduction
Decorative and protective coatings are used in a great variety of applications, ranging
from the familiar such as coatings for buildings, furniture, automobiles, and large
industrial structures, to less well known applications such as removable coatings, paper coatings, and specialized coatings for optical fibers and electronic components.
Most coating applications have historically utilized solution polymers as the binder
component. However, concerns over pollution, the toxicity of solvents, and ease of
use and clean-up have driven the development of new emulsion polymer technologies to meet the needs of the coatings industry. The use of emulsion polymers for
coating applications has increased tremendously over the past fifty years and they are
now represented in nearly every segment of the industry. In fact, coatings based on
emulsion polymers frequently set the performance standards and lead the market in
many areas.
The objective of this chapter is to give the reader an overview of the use of emulsion polymers in decorative and protective coatings. Because of the great variety of
specific applications, it will not be possible to address them all, and we have chosen
instead to focus on selected application areas which we believe will provide the reader with a useful foundation in a variety of coating applications.
6.1.1
Market Overview
The development, manufacture, sale and application of decorative and protective

coatings comprise a large business and we estimate that approximately 20 billion
liters of decorative and protective coatings are manufactured and applied each year,
representing world wide sales of about $60 billion US [1]. Annual growth is typically
the range of 13 % world wide, and is generally linked to the combined gross domestic product of the major industrialized and developing nations. Growth rates for
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6 Applications for Decorative and Protective Coatings
water based coatings have been higher, in the 36 % range, with most of the extra
growth due to the switch from solvent based coatings.
We can obtain an estimate for the annual world wide production of emulsion polymers for decorative and protective coatings as follows. If we assume that water based
coatings make up about 50 % of the total world wide volume, then approximately
10 billion liters of water based paint are manufactured each year. To estimate the
amount of emulsion polymer manufactured to yield this amount of coating material,
we can estimate an average water based paint has about 30 % volume solids, with
the dry volume of binder representing about 50 % of this value. This yields an estimated 1.5 billion liters of solid emulsion polymer produced per year. Assuming an
average polymer dry density of 1.1 kg L1 and an average emulsion solids level of
50 % by weight, it follows that the world wide production of emulsion polymer for
coating applications is about 3 billion wet kg (67 billion wet pounds) per year. While
this is admittedly a rough estimate, it nevertheless serves to illustrate the enormous
size of the water based coatings market and the large amount of polymer emulsion
needed to supply it.
6.1.2
Coating Industry Trends
The most significant trend in the decorative and protective coatings markets has
been the move to more environmentally friendly coating materials. The shift away
from traditional solvent borne technologies to newer technologies based on waterborne emulsion polymers, high solids coatings, and powder coatings is a key consequence of this trend. This change has been driven by a variety of regulatory pressures
aimed at reducing air pollution by lowering the volatile organic content (VOC) of
coating materials. Related to these pollution concerns is the desire to increase the
safety of the end use application process, particularly in the area of decorative coatings for homes and offices. Again, this has caused a shift away from traditional solvent borne technologies toward newer technologies with improved health and safety
profiles. Finally, world wide economic conditions have led to consolidation in the
paint manufacturing industry, and its associated raw material suppliers [2]. These
economic factors have created a strong movement towards cost reduction and increases in production and distribution efficiency across the coatings industry. In our
view, the combination of continued technical innovation with improved cost efficiency presents the central challenge to the coatings industry as we move into the
twenty-first century.
6.1.3
Coatings Provide Decoration and Protection
It is common to divide the general class of coatings into two subclasses: decorative
and protective coatings. While this division can be useful, it can be also be misleading; the vast majority of coatings systems provide both decoration and protection.
Automotive coatings systems provide a familiar illustration of this dual role: they are
6.2 Overview of Coating Formulations
foremost a protective coating, and must protect the automobile body from damage
by weathering and the environment; and yet, the color and appearance of automotive
finishes are vital factors which influence the customers purchase decision. Interior
decorative finishes provide an example at the other end of the decorative-protective
continuum. While used primarily for decorative purposes, the stain resistance and
cleanability of interior finishes are important performance characteristics which often provide differentiation in this competitive market.
6.2
Overview of Coating Formulations
Decorative and protective coatings consist of three main components:

(i) pigment, which provides color and opacity to the coating
(ii) binder, which holds the film together and provides coating integrity; and
(iii) carrier liquid, which provides as the liquid character of the coating while in the
wet state (before drying).
In this chapter, we will focus on coatings utilizing emulsion polymer binders, and
consequently, water will be the carrier liquid. These types of coatings are also commonly referred to as latex paints, presumably in reference to the similarities in appearance between the emulsion polymer binders and unprocessed natural rubber.
Commercial paint formulations are usually complex and typically contain more
than the three main components described above. These formulations usually have
on the order of 1020 raw material components, the specific nature of which depends on the intended application. A more realistic formulation would include: dispersed solids such as pigments and fillers stabilized by a polymeric dispersing agent,
a dispersed emulsion polymer acting as the binder, a thickener to provide proper
rheology, coalescents and co-solvents to promote film formation and optimize the
drying process, surfactants to improve colloidal stability and promote substrate wetting, a biocide to prevent microbial spoilage, a defoamer to reduce foaming during
manufacturing and application, and a neutralizing agent to adjust the pH. Many optimized formulations contain more than one member of each of these classes. The
primary technical challenge of coatings formulation is to develop cost effective coating formulations which are stable indefinitely in the wet state, apply correctly to the
substrate, dry into defect free films, and meet the appearance and performance requirements of the intended application.
6.2.1
Volume Solids and Pigment Volume Content
The relative ratios between the volumes of different formulation components control
many of the key appearance and performance properties of a coating [3, 4]. Volume
solids is the simplest of these relationships; it is the ratio between the volume of solid components in a coating and the total volume of the wet coating. It typically is reported as a percentage. Volume solids is a useful quantity because it allows one to
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calculate the thickness of a dried coating from the applied wet paint thickness, or
from the spread rate (the volume of wet coating applied per unit of area). It can also
be used to estimate the quality of a coating when comparing coating formulations of
a given class. Since water is an inexpensive raw material, formulations high in water
content (and low in volume solids) tend to have lower raw material costs. Typical
emulsion polymer coatings for decorative and protective applications have volume
solids in the range of 2545 %, with values ranging up to 60 % for some specialty applications.
The pigment volume content (PVC) is another useful volume relationship which
is frequently used in coatings formulation development. It is the ratio of pigment
and extender solids to the total coating solids (pigment, extender, and binder solids),
and like volume solids, is usually reported as a percentage. Coatings with low PVCs
have a high binder content, and coatings with high PVCs have a low binder content
with higher levels of pigment and extender. It is important to recognize that PVC
represents a property of the dry film, rather than the wet coating.
PVC is an important quantity because it relates to many of the performance properties of a dry paint film. If several versions of a particular formulation are prepared
with different PVCs, ranging from lower to higher values, a transition point will be
observed at which many performance features of the coatings change abruptly. This
point is termed the critical PVC, or CPVC, and, in conceptual terms, represents the
PVC where the polymeric components of a film no longer form a continuous phase
surrounding the pigment and extender particles. Above CPVC, the dry coating begins to develop small voids between the solid components of the film, leading to an
abrupt change in the performance features of the coating. The value of CPVC for a
coating depends somewhat on the property used to measure it, and thus it is not a
truly fundamental characteristic of a film. Nevertheless, it has proven to be a useful
and practical conceptual tool for coatings formulation development.
Figure 6-1 is a scanning electron micrograph which provides a vivid illustration of
the differences between above and below CPVC coatings: Figure 6-1A shows the
smooth, polymer rich surface which is typical of a water based enamel formulated
significantly below CPVC; the white spots are TiO2 particles sticking through the
surface of the gray polymer matrix. Figure 6-1B shows the surface of a highly extended, above critical, flat ceiling coating at the same magnification. Note the high
porosity and variety of extenders in the above CPVC coating. The differences in the
surface features of these two emulsion polymer coatings are striking, and suggest
that these two types of coatings would have very different performance profiles.
The value of the CPVC for a particular formulation will depend on the chemical
and physical nature of the pigments, extenders and the binder. To illustrate this, we
consider two paints formulated with the same total volume of pigment and binder
(equal PVC). In one case the paint is formulated with a smaller particle size (PS) pigment, and in the other case the paint is formulated with a larger PS version of the
same pigment. The CPVC of the paint with the smaller PS pigment would be lower
than the CPVC of the paint with the larger PS pigment. This is because the higher
surface area of the smaller PS pigment will require a higher level of polymer to uniformly cover the pigment surfaces. This results in a higher binder demand, and low-
Field Emission Scanning Electron

Micrographs of Below and Above CPVC Coatings. (A) shows the surface image obtained
from a gloss enamel coating which has been
formulated significantly below CPVC. (B) shows
Fig. 6-1
the surface image obtained from a flat ceiling

coating which has been formulated significantly
above CPVC. Note the porosity and variety of
extenders present in the coating formulated
above CPVC.
ers the PVC at which CPVC is reached. Comparing the actual PVC of a coating to the
CPVC can provide useful information regarding a coatings physical properties and
suitability for a particular application. Coatings formulated at PVCs below CPVC
tend to have higher gloss, lower porosity, better flexibility and better barrier properties. Coatings formulated above CPVC generally have lower gloss, higher porosity,
lower flexibility and lower total cost. Since PVC level is usually adjusted upward by
increasing the levels of low cost extenders, PVC can provide a useful gauge of formulation cost (and quality). This measure is most useful for coatings formulated
above CPVC. PVC is a less useful measure of quality in coatings formulated below
CPVC, since these coatings contain little or no low cost extenders and consist primarily of higher cost resins and pigments.
6.2.2
Polymer Matrix
The polymer or binder component holds the coating together and provides many of
the performance features needed for specific coating applications. A high molecular
weight polymeric material is generally used as the binder in order to provide the
toughness and resistance properties needed to protect the substrate and ensure a
durable coating. In practical systems the minimum molecular weight of thermoplastic polymers targeted for coating applications is around 50 000 g mol1 [57]. Polymers with molecular weight below this value generally do not have the required
toughness properties needed for coating applications: lower molecular weight crystalline materials are generally too brittle and can chip or flake, while non-crystalline
materials such as amorphous waxes do not have high enough moduli to provide the
film integrity needed for most coating applications.
Decorative and protective coatings are generally designed to perform their function over the temperature range of 20 C to +45 C. The polymers used for coating
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applications are usually random copolymers or terpolymers with monomer compositions such that the polymer glass transitions, Tg, fall in the middle to upper end of
this range. Polymers with glass transition temperatures below 0 C are not useful in
most coating applications because their films are tacky and weak under normal
ambient temperature conditions. Polymers with Tg significantly above 50 C tend to
be brittle and inflexible under normal ambient conditions and are less commonly
used in coating applications. These generalizations are most applicable to thermoplastic polymers, but the concepts can also be applied in a less formalized way to
thermoset coatings (temperature dependent reactive polymerization systems).
6.2.3
Film Formation
Coatings based on emulsion polymers exist as stabilized colloidal dispersions while

in the wet state. Upon application to the substrate, water evaporates and the film
dries and cures into the final coating. Properly designed and formulated, the wet
paint is stable indefinitely; however, the drying and film formation processes are effectively irreversible and result in a final film which is a tough, pigment-polymer
composite. The irreversibility of the film formation process is a key technical factor
underlying the successful utilization of emulsion based polymers for decorative and
protective coating applications. If film formation were reversible, then dried coatings
could be degraded by contact with liquid water; the ubiquity of water in our environment would make the utility of such coatings very limited.
Film formation from emulsion polymers is a complex process but for simplicity
it can be taken to consist of three phases. In the first step, water evaporates from
the continuous phase of the liquid coating and the polymer and pigment particles
begin to crowd together. The effective volume solids of the coating rises significantly. In the second phase, the latex and pigment particles begin to pack together
to create a contiguous film. In the third and final phase, interstitial water diffuses
out of the film and the emulsion polymer particles coalesce into a continuous,
inter-particle polymer network. The detailed physics and chemistry of the film
formation process are still not completely understood and are affected by many
factors [810]. Empirically, it has been observed that if the polymer Tg is higher
than the ambient film formation temperature, the final coalescence step of the
process may break down, resulting in a poor quality film with diminished integrity.
The minimum temperature at which an emulsion polymer will form a good film is
referred to as the MFFT (minimum film formation temperature) and is generally
a few degrees lower than the polymer Tg. It should not be a surprise that there
is a general relationship between the polymer Tg and the MFFT. Since film formation involves the interpenetration of polymer chains between adjacent polymer
particles, a reasonable amount of chain mobility must exist for this process to
proceed. However, the MFFT of an emulsion polymer is not a precisely defined
physical quantity and its value can depend on several factors in addition to Tg
including polymer molecular weight and composition, as well as the drying rate
of the applied coating. Hence, MFFTs are usually determined empirically by moni-
toring film formation as a function of temperature under a set of standardized drying conditions.
Most coatings are applied under ambient temperature conditions (either on a job
site or in a factory) with typical application temperatures between 10 and 40 C. To
ensure good film formation at the lower end of this range, polymer Tg values would
need to be in the 1015 C range. In practice, it has been found that polymers with
higher Tg are usually needed to provide optimized performance in many coating applications, particularly for coatings formulated at lower PVCs where the binder content is high. This presents a problem: polymers with desirable dry film performance
frequently have Tg which are too high to form a good film under typical drying conditions. To circumvent this problem, coatings formulators temporarily lower polymer Tg and MFFTs by use of coalescing agent. Coalescents work by partitioning into
the emulsion polymer particles, disrupting the packing of the polymer chains, and
thus lowering the effective polymer Tg. After the film is applied, the coalescent will
slowly diffuse to the film surface and evaporate, allowing the effective Tg to rise and
yielding a tougher, more useful coating. To be effective, the coalescent must be reasonably compatible with the polymer phase and relatively low in molecular weight in
order to partition into the polymer matrix. It should also have a moderate vapor pressure: the coalescent needs to remain in the film long enough to optimize film formation, but should also evaporate from the film reasonably quickly in order to allow
performance properties to develop. The choice of a coalescent depends on the polymer composition, the coating formulation and the intended application. Oxygenated
solvents of moderate polarity are commonly used for this purpose; these include various ether-esters of propylene and ethylene glycols, and ester-alcohols.
6.2.4
Typical Polymer Compositions
A variety of polymer compositions are used as binders in decorative and protective

coating applications. By definition, emulsion polymers are based on vinyl monomers, but even with this restriction there are a number of different polymer classes
which can be used for a given application. The choice of polymer system depends on
many factors, which we will highlight below in the context of specific examples of
coating applications. In this section we give an overview of the major emulsion polymer classes and discuss their general performance characteristics.
Styrene-butadiene copolymers
Historically, styrene-butadiene copolymers were the first emulsion polymers to be used
for coating applications. These polymers were based on technology developed for synthetic rubber production during WW II. Typical polymer compositions were 65 %
styrene with 35 % butadiene. While paints based on styrene-butadiene emulsion
polymers opened the door for the development of synthetic latex paints, their cost-performance profiles were not particularly competitive with the solvent borne coatings
present at that time or with the other emulsion polymer technologies which would be
developed later. They now occupy only a very small segment of the coatings market.
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Vinyl acetate copolymers

Vinyl acetate (VA) homopolymers were also used in early latex paints, and like
styrene-butadiene polymers, were also not particularly successful in the market. The
main problems were that the high Tg of VA homopolymers made it difficult for these
coatings to form strong, high quality films, and the mottling and loss of film integrity caused by hydrolysis of VA when applied over masonry (alkaline) substrates.
However, vinyl acetate can be copolymerized with butyl acrylate (BA) in an emulsion
polymerization process, resulting in internally plasticized copolymers with MFFTs
in the ambient temperature range and improved resistance to hydrolysis. When
large quantities of BA monomer became commercially available in the 1960s, the
use of VA-BA emulsion polymers in coating applications increased substantially.
Typical vinyl acetate-butyl acrylate copolymers compositions are 80 % VA with 20 %
BA by weight. Because of their relatively low cost, VA-BA copolymers have proven to
be very successful in interior decorative paint applications. While more resistant
than VA homopolymers, VA-BA copolymers can still be degraded by alkaline hydrolysis and their polar character can yield films which are relatively water sensitive.
These factors can limit the use of VA-BA copolymers in demanding exterior applications, although they are often used for less demanding exterior coatings when low
raw material costs are a primary formulation factor.
Vinyl acetate can also be copolymerized with ethylene (E) in an emulsion polymerization process. Again, ethylene serves as an internal plasticizer for VA, lowering the
Tg of the copolymer into the useful ambient temperature range. Since ethylene is a
gas at ambient temperature, VAE emulsion copolymers need to be manufactured in
specialized reactors, designed for high pressure use. Typical VAE copolymers used
in coating applications are about 90 % VA with 10 % ethylene by weight. While ethylene is a low cost monomer, the cost advantage relative to BA can be lost because of
the higher manufacturing costs associated the use of pressurized reactor systems.
The performance profiles of VAEs are similar to that of VA-BAs; like VA-BA copolymers, VAEs have been most successful in interior decorative coatings.
Styrene acrylic copolymers
Homopolymer styrene has a high Tg (100 C) and thus needs to be copolymerized
with a soft monomer for use in coating applications. Most frequently, butyl acrylate
is chosen for this purpose, and styrene-butyl acrylate copolymers used in coating applications typically have a composition of around 50 % styrene with 50 % butyl acrylate by weight. Styrene is a relatively low cost monomer (although styrene costs have
fluctuated widely over the years) which is produced widely around the world. Because styrene is relatively hydrophobic, paints based on styrene acrylic polymers
tend to be resistant to water transport and provide good barrier properties, particularly in comparison to vinyl acetate polymers. However, styrene has a strong absorption band in the near UV region of the electromagnetic spectrum, and photons of
this wavelength are energetic enough to induce photochemical processes which ultimately lead to polymer degradation and reduced exterior durability. In spite of this
drawback, the exterior durability of styrene acrylics is often adequate to meet the performance requirements for many exterior applications, particularly those where low
formulation cost is a primary consideration. Their barrier properties and resistance

to alkaline hydrolysis make styrene acrylics particularly popular in coatings for masonry applications, and often for stain blocking primers. Styrene acrylics are also
commonly used in industrial maintenance applications, where their good barrier
properties help provide effective corrosion resistance when applied over ferrous substrates.
Acrylic copolymers
Homopolymers of methyl methacrylate have a high Tg (100 C) and, like styrene and
VA, are too hard for typical coating applications. Again, butyl acrylate is commonly
used to provide internal plasticization, and to bring the Tg of acrylic copolymers
down into the ambient temperature range. Typical acrylic compositions for coating
applications are around 50 % methyl methacrylate and 50 % butyl acrylate by weight.
Unlike styrene, acrylic polymers do not absorb light in the near UV region, and thus
they are resistant to photochemically induced polymer degradation processes. As a
class, acrylics generally exhibit the best exterior durability of emulsion polymers
commonly used in coating applications. However, methyl methacrylate is a higher
cost monomer than VA or styrene, and coatings based on acrylic binders tend to have
higher raw material costs. Acrylic copolymers are used in a wide variety of coating
applications; they are most popular in exterior applications and can be engineered to
provide cost-effective performance features for interior applications as well.
Specialty monomers
Most emulsion polymers used in coating applications are based on the general
copolymer compositions outlined above. However, commercial polymers usually utilize small amounts of specialty monomers to provide added performance features
desirable for specific applications.
In the wet state, emulsion polymer coatings exist in the form of a densely crowded
colloidal dispersion. Good colloidal stability (resistance to particleparticle aggregation processes) is required in order to provide long term storage stability and to deliver the intended performance features.
Colloidal stability can be enhanced by utilizing coulombic or steric stabilization
methodologies. Coulombic stabilization is the most commonly used method, and involves including a small amount of ionizable species (<10 %) in the polymer composition. Usually an acidic monomer such as acrylic or methacrylic acid is used, which
upon neutralization with a suitable base, provides a layer of net negative charge on
the particle surface. The coulombic repulsion between these negatively charged particles can provide an effective barrier to thermally induced aggregation processes.
Most anionic surfactants associate with the surface of dispersed emulsion particles,
and they can also be used to increase coulombic stability in emulsion polymer systems.
Steric stabilization is based on attaching low molecular weight, water soluble polymers to the particle surface. This layer of soluble polymers on the particle surface
provides an entropically based repulsive interaction between particles, thus conferring additional colloidal stability. Both coulombic and steric stabilization inhibit un-
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desired particle aggregation in the wet coating and this enhances storage and shear
stability, as well as helping to optimize the film formation process.
A wide variety of other specialty monomers are also used to provide specialized
performance properties for coating applications. For example, amine functional
monomers can be used to improve adhesion to aged alkyd substrates. Specialized
monomers can also be used to improve exterior durability, for example VEOVA
(vinyl ester of vesatic acid) monomers can improve the hydrolysis resistance of vinyl
acetate polymers, and n-butyl methacrylate can be used to enhance the durability of
BA-MMA acrylics. Polymer hydrophobicity can be fine tuned by varying the levels of
hydrophobic and hydrophilic monomers in the composition and styrene or ethyl
hexyl acrylate are used to increase film hydrophobicity and reduce water permeability in BA-MMA systems. Specialty monomers are also used to provide specific chemical functionality to polymer compositions. For example, hydroxyethyl methacrylate
can be used to provide hydroxyl functionality to acrylic resins, allowing these polymers to be used in cross-linkable thermoset coatings which cure via melamine
chemistry. While specialty monomers are used at relatively low levels in polymer
compositions, they frequently provide the performance features needed for the successful application of emulsion polymers in many coating areas.
6.2.5
Pigments, Extenders, and Additives
While the polymeric binder is usually a major component of a coating formulation,

it is important to recognize that the other components (pigments, extenders, and additives) also play a vital role in ensuring a coating will meet the desired cost and performance targets. In this section we will give a brief overview of these other components, with the aim of providing the reader with a background sufficient to understand the formulations and examples discussed later in this chapter.
Pigments provide the color and hiding properties of a coating. They can be either
organic materials, such as phthalocyanine blue and carbon black, or inorganic materials such as titanium dioxide (TiO2) and iron oxide [11]. For coatings based on emulsion polymers, pigments usually exists as a colloidal dispersion of sub-micron or micron sized particles. Pigments are dispersed into a liquid by a high shear rate grinding processes, usually in the presence of specific dispersing agents (specialized surfactants or low molecular weight polyacid resins) which provide colloidal stability
and help optimize color efficiency. It is the selective absorption and scattering of visible light by the pigment particles which provides color and opacity to a coating.
TiO2, the most common pigment used in coating applications, gives a white color
and excellent hiding because its high index of refraction and carefully optimized particle size allow it to uniformly and efficiently scatters light across the visible spectrum. Colored pigments function by absorbing a portion of the visible light spectrum, and the unabsorbed spectral components are scattered back from the film, giving rise to its color. Pigments make up a substantial portion of a coatings total raw
material cost, and they are carefully processed and formulated in order to maximize
their performance.
Extenders provide a low cost way to adjust the solids level of a coating formulation.
For example, coatings formulated above CPVC generally contain high levels of extenders, because it would be cost prohibitive to raise the PVC this high by use of
TiO2 alone. Extenders are inorganic materials which are processed to yield particle
sizes on the micron scale. Functionally, extenders differ from inorganic pigments
because they do not significantly absorb or scatter visible light. Like the binder and
pigment components, the extenders in an emulsion based coating exist as a stable
dispersion in the water phase. A high shear rate milling process, aided by dispersing
agents, is used to create the dispersion. A variety of extender materials are commonly used in coating applications; these include: calcium carbonates, clays, feldspars,
silicas, and talcs [12]. While extenders are relatively inexpensive, they can have a significant impact on the performance of a coating. Careful selection of extender components is needed in order to optimize the cost-performance balance of a coating formulation.
Dispersants provide enhanced colloidal stability to pigment and extender particles
when formulating coatings based on emulsion polymers. Dispersing resins also facilitate the wetting and breakdown of pigment and extender agglomerates in the initial milling and/or grinding process and help to stabilize and reduce the viscosity
of the millbase (the millbase is a concentrated dispersion prepared from the pigment
and extender powders). Dispersants are generally low molecular weight, water soluble, vinyl resins with high levels of acid functionality. They are usually neutralized
with a base such as ammonium hydroxide, sodium hydroxide or potassium hydroxide, and are used at levels of 0.5 to 1.0 % by weight solids on pigment and extender
solids. In coatings based on emulsion polymers, dispersants act by increasing the
coulombic stability of the pigment particles; dispersing resins associate with polar
functional groups on the pigment surface, and the ionized acidic groups on the resin
backbone provide strong anionic stabilization to the particles under neutral or basic
pH conditions.
Thickeners are used to provide emulsion based coatings with the desired application rheology. Coatings formulated with emulsion polymers generally have volume
solids in the range of 2540 %, and in the absence of a thickening system, this range
of volume solids would be too low to provide adequate viscosity for most coating applications. The proper choice of a thickener and optimizing its level allows the coatings rheology to be adjusted to meet the needs of the intended application. There are
three main classes of thickeners or rheology modifiers which are commonly used in
emulsion polymer coatings: Cellulosic (a class of modified natural products, usually
hydroxy ethyl cellulose, or HEC), HASE (a class of synthetic polymers termed hydrophobically modified alkali swellable emulsions) and HEUR (a class of synthetic
polymers termed hydrophobically modified ethylene oxide urethanes). Cellulosics
are relatively high molecular weight water soluble polymers which thicken by raising
the viscosity of the water phase of the coating. HEC polymers were one of the original materials utilized for thickening water based coatings and they are still in common use, primarily in low sheen decorative coating applications. HASE thickeners
are high molecular weight emulsion polymers which are activated, or swelled, by
neutralization with a base such as ammonia. In contrast to conventional HEC, the
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HASE polymer backbone is modified by pendant hydrophobic functional groups,

which can associate with hydrophobes from other thickener molecules, hydrophobes
from surfactant molecules, and with hydrophobic domains on the surface of the
emulsion polymer particles. This hydrophobic association gives HASE thickeners
improved efficiency, and helps them resist volume exclusion flocculation, an undesirable aggregation process associated with high molecular weight, non-associating
polymers. HASE thickeners are cost effective and they are used in a variety of decorative coating applications. However, the alkali swellable component of their composition can increase the water sensitivity of a film, and they are not generally preferred
for demanding exterior applications. HEUR thickeners are also hydrophobically
modified synthetic polymers, but they are lower in molecular weight (50 000 g mol1)
and do not have the alkali swellable component of the HASE thickeners. Because of
their lower molecular weight and associative character, HEUR thickeners make a
positive contribution to the colloidal stability of a coating. They are particularly useful for demanding applications of decorative and protective coatings where higher
gloss, water resistance, and effective barrier properties are needed. Again, coating
manufactures careful optimize the rheology modifier package in order to ensure that
the coating applies correctly, and that it meets the appearance and performance
needs of the intended application.
Opacifying aids are frequently included in coating formulations to enhance the
hiding performance of TiO2. At low TiO2 levels, the opacity or hiding power of a coating increases linearly with TiO2 content up to about 10 PVC. Above this level, individual TiO2 particles begin to crowd or interfere with each other, and while total hiding continues to rise, hiding efficiency (hiding scaled to the amount of TiO2) starts to
fall off. In spite of this decrease in efficiency, coatings manufacturers generally utilize TiO2 levels in the range of 1525 PVC to provide adequate wet and dry film opacity. Opacifying aids work by improving TiO2 efficiency, and thereby allow coating
manufacturers to reduce formulated raw material costs while maintaining hiding
performance.
Common opacifying aids fall into two main classes: hollow sphere particles and
small particle size extenders. Hollow sphere particles are sub-micron sized hollow
polymer beads which enhance TiO2 hiding in the dry film by bringing a low index of
refraction air void in close proximity to the TiO2 particle. (In the wet state before the
film dries, the central air void is filled with water, and the hiding contribution is substantially reduced.) The air void effectively increases the difference in refractive index
between the TiO2 scattering centers and their surrounding medium, thereby increasing scattering efficiency and improving hiding. Since TiO2 levels are usually reduced when hollow sphere opacifying aids are utilized, hiding efficiency is also improved through a reduction in TiO2 crowding. Hollow sphere particles also make a
direct contribution to hiding, because their central air voids provide a certain amount
of intrinsic scattering to the dry film.
Figure 6-2 presents a transmission electron micrograph of a commercial hollow
sphere opacifying aid. The sample is presented as seen from above, with the polymer
shells appearing as a dark rings and the voids as the lighter cores. The particle size is
quite uniform with particle diameters of roughly 300 nm.

Fig. 6.2 Transmission Electron Micrograph of a Hollow
Sphere Opacifying Aid. Sample
was prepared by diluting polymer dispersion with water and
then drying a small quantity on
an electron microscope sample
grid. Contrast was increased by
staining with RuO4. Particles
are approximately 300 nm in
diameter. Polymer shells
appear as dark rings, and the
hollow cores appear as the
light areas within the rings.
Small particle size extenders are the other class of opacifying aids; acting as spacers, they increase the average distance between TiO2 particles in a film, thereby reducing crowding effects. The primary particle size of these specialized extenders is
quite small (typically <0.5 m), and the colloidal components of a coating need to be
properly formulated and stabilized in order for these materials to work effectively.
Biocides protect coatings from attack by microbial organisms. In the wet state, water based coatings possess the basic ingredients needed to support microbial growth:
water, a source of carbon and nitrogen, and trace minerals. The use of anti-microbial
agents, or biocides, is generally required to prevent water based paints from spoiling
while being transported and stored. A variety of materials are used as in-can preservatives for water based coatings; in general, preservatives used in these applications
are electrophilic compounds which function by reacting with nucleophilic groups
within the cell or on the cell surface, thereby disrupting the function of vital cellular
components. Isothiazolones, and materials based on formaldehyde are most often
used for this purpose, although other chemistries are used as well. Preservatives are
used at low levels and generally do not affect the performance properties of a coating,
unless they are inactivated and are unable perform their function.
Paint film mildewcides are commonly used in exterior coatings formulations to
prevent defacement of the coating surface by mold and mildew. The surface of an exterior coating can accumulate nutrient compounds from the local environment; they
may leach out from the substrate, or they may be deposited by rain or from the atmosphere. These materials, and the coating itself, support microbial growth on the
paint film surface. The microbial growth process can eventually lead to unsightly
mildew and algae growth on the coating surface, seriously affecting decorative performance, and in severe cases, causing deterioration of the film itself. Coatings
based on vinyl emulsion polymers have better resistance to microbial growth than
traditional alkyd coatings, but paint film mildewcides are usually included in exterior formulations to provide additional protection. (Apparently, the natural oil components of alkyd resins make them more readily metabolized by microorganisms, leading to poorer intrinsic mildew resistance.) In the past, paint film mildewcides based
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on organomercury compounds provided cost effective protection in emulsion polymer coatings, but environmental and health concerns now strongly limit their use.
Modern organic mildewcides have significantly improved environmental risk profiles; they partition strongly into the polymeric domains of the coating, and if they
are released into the environment by the weathering process, they are present at extremely low concentrations so that they can be broken down and metabolized by microorganisms in the soil. The most common organic paint film mildewcides in use
today are based on iodopropynylcarbamate, isothiazolone and chlorothalonil
chemistries. Over the life of a film, these biocides slowly diffuse to the coating surface where they act to control microbial growth. Combinations of organic biocides
are sometimes used to provide increased protection against a broad spectrum of microorganisms, and formulators commonly include zinc oxide in order to provide
longer term protection from mildew growth. Used properly, modern paint film
mildewcides offer a safe and cost effective means to significantly extend the service
life of exterior coatings.
Defoamers are used to prevent or to dissipate foam in coatings based on emulsion
polymers. Small air bubbles can be introduced into the liquid coating during the
manufacturing or application processes. If these bubbles are stabilized or long lived,
they can interfere with the efficiency of manufacturing, or leave unwanted voids in
the dried film. Unfortunately, the surfactants which are used in the manufacture of
emulsion polymers and water based coatings can also act to stabilize foam. Defoamers are used in a formulation to destabilize and to speed the breakup of foam in
the liquid coating. They are generally hydrocarbon or silicone based dispersions or
emulsions which have limited compatibility with both the water and polymer phases
of the coating. This marginal incompatibility is an important factor in defoamer effectiveness, and it must be properly balanced or it can result in film defects or loss of
activity. While typically used at low levels (<1 % by weight), defoamers can significantly enhance the paint manufacturing process, as well as improving the application, appearance and performance characteristics of a coating.
Wetting aids are used to improve the ability of water based coatings to form defect
free films over a variety of substrates. Pure water has a high surface tension,
73 mN m1 [9], and while the surfactants present in a water based coating can reduce
this to values in the 2530 mN m1 range, this may not be adequate to allow proper
wetting (and thus adhesion) to low surface energy substrates such as plastics or certain re-paint surfaces. Also, surfactants can potentially interact with all the colloidal
materials in a coating formulation (pigments, extenders, thickeners and defoamers)
this can affect the amount of free surfactant available to reduce the surface tension.
The equilibrated surface tension of a formulated coating will ultimately depend on
the complex distribution of surfactants molecules between these colloidal particles,
the water phase and the coating surface, and the judicious use of wetting aids can be
used to supplement colloidal stability and to promote proper wetting of the substrate. Typically wetting aids are surfactants or very low molecular weight oligomeric
polymers. A wide variety of non-ionic and ionic surfactants are used, including hydrocarbon and silicone based materials. They are generally selected by a combination of previous experience and direct testing. Different wetting aids are used to ad-
6.3 Decorative Coatings
dress a variety of coating problems, including poor substrate adhesion, poor flow and
leveling and poor color acceptance. While typically used at low levels (<1 %), they can
play a vital role in enabling water based coatings to meet specific appearance and
performance requirements.
6.3
Decorative Coatings
The primary role of decorative coatings is to enhance the esthetic appeal of homes,
offices and other architectural structures by providing color, texture and sheen to
interior and exterior surfaces. Decorative coatings are commonly classified by their
intended application, and these include interior wall, interior trim, exterior wall and
exterior trim. The sheen level of the coating is also commonly characterized, and
these terms include flat, semi-gloss and gloss. These distinctions are not rigid
or comprehensive, and coating manufactures commonly break these classes down
further, or combine them, in order to enhance the marketability of their products.
There are also many kinds of more specialized decorative coatings, such as masonry
finishes, clear and stain finishes for wood, floor paints for masonry and wood, driveway sealers and arts and crafts finishes. Space limitations prevent a detailed discussion of these specialized coating applications, but much of the information we present here can be easily adapted to these coatings.
6.3.1
Emulsion Polymers in Decorative Coatings
The history of decorative coatings is long one, arguably extending back to prehistoric
times with paintings on the walls of cave dwellings. Focusing on more recent times,
solvent borne drying oils and alkyds were the predominant polymer technologies
used throughout most of the twentieth century. However, rising environmental and
health concerns, coupled with improvements in the performance of emulsion polymer coatings, have allowed water based coatings to move into the leading positions
in the decorative application areas. While emulsion polymers are now the market
leaders in most decorative applications, there are still a variety of technical issues
which remain to be addressed by both raw material suppliers and paint manufacturers. Clearly, regulatory pressure to drive down VOC emissions continues to increase
throughout the world, and the challenges of balancing the often conflicting objectives of product cost, product performance and product differentiation remain.
6.3.2
Polymer Compositions used for Emulsion-based Decorative Coatings
A variety of thermoplastic emulsion polymers are used in decorative coating applications, with VA-BAs, EVAs, styrene acrylics, and acrylics being most popular. VA-BAs,
EVAs and styrene acrylics are commonly used for interior flat wall coatings, with the
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choices between them generally based on regional economic and performance characteristics. Acrylics and styrene acrylics are the preferred chemistries for exterior
applications, again with regional economic factors and performance characteristics
driving specific choices. Acrylics and styrene acrylics are both used for interior and
exterior gloss and semi-gloss applications, while for interior semi-gloss applications,
VA-BAs, acrylics and styrene acrylics are commonly used. These are generalizations,
and the specific choices made by paint formulators are based on a complex mixture
of factors, including regional custom, local availability, raw material cost, and specific performance needs.
6.3.3
Regional Distinctions in Decorative Coatings
There are significant regional distinctions in the formulation of decorative coatings.

Differences in building materials and, consequently, the substrates to which coatings are commonly applied, underlie many of these distinctions. For example, North
America (NA), Australia New Zealand (ANZ) and Scandinavia all have relatively
high levels of wood substrates, whereas masonry substrates are more common in
Europe, Latin America (LA) and Asia. Substrate differences are a major factor in the
preference of acrylics for exterior wood applications in NA, ANZ and Scandinavia,
the use of elastomeric wall coatings for masonry applications in Europe, and the
choice of styrene acrylics for masonry applications in LA and Asia.
The availability of supplies of low cost monomers is another important factor affecting the choice of polymer composition; this drives the use of VA-BA polymers for
the low cost interior flat segments of NA and ANZ, and the use of styrene acrylics for
decorative segments in Europe and Asia. In Latin America, decorative paints are
commonly designed for both interior and exterior applications, and styrene acrylics
and VA-BA polymers predominate in these markets. Regional economic factors also
influence the choice of polymer used in coating applications: differences in raw material costs, and in labor costs, can affect how end users balance the higher initial
costs associated using a more durable, high performance coating, versus the higher
deferred costs associated with using a less durable coating having a more frequent
re-paint cycle.
6.3.4
Market Size of Decorative Coatings
Decorative coatings, as defined here, account for roughly 40 % of worldwide coatings

production. The ratio can vary from country to country; heavily industrialized countries have a relatively higher proportion of protective and product finishes, while less
industrialized countries often have a higher proportion of decorative finishes. Starting with the world wide coating production estimate of 20 billion liters per year [1],
and taking the fraction of decorative finishes to be 40 %, would give the total production of decorative coatings to be roughly 8 billion liters per year worldwide. Assuming that about 50 % of this is based on emulsion polymer technology leads to an esti-
6.4 Interior Decorative Coatings
mated annual production of about 4 billion liters of water-based decorative coatings

world wide. We estimate the North American market to be a third of this value or
about 1.5 billion liters per year. If we estimate the average retail selling price to be
$45 US per liter, this gives a total NA market value of $68 billion US per year for
decorative coatings. The volume of the European decorative coating market is roughly comparable in size to the North American market. Taking the annual European
production estimate to be also 1.5 billion liters per year, and assuming an average
retail selling price of roughly 45 Euros per liter, would give a total European market
value of about 68 billion Euros per year for decorative coatings. Again it is important to emphasize that these are very rough estimates, and are intended to give the
reader a general picture of market size.
6.4
Interior Decorative Coatings
Interior decorative paints are designed to provide texture, sheen and color to the interior walls and ceilings of homes and offices. Paints based on emulsion polymer
technology now account for most of this segment. The popularity of water based
paints in interior decorative applications is due to many factors, including their ease
of use, low odor, fast dry, good appearance and color stability, and the ease of soap
and water clean-up. Paints for this application are designed for a variety of specific
applications such as kitchen and bath, wall, trim and ceiling; they also provide different sheen levels such as flat, satin, semi-gloss and gloss. Coatings manufacturers
produce a wide variety products to meet the different needs of this large market segment, and this in turn requires a correspondingly large number of formulations and
raw materials. Because of space limitations, we will focus our discussion on two of
the major segments of the interior decorative market, flat interior wall paints and interior trim enamels, and use them to highlight performance and formulation concepts of this market segment.
6.4.1
Key Performance Features
Interior flat wall coatings have a low or flat sheen, and they are usually formulated
with an 85 gloss level below about 4 %. Low sheen levels are usually achieved by using large particle size extenders at relatively high PVCs. While low sheen levels help
to hide defects in the substrate, differences in sheen and color are readily observable
in these coatings, and thus sheen and color uniformity of the applied coating are key
performance attributes. Good application characteristics are important as well; interior flat wall paints are frequently spray applied in new construction applications,
and are generally applied by roller in re-paint applications. Formulating with associative thickeners (typically HASE) can help reduce roller splatter, an important characteristic in re-paint applications. End users expect decorative coating to have good
hiding characteristics, and while true one-coat hiding remains an elusive goal, coat-
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ing manufacturers carefully balance hiding performance and cost in these formulations. Interior flat coatings also need to have good cleanability characteristics, since
they are routinely applied to living areas (with higher potential for dirt and stains),
and the coatings ability to be easily cleaned can add significantly to its service life
and user satisfaction.
Enamel coatings are frequently applied to trim surfaces such as doors, window
frames, decorative moldings around doors and windows, base boards, cupboards
and shelving. These surfaces often have a high level of day to day human contact and
a tougher, more resistant coating is needed to provide substrate protection, film integrity and optimum appearance characteristics. Trim enamels are frequently brush
applied so good flow and leveling characteristics are important. Enamels are generally formulated at higher sheen levels, with values for semi-gloss and gloss coatings
ranging from 3085 % at 60, respectively. They are applied over a variety of substrates, including aged alkyd, aged water based enamels, primed wood or metal, and
thus they must have good adhesion characteristics. It is also desirable that the coatings hardness develop quickly so that objects can be placed on painted surfaces
without marking the film. Trim enamels should also have good block resistance so
that adjacent painted surfaces can be pressed into contact without sticking to each
other. Finally, because they are applied in high use areas such as doors, windows and
kitchen areas, trim enamels need good stain resistance and cleanability.
6.4.2
Interior Decorative Coating Formulations

Flat Interior Wall Coatings
Cost is one of the most important factors for interior flat coatings and drives many of
the choices in formulations and raw materials. Vinyl acetate and styrene based
copolymers are most frequently used as binders for this market and cost considerations also drive the use of relatively high levels of low cost extenders. Thus, PVCs are
generally high, and are usually above CPVC. Opacifying aids are commonly used to
help achieve high hiding levels, and they also help to lower raw material costs by reducing TiO2 levels. Rheology modifiers are chosen to provide the desired rheology
profile, with HASE and cellulosic thickeners being most commonly used. A coalescing agent is usually included to enhance film formation, although recently developed
binders for interior flat coatings can often be formulated with very little or no added
coalescent. Propylene glycol is commonly used as a pigment grinding aid, and to improve the freeze thaw resistance of the wet paint during storage. Finally, anionic and
non-ionic surfactants are commonly added to optimize colloidal stability and enhance color development and uniformity. Table 6-1 provides an example of a typical
interior flat coating formulation.
Interior Enamels
Polymer performance plays a more significant role in the formulation of enamel
coatings than in flat coatings, since the polymer component makes up a higher volume fraction of the dried film. Acrylic and styrene acrylic emulsion polymers are

Tab. 6-1
Interior decorative flat formulation.
Material
Weight %
Grind
Water
Propylene Glycol
Dispersant
Defoamer
Biocide
Aminomethylpropanol
Titanium Dioxide
Calcined Clay Extender
Calcium Carbonate Extender
Grind sub-total
13.56
4.07
0.52
0.18
0.16
0.18
10.73
13.65
9.04
52.09
Let down
VA-BA Emulsion Polymer
Hollow Sphere Opacifying Aid
Coalescent
Defoamer
Water
HEUR Thickener
Ammonia (28 %)
HASE Thickener
Total
Property
Total PVC
Volume Solids
Weight Solids
Comments
Prepare in a high speed disperser
19.72
6.84
1.34
0.18
16.58
1.72
0.18
1.36
100.00
Grind and freeze-thaw aid

Polyacid
Hydrocarbon dispersion
Isothiazolone preservative
Base, grind aid
Interior grade
Coarse grade
Add to grind with good agitation

55 % Solids
Ester alcohol, film formation
25 % solids
Base
Emulsion
Value
63 %
33 %
47 %
most commonly used in this segment, with vinyl acrylics playing a role in the lower
performance/lower cost end of the market. Performance considerations limit the
PVCs of these coatings, and enamels are formulated significantly below critical PVC,
generally in the range of 1525 % PVC. Extenders and opacifying aids are not commonly used in gloss enamel coatings, and are used to a limited extent in semi-gloss
coatings. HEUR and HASE thickeners are often used as rheology modifiers; they
provide excellent flow and leveling with brush application and generally allow for
higher gloss levels. The harder polymers used in enamel coatings generally require
higher levels of coalescing agents to provide good film formation. Again, anionic and
non-ionic surfactants are commonly added to optimize colloidal stability and enhance color development and uniformity. Table 6-2 provides an example of a typical
interior/exterior gloss enamel formulation.
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Tab. 6-2
Interior/exterior decorative gloss enamel.
Material
Weight %
Grind
Propylene Glycol
Water
Biocide
Dispersant
Surfactant
Defoamer
Titanium Dioxide
Grind sub-total
3.36
2.43
0.10
1.12
0.10
0.02
21.28
28.39
Let down
Acrylic Emulsion Polymer
Water
Diethylene glycol butyl ether
Coalescent
Phosphate Surfactant
HEUR Thickener A
HEUR Thickener B
Defoamer
Total
Property
Total PVC
Volume Solids
Weight Solids
50.67
15.16
0.58
2.50
0.09
2.36
0.19
0.05
100.00
Comments
Grinding aid
Hydrophobically modified polyacid
Non-ionic pigment wetting aid
Silicone emulsion
Universal Grade

Specialized gloss enamel vehicle
Co-solvent
Ester alcohol, film formation
Wetting Aid
20 % solids
25 % solids
Silicone emulsion
Value
21 %
32 %
45 %
6.4.3
Standard Application and Performance Tests
Many specialized tests have been developed to measure the application, appearance
and resistance properties of interior decorative coatings. The reader is referred to
the specific ASTM and ISO test methods given in Tab. 6-3, and the cited references [1314] for a more detailed description of test method protocols. Our objective
in this section, and in the subsequent application and performance test sections, will
be to identify the key performance features and to give the reader an overview of how
these tests are conducted.
Decorative coatings are often stored for long periods of time under sub-optimum
conditions before they are sold or applied. In the warmer regions of the world, coatings are frequently stored in warehouses where temperatures can reach 45 C for extended periods of time. In the colder regions of the world, coatings can be subjected
to repeated freeze-thaw cycling when stored at an unheated job site. Heat age and
freeze-thaw stability testing protocols have been developed to assess the storage stability of coating products. Heat Age Stability is tested by placing the paint in an oven
for a specific time and temperature, and then testing the coating for key performance

Tab. 6-3
Selected coating applications test methods.
Application test
ASTM method*
ISO method**
Freeze-thaw resistance
Heat age stability
Low temperature film formation
Gloss
Color acceptance
Hiding
Block resistance
Print resistance
Adhesion qualitative
Adhesion quantitative
Scrub resistance
Stain removal (top coat)
Stain blocking (tannin)
Durability exterior
Durability accelerated
Corrosion exterior
Corrosion accelerated
Tensile testing
Permeability testing
Early washout (traffic paint)
No pickup test (traffic paint)
D2243
D1849
D3793
D523
D5326
D344, D2805
D4946
D2064
D3359, D6677
D2297, D4541
D2486, D4213
D3450, D4828
D6686
D660, D661, D662, D772, D3719, D4214
D4141, G26, G53, G151
D610, D1014
D2803, D4587, G85
D2370
D1653
D 1640 Modified
D711,D713
1147
2813
2814, 6504
3678
2409
4624
11998
4586
4628
4892, 11341
4628
7253, 11997
7783
** ASTM test methods can be obtained from the ASTM web site http://www.astm.org
** ISO test methods can be obtained from the ISO web site http://www.iso.ch
properties. Many different time-temperature protocols are used; two common ones
are 10 days at 60 C or 30 days at 50 C. Freeze-thaw stability is tested by subjecting
the coating to repeated freeze-thaw cycles, typically 35 cycles of temperature
changes between 20 C and room temperature; changes in viscosity and other key
performance properties are then evaluated.
Decorative coatings are commonly applied by brush, roller, or spray techniques,
and coatings manufacturers generally design their products to perform well when
applied by any of these methods. Testing protocols include laboratory testing under
carefully controlled conditions, and field trials under realistic application conditions.
The objective is to develop a coating which applies correctly, has a rheology profile
which allows good flow and leveling, without excessive sagging, and provides a uniform coating to the substrate. Application properties are particularly important with
products designed for professional painters, since these features are vital to reducing
call backs and maintaining high productivity.
Good initial appearance is an important factor in determining customer satisfaction in any coating application, but is particularly vital for decorative finishes. The
applied coating is expected have the right color and the right sheen level. Defects in
the applied coating should be minimal, and easily repairable. A variety of standardized laboratory instruments have been developed to measure sheen, hiding and color development (Tab. 6-3). Also, many specialized tests have been developed to as-
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sess appearance properties under specific application conditions. For example the
color rub-up test assesses the color variability of a coating when applied by brush or
roller application techniques. Since large interior wall areas are usually painted by
brush application around the perimeters, and then filled in by roller application to
the center sections, variations in color uniformity can have a significant impact on
end user satisfaction. In laboratory testing of this property, a draw-down of uniform
film thickness is first applied, and then a section of the coating is either rubbed with
the finger or brushed until the coating starts to dry. Color differences between the
low shear rate draw-down region and the high shear rate rub up or brushed region
are then assessed subjectively, or measured quantitatively with a color spectrophotometer. Problems in this area are generally related to poor colloidal stability; a lightly flocculated pigment dispersion can be temporarily dispersed by the high shear
conditions of brushing, and this can result in a color which appears different from
adjacent areas coated under the lower shear rate of roller application.
Resistance properties
In contrast to the appearance and applications properties of a coating, resistance
properties are not assessed by the user during and immediately after the application,
but rather, they impact user satisfaction by affecting the service life of the coating.
Laboratory testing plays a key role in assessing the resistance properties of coatings,
because it provides a controlled and accelerated measure of performance features
which may take years to become evident in actual end use applications. Adhesion is
a key performance factor and several tests have been developed to measure this parameter. All adhesion tests follow the general protocol of applying the test coating to
a defined substrate such as chalky or aged alkyd, steel or aluminum, allowing the
coating to dry for a specified time, and then testing the adhesion of the applied coating by attempting to separate it from the substrate. Adhesion can be tested under wet
or dry conditions (wet adhesion is usually a more severe test than dry adhesion), and
the coating is usually scored or cut in order to minimize the confounding effects of
film integrity. Cohesive failure occurs when the coating remains bound at the
filmsubstrate interface and separation occurs within the coatings itself, or by destruction of the substrate. This is generally indicative of good adhesion performance,
but it can sometimes be misinterpreted when a coating has extremely poor film integrity (giving a false positive reading). Adhesive failure occurs when the applied
coating separates from the substrate at the interface between the coating and the
substrate. Failures of this type can be assessed via subjective or quantitative measurements, such as using knife peel, cross hatch/tape pull, or a quantitative measurement of the force to peel. While it is desirable to have a coating exhibit cohesive failure in lab tests, coatings which exhibit adhesive failure often show good adhesion
performance in actual exposure testing. Experience and careful comparisons against
known standards are generally required in order to obtain useful performance predictions in these cases.
The cleanability of a coating is generally assessed by stain resistance or scrub tests.
In the stain resistance test, the coating is allowed to dry for a specified time (usually
a week) and then common staining materials such as coffee, tea, fruit juice, mustard,
ketchup, pencil, pen or felt tip marker are applied to the surface. After a specified
contact time, the coating is washed with a cleaning formulation and then is rated for
stain removal relative to controls. The scrub test assesses cleanability differently, and
measurers the ability of a coating to resist abrasion by a stiff brush and an abrasive
cleaner, or cleaning solution. A coating of defined thickness is applied to a vinyl
chart and dried for a specified time, usually a week. A specialized scrub testing machine is used to scrub the coating with a brush and a standardized abrasive medium.
The operator assesses the number of scrub cycles needed to wear through the coating to the substrate. In another variation of the scrub test, the test coating is placed in
the testing machine for a fixed number of cycles using either the abrasive medium or
a cleaning solution, and then cleaned and dried. Performance is assessed by measuring the weight of coating lost during the scrub process. Both tests are subject to
high levels of variability and carefully controlled experiments are needed to produce
accurate and reproducible results.
Block resistance is a measure of a coatings ability to resist destructive self adhesion when placed into contact with itself. This is an important feature for coatings
which are applied to windows and doors, since in these components, painted surfaces are placed in contact in routine operation. Dry time and contact pressure are
important factors affecting block resistance and are the primary variables which are
controlled in laboratory testing. The coating is cast on a non-rigid substrate such as a
coated paper chart, and allowed to dry under controlled conditions for a specified
time (typically ranging from 8 h to 4 weeks). Small squares of the coated substrate
are then cut out and placed with the coated sides facing together. A defined pressure
(generally in the form of a 0.5 kg weight on a surface area of approximately 5 cm2) is
applied for a specified period of time and temperature (typically 12 h at 25 C or 4 h
at 50 C). The test squares are then pulled apart and rated subjectively for self adhesion. Ideally, the two test squares separate with minimal force, leaving no film damage. Failure is noted when the film is visibly damaged upon separation. In a variation
of this test, the coating can be applied to a rigid substrate such as glass or metal, and
these test areas are placed together, under pressure, as described above. The force
necessary to separate the test areas is then measured quantitatively.
The print resistance test measures the ability of a coating to resist permanent imprinting caused by the placement of heavy objects, such as books or vases, on a horizontal coated surface. In this test, a coating is cast onto a metal substrate, and then a
heavily textured object, such as a rough cloth is placed on the coated surface with a
defined pressure (typically about 1 kg per 5 cm2). The test is allowed to progress for a
specified time and temperature (usually one week at 25 C, or one day at 50 C), and
then the coating is evaluated subjectively against controls for its ability to resist permanent marking or defacement.
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6.5
Exterior Decorative Coatings
Exterior decorative coatings are used to provide aesthetic and protective features to
the exterior walls and trim of houses, apartments and offices. They share many of
the application, appearance and resistance features characterizing interior decorative
coatings, with the obvious and important difference that they are expected to provide
these features while being subjected to the deleterious effects of UV radiation and
weathering. In addition, exterior decorative coatings are expected to protect their
substrates from the harmful effects of weathering for the lifetime of the coating.
Historically, alkyd and oil based coatings were commonly used in exterior decorative
applications, but over the past 30 years coatings based on emulsion polymers have
advanced and are now the preferred technology for this application. The primary
reason for this is the superior durability of acrylic emulsion polymers (and to a lesser
extent vinyl-acrylic and styrene-acrylic polymers) in exterior applications. Alkyd and
oil based coatings rely on oxidative cure processes to develop resistance properties.
While the cure processes are quite efficient, they can eventually lead to film embrittlement and subsequent cracking over dimensionally unstable substrates. Additionally, most alkyd resins are made by the esterification of phthalic anhydride with unsaturated fatty acids or natural drying oils. The UV absorption characteristics of
these materials make them quite susceptible to UV degradation, leading to poor tint
retention and premature chalking. Finally, the ester linkages of oil and alkyd based
coatings are susceptible to alkaline based hydrolysis, a polymer degradation process
which can be accelerated by the basic pH conditions present in many masonry applications, particularly over freshly prepared concrete. Acrylic based polymers are more
resistant to these different degradation processes and, consequently, have become
the performance standards for exterior decorative coatings.
6.5.1
Exterior durability is the key factor which differentiates the performance of exterior
decorative coatings. This is primarily manifested in three important areas: tint and
gloss retention the ability of a coating to maintain its original color and gloss level
during exposure, chalk resistance the ability of a coating to resist the surface powdering caused by UV and moisture induced polymer degradation, and resistance to
cracking and adhesion loss the ability of a coating to resist grain cracking and the
subsequent flaking and loss of adhesion when applied over wood substrates. Good
dirt pick-up resistance is also important; the coating should be resistant to darkening
caused by adsorption of dirt and soot from the external environment. Adhesion to a
variety of architectural substrates is also an important performance feature, particularly in re-paint applications where weathered substrates present particular challenges. Because exterior coatings are generally viewed from a distance, appearance
properties such as flow and leveling are somewhat less important than they are in
many interior applications. Of course, most of the other performance features de-
6.5 Exterior Decorative Coatings
scribed above for interior decorative coatings also apply to their exterior counterparts.
6.5.2
Exterior Decorative Coating Formulations
Acrylic emulsion polymers are generally preferred for exterior decorative applications because of their good exterior durability characteristics. Styrene acrylics and
vinyl acrylics are also popular, particularly in regions of the world where lower labor
costs reduce the economic barrier to a more frequent re-paint cycle. In contrast to interior flat paints, exterior flat paints are generally formulated below CPVC in order to
provide improved durability. Because good moisture resistance generally is required
for exterior applications, cellulosic and HEUR thickeners are generally chosen as
rheology modifiers for exterior applications; cellulosics are commonly used in exterior flat formulations, while HEURs are commonly used in gloss and semi-gloss
formulations. Durable grades of TiO2, coated with inorganic materials to provide
improved UV resistance, are generally chosen for exterior applications. The choice of
extenders can also have a significant impact on the performance of exterior coatings.
Based on our experience, the tint retention and chalk resistance of exterior flat coatings can be enhanced by favoring the use of coarse silica or nephiline syenite over
clays. Calcium carbonates generally have good tint retention, but they can degrade in
regions with acid rain, sometimes leading to poor dirt pick-up resistance. Carbonates
can also can show frosting (the appearance of a hard white exudate, visible on tinted
films) in horizontal face down applications. Finally, a paint film mildewcide is generally included in exterior formulations, particularly in flat and satin formulations, to
minimize mildew growth on the coating after application. A typical formulation for
an exterior flat decorative coating is given in Tab. 6-4.
6.5.3
Exterior exposure testing is the most direct and reliable method to evaluate the durability of exterior decorative coatings. The most representative and general exposure
protocol is to actually apply the coating to test homes or buildings, and to then evaluate the performance over a long period of time. However, the cost and logistics of
such large scale trials limit their use, and the vast majority of exterior exposure testing is done via controlled exposure experiments carried out at established exposure
sites around the world. Most raw material suppliers and many coating manufacturers have set up their own exposure sites, or use commercial exposure services, to
provide this capability. A typical experimental design for an exposure experiment
would include experimental and control coatings which are applied, in replicate, to
test areas (on the order of 15 cm 30 cm) over a variety of representative substrates.
The choice of substrates depends on the intended market segment and region, but
normally would include several different types of wood and masonry in both new
and re-paint applications. In the Northern hemisphere, South vertical exposures are
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Tab. 6-4
Exterior decorative flat formulation.
Material
Weight %
Grind
Cellulosic Thickener (2.5 %)
Water
Dispersant
KTPP
Non-Ionic Surfactant
Defoamer
Biocide
Mildewcide
Titanium Dioxide
Zinc Oxide
Nepheline Syenite Extender
Functional Extender
Grind sub-total
10.71
7.17
1.52
0.08
0.08
0.17
0.14
0.25
21.09
2.11
16.87
0.42
60.64
Let down
Acrylic Emulsion Polymer (60 %)
22.86
Ester Alcohol Coalescent

Ethylene Glycol
Defoamer
HEC Thickener
Water
Total
Property
Total PVC
Volume Solids
Weight Solids
0.83
0.25
0.17
8.07
7.17
100.00
Comments
HEC thickener
Co-dispersant
Pigment wetting aid
Isothiazolone mildewcide
Exterior universal grade
Mildew protection
Coarse grade
Thixotropic clay

Enhanced adhesion to alkyd and
chalky re-paint
Film formation
Co-solvent and freeze-thaw aid
2.5 % in water
Value
50 %
35 %
54 %
commonly chosen to accentuate failure modes which are linked to UV exposure;

these include gloss loss, grain cracking, chalking and color fading. North vertical exposures are used to evaluate mildew resistance and discoloration by dirt pick up.
Exterior exposure testing is not a rapid process; some failure modes can take several years to develop. Exposures at South 45 can be used to accelerate failure modes
linked to UV radiation and moisture; this exposure angle increases the flux of UV
energy incident on the sample, as well as increasing the intensity and duration of
moisture contact brought about by the daily dew cycle and rain. However, 45 exposures are generally uncommon in real world applications, and the data obtained
from these experiments should be interpreted with caution. By using specialized
exposure techniques such as: exposing samples at South 45, selecting woods with
poor dimensional stability as substrates, and applying thinner layers of coating (one
coat applications), coatings scientists can accelerate the exposure testing process.
However, even with these methods, it can still take 2 years or more to develop a clear
picture of a coatings durability characteristics.
6.6 Elastomeric Wall Coatings
Accelerating the process for assessing the durability of exterior coatings is of obvious interest to raw material suppliers, coating manufacturers and end users. This is
currently an area of active research and a variety of efforts are under way to improve
the predictive ability of accelerated weathering protocols [15]. While a variety of exposure instruments and devices have been developed, and are commonly used to
provide accelerated exposure information, we have found that these instruments do
not always provide information consistent with exterior exposures. Accelerated exposure devices have proven to be most useful when evaluating specific failure modes,
and comparing the performance of coatings of similar composition, applied over dimensionally stable substrates.
6.6
Elastomeric Wall Coatings
Specialized elastomeric wall coatings were first introduced into European markets in
the early 1980s. Their function is to enhance the appearance and durability of exterior masonry surfaces present on large buildings such as apartments, hotels and offices. These types of structures often have large uniform surfaces which can be disfigured by small cracks and fractures, caused by uneven thermal expansion and contraction. Elastomeric coatings improve the appearance of masonry surfaces by covering these small cracks with a smooth elastic film, and they enhance the durability of
masonry substrates by preventing the intrusion of water into these defects.
6.6.1
Elastomeric wall coatings are designed provide a high quality decorative and protective finish for large masonry surfaces. The elastic character of these coatings, along
with the use of thicker applied films, allows them to bridge cracks in the substrate
and to stretch and shrink with thermally driven building movement. Elastomeric
coatings also prevent the penetration of wind driven rain and water into the substrate
by sealing these cracks, thus improving the durability of the underlying masonry material. Emulsion polymers used for elastomeric wall coatings generally have low Tg
(typically less than 20 C) in order to provide the elastic character needed for effective crack bridging. The use of such soft polymers would normally lead to coatings
with poor dirt pick up resistance and tackiness, but proprietary technologies are usually employed to address these problems. Elastomeric coatings can significantly enhance the durability of many masonry surfaces, and because masonry construction
is widely used around the world, the use of elastomeric wall coatings has grown significantly over the past 20 years.
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6.6.2
Typical Elastomeric Wall Coating Formulations
Elastomeric coatings are formulated to yield tough films which maintain a balance of
tensile strength and elongation characteristics across a broad temperature range
(10 to +30 C). These coatings are generally formulated at relatively low PVCs (typically in the range of 3045 %) to provide the dried film with good elasticity and barrier properties. These coatings are formulated with relatively low levels of hiding pigments, since thick coatings are generally utilized. They are usually extended with
fillers such as calcium carbonate. Volume solids are typically high, in the in range of
50 % to 60 %, in order to provide for thicker dried films. For optimum long-term performance, it is recommended that the total dry film thickness be in the range of 300
to 500 m, much thicker than typically used in architectural applications. Coatings of
this thickness need a carefully optimized rheology profile in order to prevent sagging
during the application and drying processes. Cellulosics, either alone or in combination with HEUR thickeners, are generally preferred for this application. An effective
paint film mildewcide is also need in order to prevent discoloration of the coating
surface by mildew growth. Elastomeric wall coatings are generally formulated to be
applied by professional painters using either roller or spray application techniques.
A typical elastomeric coating formulation is given in Tab. 6-5.
Tab. 6-5
Elastomeric wall coating formulation.
Material
Weight %
Grind
Water
Ethylene Glycol
Dispersant
KTPP
Defoamer
Titanium Dioxide
Zinc Oxide
Grind sub-total
5.67
2.75
0.44
0.09
0.35
6.20
26.12
2.21
43.84
Let down
Surfactant
Defoamer
Mildewcide
HEC Thickener
Water
Total
Property
Total PVC
Volume Solids
Weight Solids
Comments
Prepare with high speed disperser
0.55
54.20
0.09
0.18
0.27
0.89
100.00
Value
31 %
49 %
61 %
Grind aid and freeze-thaw

Polyacid
Co-dispersant
Exterior Grade
Fine grade
Mildew protection

Wetting aid, non-ionic
Specialized elastomeric vehicle
Isothiazolone class
Solid
6.7 Primer Coatings
6.6.3
The tensile and elongation properties of an elastomeric coating are important

performance features which characterize the coatings ability to bridge cracks in the
substrate. These properties are commonly evaluated in the laboratory at ambient and
below ambient temperatures by use of a tensile testing instrument (Instron type or
equivalent). Testing is performed at a constant rate of jaw separation with load cells
adequate to measure the tensile forces generated. Testing sample dimensions are
usually about 500 m thick 2 cm long 1 cm wide, and samples are cut with a die
from a dried film which was drawn down over a Teflon release plate. The sample is
fastened between the jaws of the tester and is stretched apart at a constant strain rate
until it breaks. Values for the percent elongation and tensile strength at break are
then calculated. These values depend somewhat on the strain rate used; generally,
lower strain rates yield higher values for elongation, coupled with lower values for
tensile strength at break.
The permeability of an elastomeric coating is crucial for determining whether the
coating will allow adequate passage of water vapor through the coating. In the laboratory, permeability is evaluated by sealing a dried paint film of specified thickness
over a cup of water and placing the assembly in a constant temperature and humidity room. Water loss from the cup, through the film, is measured by mass difference
over the course of one week. Permeability is then calculated from the rate at which
water is lost through the film.
6.7
Primer Coatings
Primer coatings are used to provide a functional boundary layer between the substrate and the topcoat. Coating manufacturers design a variety of specialized primers
to enhance total system performance for a variety of coating applications. Primers
generally provide many or all of the following features:
(i) they promote effective adhesion to a variety of substrates;
(ii) they prevent the transport of a variety of different types of colored stains from
the substrate to the topcoat;
(iii) they enhance corrosion resistance;
(iv) they serve as a flexible linkage between dimensionally unstable substrates and
the topcoat; and
(v) they reduce irregularities and imperfections in the substrate, providing a
smoother and more uniform surface for the topcoat.
Decorative and protective primers generally have demanding performance specifications, and are usually formulated at relatively low PVCs and high volume solids.
They usually are not designed to provide high hiding or intrinsic weathering resistance, since the topcoat can be independently optimized to provide these and other
performance features.
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6.7.1
Primer vehicles based on emulsion polymer technology were introduced in the

1970s and have shown a steady increase in market share over the past 30 years. They
are used in a variety of exterior and interior coating applications. Stain blocking
primers are one of the most popular types, and are used to prevent discoloration of
topcoats by a variety of materials, including tannin stains from wood, childrens
marker stains, water stains and nicotine stains. Water based primers generally block
the transport of stains by two principle mechanisms:
(i) the primer acts as a physical barrier and blocks the migration of stains from the
substrate to the topcoat (this is similar to the way in which solvent based primers
block stain transport); and
(ii) the primer is formulated with specialized ingredients, such as zinc oxide or other functionalized extenders, which lock (by interacting with) stain molecules into
the film.
While the stain may be visible at the surface of the primer coating after drying, it is
effectively locked into the film and does not lead to discoloration of the topcoat.
Binders for stain blocking primers are usually based on relatively hydrophobic emulsion polymers with acrylic or styrene acrylic compositions. Primers are expected to
have excellent adhesion, and water based primers are formulated to adhere to a variety of substrates including metal, wood, and chalky or aged re-paint surfaces. Since
this level of performance may not be needed, or achievable, in many topcoat formulations, the use of specialized primers offers a flexible and cost effective way to meet
the performance needs of many different coating applications with a limited number
of optimized topcoat products.
6.7.2
Primer Formulations
Primers based on emulsion polymers typically are formulated with PVCs in the
range 25 to 45 % and volume solids in the range 30 to 40 %; lower PVCs and higher
volume solids formulations are preferred because these characteristics provide
tighter and more flexible films. Primer formulations frequently (but not always)
contain some type of reactive pigment or specialized extender to enhance performance features: stain blocking primers frequently utilize functionalized extenders to lock stains while anti-corrosive primers utilize reactive pigments to passivate
ferrous substrates. The performance characteristics of primers can be greatly affected by the choice of thickener and dispersant; HEUR rheology modifiers along with
relatively hydrophobic dispersants are generally preferred in this application. In general, effective primers are formulated with a high degree of colloidal stability and reduced levels of water sensitive materials in order to improve performance characteristics. Table 6-6 illustrates a typical formulation used in stain blocking primer applications.
6.7 Primer Coatings

Tab. 6-6
Stain blocking decorative primer formulation.
Material
Weight %
Grind
Water
Biocide
Dispersant
Defoamer
Titanium Dioxide
Dispersant
Zinc Oxide
Grind sub-total
4.90
0.15
0.89
0.17
14.67
4.90
0.21
1.18
27.07
Let down
HEUR Thickener A
Ester Alcohol Coalescent
Ethylene Glycol
Biocide
Defoamer
Thickener B
Ammonia (28 %)
Water
HEUR Thickener A
HEUR Thickener B
Total
Property
Total PVC
Volume Solids
Weight Solids
Comments
0.25
65.16
1.40
2.73
0.19
0.39
0.20
0.10
1.24
0.25
1.03
100.00
Exterior grade
Coarse grade
Acrylic acid type
Functional extender stain blocking

25 % solids
Specialized primer vehicle
Film formation
Co-solvent and freeze-thaw aid
Isothiazolone mildewcide
HASE (30 %)
pH adjustment
25 % solids
20 % solids
Value
19 %
37 %
49 %
6.7.3
Application testing for stain blocking primers is focused on the ability of the primer
to block stains and to provide a suitable substrate for the topcoat. Laboratory testing
for tannin stain resistance is performed by applying the primers, along with a suitable topcoat, to wooden panels with high tannin levels such as western red cedar or
redwood. The panels are allowed to dry for a short time and they are then placed in a
high moisture environment such as a fog box or mist chamber. Because of the high
degree of panel to panel variability inherent with a natural substrate such as wood, a
careful experimental design (comparisons on the same panel, replication, etc.) is
needed to obtain meaningful results. After the panels are removed from the fog box
and allowed to dry, the performance is rated by a visual comparison against the controls. Laboratory testing of marker stain resistance is done in a similar manner; the
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performance of primer-topcoat combinations are evaluated for their ability to resist

discoloration relative to a set of pass and fail controls. Testing is usually carried out
with several water based and solvent based markers, which are applied to draw-down
charts. The trial primers are then drawn down over the test area, allowed to dry for a
short period (usually 24 h) and then coated with a suitable topcoat. Samples dry
overnight and are then rated relative to controls by a visual comparison.
6.8
Protective and Industrial Coatings
The distinctions between protective and decorative coatings are often a matter of degree, and for our purposes, we will define protective and industrial finishes as coatings which are applied to large industrial structures, such as bridges and factories, or
to products produced in an industrial production process. We will not include automotive coatings in our current discussion, since they are covered in Chapter 7 of this
volume. Even with these limitations, there are a great number of different types of
application areas which use protective or industrial coatings; these include coatings
for industrial structures, machinery and equipment, metal containers, wood furniture and flat stock, and more specialized applications such as coil coatings, marine
coatings and traffic marking coatings. The performance requirements of coatings
designed for protective and industrial applications are generally more demanding
than those of decorative coatings. Because of this, and the wide variety of applications, the shift to coatings based on waterborne emulsion polymers has not been as
pronounced as it has been in the decorative area. Solvent borne coatings are the historical market leaders in protective and industrial coating markets, and they still hold
this position in most applications. However, new developments in polymer design
and formulation technologies have allowed waterborne finishes to make significant
inroads into many areas of protective and industrial coatings. This, coupled with an
increasingly stringent regulatory environment, has led to significant growth in the
use of waterborne coatings for these applications.
6.8.1
Copolymers used in Protective and Industrial Coatings
A variety of synthetic polymer resins are used in coatings for protective and industrial
finishes, with solvent-borne alkyds, acrylics, urethanes, epoxies and polyesters being
most common. Recently, high solids coatings (based on solvent borne polymers
designed for formulation with low levels of solvent) and powder coatings have also
made significant inroads into the protective and industrial coatings areas. In the context of waterborne coatings, acrylic emulsion polymers are the most common compositions chosen for these applications, although significant amounts of waterborne
epoxies, polyurethanes and emulsified alkyds are also used. Acrylic emulsion polymers for protective and industrial coating applications are generally designed with Tg
in the range 30 to 60 C, significantly higher than binders used for decorative appli-
6.8 Protective and Industrial Coatings
cations. Thermosetting acrylic systems, which utilize melamine or other types of

crosslinking chemistry, are also used in many factory applied, oven bake applications. Since most protective and industrial finishes are applied to dimensionally stable substrates, polymers with harder compositions can be utilized in order to provide
improved performance characteristics, without suffering the drawbacks usually associated with using higher Tg polymers in many decorative applications.
6.8.2
Market Size
Based on the analysis presented in the earlier sections of this chapter, coatings used
in protective and industrial (non-decorative) applications represent about 60 % of annual world wide production, or roughly 12 billion liters per year. Assuming that automotive and other applications outside the traditional finish applications represent
roughly a third of this value, we estimate the world wide annual production to be approximately 8 billion liters per year for protective and industrial finishes, as we have
defined them. North American production is estimated to be about 1/4 to 1/3 of this
value, or roughly 2 to 3 billion liters per year. The penetration of waterborne coatings
has been less in these markets than in decorative areas; assuming a value of 25 %
yields an estimated annual production rate for waterborne protective and industrial
finishes to be on the order of 2 billion liters world wide, and 0.50.7 billion liters per
year in North America. Again, we emphasize the approximate nature of these estimates and provide them to give the reader a general idea of market size.
6.8.3
Industrial Maintenance Coatings
Industrial maintenance coatings are designed to provide corrosion control and extend the service life of large metal and concrete structures associated with manufacturing, chemical processing and transportation. Typical applications include bridges,
storage towers, water tanks, chemical plants, oil refineries, water treatment plants,
and electrical power plants. Solvent borne coatings predominate in this high performance application, with alkyds historically holding the largest share, and epoxies
and urethanes showing very good growth in recent decades due to their strong performance profiles. The use of waterborne coatings in the light and medium duty
segments of this market has grown significantly over recent years, and we estimate
they now account for approximately 20 % of these segments in North America.
6.8.4
Early water based coatings for industrial maintenance applications utilized polymers
developed for exterior decorative coatings. Although these polymers provided good
gloss and tint retention in exterior applications, they were not optimized to provide
good corrosion or chemical resistance. Better barrier properties were needed to im-
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prove these performance features, and specialized maintenance binders were developed by reducing polymer molecular weight (to promote improved film formation)
and utilizing more hydrophobic compositions (to provide better resistance to water
and ion transport). A properly balanced composition is needed for optimum performance in maintenance applications; all acrylic polymers provide excellent durability characteristics, but are generally supplemented with more hydrophobic
monomers such as styrene or ethylhexyl acrylate in order to provide improved barrier properties and corrosion resistance. Acrylonitrile is sometimes incorporated in
order to improve chemical resistance, particularly in applications where resistance to
gasoline and aromatic solvents is desirable. Good colloidal stability is particularly
important in maintenance coatings; these coatings are often formulated with reactive pigments which can be difficult to stabilize, resulting in reduced gloss, or poor
storage characteristics. In addition to these features, industrial maintenance coatings should show good adhesion to metal substrates, good hardness development
and enamel-like resistance to marking and abrasion.
6.8.5
Formulation Characteristics for Industrial Maintenance Coatings
Industrial maintenance coatings are usually enamels, and are formulated in a manner similar to decorative gloss enamels: they are formulated significantly below critical PVC in order to enhance gloss, barrier properties and toughness. Urethane rheology modifiers are generally used to provide a more Newtonian rheology profile
(good flow and leveling) as well as to avoid the weak flocculation and water sensitivity associated with cellulosic and HASE thickeners, respectively. A wide variety of
reactive pigments are often used to enhance corrosion resistance, particularly in
primer formulations. Many of these materials are inorganic salts, based on zinc,
calcium or barium cations with anions of phosphate, borate, or metaborate. Effective
coalescing agents are needed, since harder polymer compositions are generally used,
and a combination of two or more coalescing agents is often used to optimize film
formation, drying time and wetting characteristics. Finally, a variety of additives are
commonly included in these formulations; like decorative enamels, these can include dispersants and surfactants for pigment incorporation and stabilization, defoamers, mar aids to increase abrasion resistance and glycols for improved pigment
grinding and freeze-thaw stability. Table 6-7 illustrates a typical formulation used in
industrial maintenance applications.
6.8.6
Industrial maintenance coatings are evaluated by many of the standard stability, application and resistance tests used for decorative coatings. Like decorative finishes,
they are applied in the field and need to have good heat-age and freeze-thaw stability.
They should also have good appearance and application properties, and are generally evaluated for performance in spray, roller and brush application, as well as for
6.8 Protective and Industrial Coatings

Tab. 6-7
Yellow industrial maintenance coating.
Material
Weight %
Grind
Water
Dispersant
Defoamer
Surfactant
Ammonia (28 %)
Titanium Dioxide
Yellow Pigment
Grind sub-total
5.34
0.75
0.21
0.21
0.11
6.94
6.94
20.49
Premix
Styrene Acrylic Emulsion Polymer
Ammonia (15 %)
68.51
0.32
Let down
Add the grind to the above premix,
then add the following ingredients
Coalescent
Propylene Glycol
Methanol
Sodium Nitrite (15 %)
Ammonia (15 %)
Thickener
Total
Property
Total PVC
Volume Solids
Weight Solids
Comments
4.48
1.07
3.73
0.96
0.19
0.25
100.00

Silicone emulsion
Pigment wetting aid, non-ionic
Base
Universal grade
Yellow iron oxide
Mix the following with good agitation

Specialized maintenance vehicle
Add with good agitation

Alkyl acetate ester
Co-solvent, freeze-thaw aid
Co-solvent, freeze-thaw aid
Flash rust inhibitor
Base
HEUR (25 %)
Value
11 %
35 %
44 %
gloss, and color uniformity. Like exterior decorative finishes, the exterior durability
of industrial maintenance coatings are commonly evaluated by exterior exposure
testing, with particular emphasis being placed on corrosion resistance, gloss retention and color retention. In contrast to most decorative finishes, industrial maintenance coatings are also evaluated in the laboratory for corrosion resistance. Salt
spray and prohesion testing are commonly used and both of these techniques use
aqueous salt solutions and high humidity to accelerate the corrosion of steel test panels. Samples are prepared by coating steel test panels with a film of defined thickness
and then drying for a specific time under controlled temperature and humidity conditions. The test panels are then scribed to expose bare steel beneath a portion of the
coating, placed in the test chamber, and evaluated at periodic time intervals. Panels
are subjectively rated, relative to controls, for blistering and corrosion on the face and
at the scribe.
157
158
Salt spray and prohesion testing both suffer from the general problem discussed
above in regard to accelerated exposure testing: corrosion resistance in laboratory
tests does not always correlate well with performance in real world applications.
Laboratory corrosion tests use a combination of aqueous salt spray and high humidity conditions to speed corrosion processes, and there is some question regarding
whether they actually accelerate corrosion processes present under normal use conditions. Salt spray testing uses a high salt concentration (5 % NaCl by weight) and
100 % humidity at elevated temperature (35 C) to provide a more aggressive testing
environment. Prohesion testing utilizes lower salt levels (0.35 % ammonium sulfate
and 0.05 % NaCl), and alternating cycles of salt spray and drying, at ambient temperature and 35 C, respectively, to provide a somewhat more realistic, but slower
evaluation. In spite of the simplicity and speed of these tests, it is generally acknowledged that realistic exterior exposures, preferably in the form of trials on actual metal
structures such as bridges or storage tanks, are the best way to obtain useful information regarding the corrosion resistance of industrial maintenance coatings.
6.9
Traffic Marking Paints
Traffic marking paints are used to control the flow of vehicle and pedestrian traffic
on a variety of surfaces such as roadways, parking lots, walkways and airport runways. Since the late 1980s, waterborne traffic markings have enjoyed strong growth
in the United States and in parts of Europe and Asia. This is due not only to increased environmental sensitivity, but also is due to improved performance features
which have been incorporated into waterborne acrylic emulsion polymers for traffic
marking paints. We estimate the total world wide market for traffic marking paints
to be around 400 million liters per year, with the North American market representing about 120 million liters of this total. Most of the traffic paint market in North
America has shifted over to waterborne technology and the share of water based traffic coatings is now estimated to be greater than 80 %.
6.9.1
Description of Traffic Paint Market
Road-marking paints have been in use since the 1920s; however, traffic paint technologies have changed dramatically over this period. Early paints were based on oilmodified phenol-formaldehyde resins, which were later replaced by alkyds or chlorinated rubber blends. In the early 1990s, the technology shifted toward more environmentally friendly and higher performing waterborne acrylic systems. The enabling technology which allowed for the widespread use of waterborne traffic paints
was the development of fast drying acrylic emulsion polymers in the late 1980s.
These products use proprietary technology to provide waterborne traffic paints with
the ability to dry rapidly under a wide range of relative humidity and airflow conditions. Due to their acrylic compositions, they also offer improved glass bead reten-
6.9 Traffic Marking Paints
tion, which leads to better retention of retro-reflectivity (the ability of a material to reflect light back towards the source from a variety of incidence angles) and nighttime
visibility.
6.9.2
The success or failure of road-marking paints depends on their ability to:

(i) dry quickly enough to prevent damage by traffic following the striping truck;
(ii) adhere to the road surface (concrete or asphalt) during the expected lifetime of
the coating; and
(iii) retain a large percentage of the glass beads applied to the coating surface for
nighttime visibility.
In addition, various governmental agencies can mandate specific requirements for
viscosity, color, VOC content, percent solids, opacity, etc.
6.9.3
Typical Traffic Paint Formulation
Formulations for waterborne traffic markings differ substantially from those of decorative coatings. The volume solids of waterborne traffic paints are quite high,
around 60 %, in order to minimize the amount of water, and to thereby speed the
drying process. Traffic paints are also formulated near or above CPVC, in the range
of 5560 %, to provide higher porosity and increased drying speed. They contain
many of the components found in the waterborne coatings discussed previously,
such as dispersants, defoamers, and rheology modifiers. As with any paint, these
components must be chosen with care so as to not detract from the desired performance characteristics. Table 6-8 illustrates a typical formulation for paint used in traffic marking applications.
6.9.4
Fast drying is an important characteristic for traffic marking paints, and a modification of the standard coating dry-through test (also called the early washout test) is
used to evaluate the time needed for a traffic paint to become resistant to washing off
with water (presumably rain). In this test, a draw-down with a film thickness of
330 m wet is placed in a humidity chamber maintained at 90 % relative humidity
with negligible air flow. The dry-through time is defined as the time required for
there to be no surface deformation when the test operators thumb is twisted
through an arc of 90 with minimal pressure on the paint film. While the coating has
not dried in the conventional sense by this time (all moisture has not yet left the
film), the values obtained in the dry-through test provide a useful measure of the
time needed for a coating to become resistant to being washed away by rain.
159
160

Tab. 6-8
Traffic marking paint.
Material
Weight %
Grind
Acrylic Traffic Paint Emulsion
Dispersant
Wetting Agent
Defoamer
Titanium Dioxide
Grind sub-total
32.40
0.36
0.20
0.21
7.11
54.07
94.35
Let down
Methanol
Coalescent
Defoamer
HEC Thickener
Water
Total
2.13
1.31
0.18
0.68
1.34
100.00
Property
Total PVC:
Volume Solids:
Weight Solids:
Value
60 %
61 %
78 %
Comments
Utilizes rapid set technology
Ammonia neutralized, polyacid
White pigment
Coarse grade
Mix grind for 15 minutes, and add

with good agitation
Co-solvent
Ester-alcohol, film formation
Hydrocarbon type
2.5 % in water.
A traffic marking paint also needs to quickly become resistant to tire pickup after
application to the roadway. This property is commonly evaluated in the laboratory by
the no-pick-up test. In this test, a steel cylinder, outfitted with rubber O-rings, is
rolled over the surface of the drying paint film at specified times. The no-pick-up
time is defined as the point at which paint does not adhere to the rubber rings when
the cylinder is rolled across the film. The auto-no-track test is a complementary field
evaluation method which also measures the time for a traffic marking paint to become resistant to tire pickup. This test is carried out by passing a moving automobile
over a freshly applied transverse or diagonal marking line, and determining the minimum time required for there to be no indication of pick-up and re-deposition of the
line by an observer standing at a distance of 15 m.
Retro-reflectance is a quantitative measure of a traffic markings nighttime visibility. The retention of retro-reflectance is determined in the field, and is related to the
ability of a traffic marking paint to retain small, reflective glass beads which are
dropped onto the coating surface during the coating application process. It is measured either by a portable or truck-mounted retro-reflectomer. Often, specifications
will call for initial minimum values as well as some minimum throughout the lifetime of the marking. Requirements can vary, but typical initial values for white
markings are on the order of 250 mcd m2 lux1 while yellow markings are somewhat
less (ca. 150 mcd m2 lux1) owing to their lower TiO2 content.
161
References
1 Connolly, E., Ishikawa-Yamaki. M.,
2
3
Paint and Coatings Overview, Chemical

Economics Handbook, SRI International, 592.5100 C, 1999.
Tulo, A., Chem. Eng. News 2000, 78(41),
1928.
Patton, T.C., Paint Flow and Pigment Dispersion, 2nd edn, Wiley-Interscience,
New York, 1979, pp. 126204.
Wicks, Z. W. Jr., Jones F.N., Pappas,
S. P., Organic Coatings, Science and
Technology, Vol. II, Wiley-Interscience,
New York, 1994, 5564.
Wicks, Z. W. Jr., Jones F. N., Pappas,
S. P., Organic Coatings, Science and
Technology, Vol. I, Wiley-Interscience,
New York, 1992, 3548.
Hare, C. H., Protective Coatings, Fundamentals of Chemistry and Composition,
Technology Publishing Company, Pittsburgh, 1994, pp. 3762.
Friel, J. M., Acrylic Polymers as Coatings
Binders in Paint and Coatings Testing
Manual, 14th edn of the Gardner Sward
Handbook, Koleske, J. V. (ed.), American
Society for Testing and Materials,
Philadelphia, 1995, pp. 3952.
Sperry, P. R., Snyder, B. S., ODowd,
M. L., Lesko, P. M., Langmuir, 1994, 10,
26192628.
Nicholson, J. W., in: Waterborne
Coatings, in: Surface Coatings 2,
Wilson, A. D., Nicholson, J.W., Prosser,
H. J. (eds), Elsevier Applied Science,
London, 1988, pp. 138.
10 Wang, Y., Kats, A., Juhue, D., Winnik,
11
12
13
14
15
M. A., Sivers, R. R., Dinsdale, C. J.,

Langmuir, 1992, 8, 14351442.
Lowell, J. H., Coatings, in: Encyclopedia
of Polymer Science and Engineering, Vol.
3, Kroschwitz, J. I. (ed.), Wiley-Interscience, New York, 1985, pp. 615675.
Leman, A. A., Paint in: Encyclopedia of
Chemical Technology, 4th edn, Vol. 17,
Kroschwitz, J. I. (ed.), Wiley-Interscience, New York, 1996, pp.
10491069.
Koleske, J. V. (ed.), Paint and Coatings
Testing Manual, 14th edn of the Gardner Sward Handbook, American Society for Testing and Materials, Philadelphia, 1995.
Annual Book of ASTM Standards,
Vols 6.01 and 6.02, American Society
for Testing and Materials, Philadelphia, 2001.
Bauer, D. R., Martin, J. W. (eds),
Service Life Prediction of Organic
Coatings, A Systems Approach,
American Chemical Society/Oxford
University Press, Washington, 1999.
Applications for Automotive Coatings

Sunitha Grandhee
7.1
Introduction
The automotive coatings industry is faced with new challenges as we enter into the
new millennium. Environment legislation, cost and quality in addition to globalization and market constraints are driving new developments. Increasingly stringent
environmental legislation and tougher market conditions require that modern coating systems must bring, not just enhanced product performance but also reduced
overall production costs to paint producers. Daimler-Chrysler, Ford and General Motors in the United States, has formed a consortium, the United States Council for
Automotive Research (USCAR) which now is the umbrella for 11 other research consortia including the Low Emissions Paint Consortium (LEPC). LEPC is tackling the
technical challenge of developing paint-related technologies to reduce or eliminate
VOC from automotive coatings.
The movement towards lower to zero VOC involves many types of coatings technologies. Need to reduce VOC has led to change in many raw materials that were traditionally used in coatings. Furthermore, manufacturers often want their coatings
modified so that they can be used at faster production rates, baked at lower temperatures, or changed in color.
An approach to this problem is by the appropriate modification of acrylic primary
dispersions to suit automotive coating requirements or solvent-free secondary dispersions of conventional resin types like epoxies, polyesters, polyurethanes. Today,
the latest water-borne coatings are much more robust in terms of usage or application friendliness and require significantly less heating or air-conditioning than two
decades ago. They still require some additional dehydration or special kinds of flashes before going into ovens to help remove the water.
The biggest manufacturing industry in the world today is the auto industry, with
over seventy separate companies or subsidiaries, employing 4 million people. In the
United States over 15 million cars are produced annually. It is estimated that motor
vehicle production on a global basis will rise from 54.9 million in 1998 to some
59.3 million by 2003 [1].
163
164
7 Applications for Automotive Coatings
Europe
$8.9 B
Asia
$3.1 B
Africa, Middle East,

Latin America
$1.6 B
North America
$7.5 B
Fig. 7-1
Original equipment manufacturers (OEM) coatings demand
1999.
Demand for motor vehicle coatings is forecast to rise by 1.8 % per year to 2.0 million metric tons by 2003, with OEM coatings posting 1.5 % growth per year to
1.2 million metric tons.
In 1999, Europe was the largest market for coatings for OEM end markets at
$8.9 billion. North America was second having used $7.5 billion in OEM end markets. Asia, with faster economic growth than Europe or North America, last year
spent $3.1 billion on OEM coatings (Fig. 7-1). The rest of the world, which includes
Africa, the Middle East, and Latin America, consumes $1.6 billion in OEM coatings,
according to P.G. Phillips. The market for automotive OEM coatings alone is growing
at 3.2 % per year [2].
7.1.1
History of Automotive Coating
The history of automotive paint dates back to the beginning of the 20th century,
when the mass production of automobiles started [3, 4]. Mixtures of ground pigments and linseed oil like old wood coatings used for carriages and stagecoaches
were brushed on the surface and allowed to dry. The coating was then sanded
smooth and refinished in the same manner. These products were not colorful. Henry Ford always said, You can have a car any color you like as long as it is black. In
the 1920s nitrocellulose-based enamels were applied, offering a wider range of color
choices to the market.
7.1 Introduction
During the early 30s the auto industry started using stoving enamels based on
alkyd resins. These enamels were selected to improve gloss and gloss retention. The
introduction of the spray gun technique made automotive coating much faster than
using the brush method. It minimized sanding between coatings and applied the
product evenly. Alkyds as a whole proved to be more durable and faster drying than
nitrocellulose enamels. This product and process was the system of choice for most
vehicle manufacturers until the 1950s [3, 4].
In the mid 1950s the next great technology leap happened. Acrylic lacquer, while
not markedly better in terms of performance qualities over alkyd enamels, did possess one outstanding trait: it was incredibly fast drying as compared to enamels of
the time. Automobile companies such as General Motors immediately saw the production time savings as a real plus. The coating was applied to the vehicle surface
with a spray gun. At that point the product, still wet, contained a large amount of solvents. Baking the vehicle in a large oven caused the solvents to evaporate and the
product to flow to a uniform smooth finish.
In 1960 the Ford Motor Company went back to the stoving methods. They did this
after realizing that consumers made a vehicle purchase using mainly their eyes:
shiny sells. Ford also decided that they liked many of the properties that the early
acrylic resins provided. They went to work with yet another new group of suppliers to
create acrylic stoving enamels. This product was also applied with a spray gun. It
had a very high gloss, was durable and was oven cured to produce a hard and colorful surface. Using polyisocyanates dramatically magnified and improved acrylic
enamels performance qualities like gloss, hardness, durability [3, 4].
Throughout the 50s and 60s, corrosion was the major cause limiting automobiles
life span. Cationic electrodeposition of a protective coating was the major invention
in the late 1960s, eliminating corrosion as a major cause of automotive failure [5]. In
this process electrically charged paint particles are deposited from aqueous solution
onto metallic substrates by application of an electrical field. Today, 99 % of all vehicles manufactured use some type of electrocoat process.
During the 1970s Japanese and European major paint companies developed the
next technology change, the application of two-coat acrylic painting systems:
basecoat/clearcoat. They were also successful at providing the consumer with
metallics or metal flake paints. German automakers influenced this change with
their color-plus-clear combinations on such premium vehicles as Mercedes Benz.
The technology is a one-stage acrylic flat basecoat followed immediately by a high
gloss urethane crosslinked clearcoat. This results in excellent durability to corrosion
and stone chips, and very high gloss [3, 4].
In the late 80s and early 90s new laws were enacted that governed the content and
application of paints. The amounts of volatile organic compounds (VOC) were lowered using water-borne binder systems. Automotive paint systems are now well
within VOC limits and comply with EPA standards for emissions. Today approximately 14 million vehicles are coated with water-borne technology each year. Out of
the 99 North American assembly plants, 33 plants are using water-borne based
coats [6]. The main suppliers of OEM coatings are PPG, Dupont, BASF, Nippon and
Kansai Paint company.
165
166
Another approach to VOC reduction is the use of powder coatings, however, there
is a lot of cost in converting existing spray booths to suit powder application. Hence,
a variation on this theme is to use slurries of powder in water as automotive
clearcoats. A new clearcoat system has been introduced, that offers zero emissions,
is powder dispersed, and is stabilized in water [7]. This method is used commercially by Daimler-Chrysler in Europe.
Bayer recently won the Presidential Green Chemistry Challenge Award for its twocomponent water-borne polyurethane system. Generally, isocyanates, one of the raw
materials for polyurethanes, are unstable in water. Trying to make water the carrier
for isocyanates was no easy task. Bayer modified isocyanate molecules to stabilize
them in water, so customers can apply them together with polyols, just prior to painting, to make polyurethane coatings [8].
7.2
Automotive Coating Layers
Current automotive coatings are made up of a number of distinct layers (Fig. 7-2),
the coatings are either spray applied or electrodeposited.
Clearcoat
Basecoat
Primer
Electrocoat
(+)
( -)
Automotive OEM
coating layers.
Fig. 7-2
7.2.1
Spray Coating
OEM automotive coatings are those used for painting trucks and cars on fast moving
assembly lines. Stringent conditions are established for surface preparation, application and curing. Typically the clearcoat, basecoat and primer are spray applied while
the electrocoat is electro-deposited by dip application. Drying and curing usually involves energy input such as heat and UV radiation to produce coatings of higher
toughness, solvent resistance and uniformity of appearance. The layers should cure
to a desired finish and should have a wide tolerance for bake conditions. Low bake
temperatures are desired to save energy cost.
The various coating layers, with their thickness and functions, are shown in
Tab. 7-1.
Automobile bodies are generally fabricated from steel [911], therefore corrosion
protection is one of the most important functions of automotive coatings. After the
fabrication of the car body, the surface is coated (phosphate coating) by dipping into
7.2 Automotive Coating Layers

Tab. 7-1
Function and typical thickness of automotive coating layers.
Layer
Thickness
Function
Clearcoat
40 m
Basecoat
Primer
Electrocoat
15 m
35 m
20 m
Withstand solar radiation, atmospheric

pollution (acid rain, bird droppings,
aggressive chemicals like road salts and
caustic detergents)
Optimum appearance and long lasting color
Good adhesion and resistance to chipping
Long-term corrosion protection
an aqueous solution containing primary zinc phosphate Zn2(H2PO4)2 as the major

component. For parts of the exterior, plastic and rubber components are used, which
in some cases are completely coated before assembly. The use of plastics as a substitute for metals began accelerating in the 1970s to achieve a weight reduction in order
to improve fuel economy.
Polymers used as binder
Table 7-2 shows the emulsion polymers most often used in the various automotive
layers.
Tab. 7-2
Water-borne binders used for automotive coatings.
Coating
Resin chemistry
Dispersion
Type
Electrocoat
Primer
Basecoat
Basecoat
Basecoat
Basecoat
Basecoat
Epoxy-amine
Polyesters
Polyacrylics
Polyacrylics
Polyesters
Polyurethanes
Polyurethane-acrylics
Secondary
Secondary
Secondary
Primary
Secondary
Secondary
Secondary
Cationic
Anionic
Anionic
Anionic
Anionic
Anionic/nonionic
Anionic
Water-borne emulsion polymers are used in formulating automotive coatings for

electrocoat, primers and basecoats. Clearcoat polymers are primarily still solventborne. A powder dispersed in water (powder slurry) has been developed as a binder
for clearcoats [7].
For the purpose of this chapters discussion, electrocoat, is not referred to as
primer since an additional layer is present before the vehicle is top coated. Most current automotive passenger cars are coated with four coating layers in addition to the
phosphate coating, as shown in Fig. 7-2 and Tab. 7-1. Furthermore basecoat here, in
this chapter is referred to an independent layer, even though basecoat is considered
as part of the automotive topcoat system.
Automotive OEM coatings are thermosetting coatings, i.e. a chemically
crosslinked matrix is formed between the main resin molecules. This matrix cannot
be returned to its original form by use of solvent or heat.
167
168
Aqueous polymer dispersions used in automotive water-borne coatings are classified as:
primary dispersions: polymerization is carried out in the presence of water by emulsion or mini emulsion polymerization.
secondary dispersions: the polymer is synthesized in an organic solvent and later dispersed in water.
Based on the nature of the solubilizing group, the polymer is classified as anionic,
cationic or nonionic. The higher the concentration of the polar groups, the greater is
the solubility of the polymer. Incorporation of functional groups in the polymer
skeleton is necessary for stabilization in aqueous phase [12].
Formulation ingredients
The amounts of main ingredients present in a water-borne automotive coating formulation are shown in Tab. 7-3; the functions of these ingredients are summarized
in Tab. 7-4.
Tab. 7-3
Main ingredients (%) of for automotive coatings, RCA: rheology control agent.
E-coat
Solids (resins, crosslinker(s), pigments)

Solvents
Additives (RCA, defoamer, wetting agents)
Water
Tab. 7-4
1724
2 3
1 2
7180
Primer
3545
5 7
2 3
4558
Base coat
Metallic
Solid color
2325
1015
2 3
5765
2530
1015
2 3
5263
Function of ingredients in an automotive coating formulation.
Ingredient
Function
Aqueous polymer dispersion

Crosslinker
Film formation, mechanical properties

Reacts with functional groups on main resin to form
crosslinked matrix
Provides color, hiding
Provides appearance effect
Reduces viscosity, controls rate of drying and film formation
Inhibits degradation of film by sunlight
Drives crosslinking reaction
Pigment dispersion, adhesion promotion
Decrease foaming tendencies
Control leveling, sag, aligns aluminum flakes
(metallic basecoats)
Improve substrate wetting, flow, pop tolerance, etc.
Pigment dispersion
Flake pigments
Solvents
UV absorber
Catalyst
Secondary resins
Antifoamer/defoamer
Rheology control agents (RCA)
Other additives
Standard test methods

The standard test methods for automotive water-borne coatings are summarized in
Tab. 7-5.

Tab. 7-5
Test methods for automotive coatings.

Test
Method
Description
E-coat
Basecoat, primer
Basecoat, primer
Basecoat, primer
Basecoat, primer
E-coat, primer,
basecoat
Stomer
ICI cone/plate
Brookfield
Ford viscosity
Dip type
Film build
Viscosity
Viscosity
Viscosity
Viscosity
Viscosity
Thickness
E-coat
Salt spray resistance
E-coat, primer
Gravelometer
ASTM D562
ASTM D4287
ASTM D2196
ASTM D1200
ASTM 4212
ASTM D1186,
ISO 7253,
ISO 4623
ASTM B117,
SAE J2334,
DIN 53167
J 400
E-coat
E-coat
E-coat, primer,
basecoat
Hardness (pencil)
Impact (Gardner)
Humidity
Topcoat, primer
UV
ASTM D3363
ASTM D5420
ASTM D1735,
ASTM D2247,
ASTM D4585,
DIN 53209
SAE J2020
Topcoat, primer
Xenon lamp
SAE J1960
Topcoat, primer
Sunshine/
carbon arc
Tape test
Exposure
Exposure
ASTM G 152
Topcoat, primer
Topcoat, primer
Topcoat, primer
ASTM D3359
SAE J 951
SAE J 1976
Corrosion, J2334 preferred to

B117
Chip resistance testing,
testing coating flexibility,
adhesion and overall
resistance to chipping
damage by stones
Hardness
Hardness
Adhesion and appearance.
Condensing humidity (D2247)
and water soak (D1735)
Appearance (gloss, cracking ,
chalking) Weathering test
Accelerated test to check
for gloss loss
Accelerated test to check
for gloss loss
Adhesion
Durability, Florida exposure
Outdoor weathering of exterior
materials
The J tests were developed by the Society of Automotive engineers, USA (www.SAE.org)
The test methods for automotive layers are designed to stimulate conditions likely
to occur in the field and are of two types appearance and performance. Appearance
includes gloss, distinctness of image, mottle, orange peel. Performance properties
include physical properties of hardness, flexibility, impact resistance, adhesion,
stone-chip resistance, cold crack resistance i.e. stability to extremes of temperature
and humidity, curing efficiency.
Polymer dispersions are applied as coating binder mainly in three of the four
layers: electrocoat, primer and basecoat. These layers are now described in more
detail.
169
170
7.2.2
Electrocoat
Electrocoat or e-coat or Elpo is the first pigmented coating layer, which is applied
over the phosphate coating of the fabricated car steel body. It serves as a bridge
between the metal and the overlaying coating layers. This coating layer is applied
in a dip application by cathodic electrodeposition to the steel automobile body. Dip
application has the advantage to fill the smallest recessed areas of the automobile
body. This complete coverage ensures excellent corrosion protection to the automobile.
Cationic electrocoat applied by dipping process is used worldwide for coating autobodies and its adoption in 1970s and 1980s led to major improvement in the corrosion resistance of cars. Until mid 1970, electrocoat was of the anodic type [1315]. In
1976, PPG introduced the first cathodic primer, and this technology, with continuous improvement, has become the standard of the automotive industry worldwide.
Combined with the more recent introduction of galvanized sheet metal, car manufacturers are now able to offer ten years warranties against corrosion.
Requirements
Current systems are characterized by excellent corrosion protection, good throwing
power and good filling properties at film thickness of ca. 20 m.
Polymers used
The resins used in electrocoat, must have excellent hydrolytic stability and resistance
to salt accelerated corrosion and the chemical composition of the resin also allows
for excellent adhesion of the next coating layer. Most current cathodic systems are
based on modified epoxy resins containing amino groups. These are dispersed in
water by neutralizing the amino groups with organic acids such as formic, acetic or
lactic acid. Bisphenol A epoxy resins are reacted with polyamines to yield a resin with
amine and hydroxyl groups. The resulting polymer is reacted with a polyisocyanate,
which is partially blocked with an alcohol (e.g. 2-ethylhexyl alcohol). Salts are formed
with the amine groups with a low molecular weight carboxylic acid. The epoxy backbone is made flexible by various ways by incorporation of polyester and polyether
diols [16], acrylic grafts [17]; low-Tg aliphatic epoxies [18]; fatty acids [19] and fatty
monoepoxies [20].
The resins are crosslinked by blocked isocyanates, Mannich reactions or re-esterification. Blocked isocyanates which are used as crosslinking agent are stable in the
slightly acidic water system, whereas melamine formaldehyde resins are not. During
baking, the blocked isocyanate reacts with a hydroxyl group to form a urethane
crosslink. Amine-substituted resin binders provide greater corrosion protection for
steel, perhaps owing to strong interaction between the amine groups and the substrate surface that increases wet adhesion, which is the most critical factor for corrosion protection.
Cationic polyurethane dispersions are obtained by incorporating tertiary amine
functionality into the backbone, either by introducing tertiary amine groups in the
diol, instead of a carboxylic group, followed by quaternization with an alkylating

agent or protonation with a suitable acid [21].
Other coating systems contain cationically modified copolymers obtained by polymerization of acrylic monomers in presence of unsaturated polyurethane macromonomer [22], and water-dilutable dispersions of cationically modified and urethane
modified methacrylic copolymers obtained by solution polymerization [23].
Composition
Most of the commercial cathodic electrocoat formulas are two-pack formulas
consisting of a pigment dispersion intermediate and the principal resin components [24].
Pigment dispersion:
Aqueous dispersion resin (epoxy amine isocyanate adduct)
Extenders
Anticorrosive pigments
Organometallic oxides
Deionized water
Principal resin component:
Epoxy amine adduct
Crosslinker
Organic acid
Organic solvent
Deionized water
1015 %
2030 %
37 %
12 %
6546 %
2025 %
1012 %
0.51.0 %
13 %
6869 %
Pigments commonly used are titanium dioxide and extender pigments. Special
lead-containing pigments e.g. silicates are used as anticorrosive agents. Lead also catalyzes the curing reaction, however the trend nowadays is eliminate lead from electrocoat. Solvent content is low (typically less than 2 % based on total volume). The
solids content is ca. 20 %.
The application technique allows coating of complicated shapes and even internal
areas. A coating of uniform thickness is obtained after baking at 150180 C for ca.
20 min.
Application
The car body is coated on a production line by immersing the body in a tank containing the aqueous primer dispersion and subjecting it to a direct current charge.
The applied voltage causes the dispersed particles and pigments to migrate to the car
body. As they are deposited, the consequent transfer of electrons provides an electrically neutral film deposit. During the process electroendoosmosis occurs, squeezing
the water out of the deposited coating and leaving it in a firm state. With this process,
improved uniform coverage is achieved in recessed areas and on sharp edges as well
as on flat surfaces. The body is baked to coalesce and cure the primer film with much
less sagging occurring.
171
172
Electrocoat bath:
Coatings stable at a pH a little below 7 are preferred.
Viscosity:
2050 mPa s at 25 C
Bath solids:
1525 % (1 h at 110 C)
Water:
64 % Deionized water
Solvents:
14 % Organic solvent
Bath pH:
5.06.0
Bath conductivity (20 C):
0.81.5 mS cm1
Cure schedule at metal temperature:
165170 C for 20 min
7.2.3
Primer
Primer or primer surfacer is spray applied over the electrocoat before applying the
basecoat. The main function is to minimize surface roughness and improve adhesion of the basecoat. The uniform thickness provided by the e-coat, makes it smooth
and glossy which makes the adhesion to basecoat very difficult. The primer also protects the light sensitive cathodic electrodeposition layer from exposure to light.
Historically the basic function for spray primers has been corrosion resistance and
preparation of a surface to receive a top coat. With the advent of electrocoat in the automotive industry corrosion resistance has become less of a issue for spray primers.
The corrosion function of spray primers has centered around protecting against
sanding cut throughs (sanding to bare metal) on the electrocoat primer. Presently
the main purpose of spray primer is the preparation of a surface to receive a top coat
(basecoat/clearcoat). Other properties that are presently of great concern for spray
primers are yellowing, adhesion, chip resistance, sandability, leveling, UV durability
and smoothness of the coating with respect to the surrounding coatings (electrocoat
and topcoat).
A current trend is to use color key primers; the colors are picked for use under a
group of top coats with related colors. A chip-resistant primer called anti-chip is frequently applied over the electrocoat on the lower parts of the car body. It is designed
to be especially resistant to impact by stones thrown up from a road against the car
body.
Requirements
The primer must have good chip resistance and exterior durability. Weakness in the
layer will lead to UV radiation degradation causing loss of adhesion of primer to
basecoat/clearcoat and ultimately delamination.
Polymers used
The development of chip resistant water-borne primer-surfacers has benefited from
the use of predominantly water-borne polyester and polyester-polyurethane resins.
Polyesters which are dissolved or dispersed in water by neutralizing acid groups
with amines are crosslinked with a suitable melamine resin. Aqueous polyurethane
or acrylic modified polyurethane systems are also slowly entering the primer market.
Water-borne polyesters used for automotive coatings have both hydroxyl and carboxylic groups as terminal groups. Usual acid numbers are in the range of 3560 mg
KOH g1 resin, to give amine salt solutions in solvent that can be diluted with water
to give reasonable stable dispersions of aggregates of resin molecules swollen with
water and solvent. To give acid functionality, 2,2,-bis(hydroxymethyl)propionic acid
is used as one of the diol components. Hydrolytic stability is also affected by the
choice of the polyol. In addition to the steric effect, it has been shown that polyols
with low water solubility give polyesters that are more stable against hydrolysis
under basic conditions than those with higher water solubility, presumably because
the polymers are more hydrophobic.
Since many of the polymers are hydroxyl functional, they are cured with various
melamines and blocked isocyanates. The polymers are mainly stabilized in the water
phase by neutralization of anionic groups with amines which are volatile (dimethylethanolamine, 2-amino-2-methyl-1-propanol).
To avoid emulsifiers, the polyesters are copolymerized with hydrophilic monomers. In the case of linear high molecular weight polyesters, often sodium 5-sulfoisophthalic acid, polyethylene glycol are copolymerized. However, the copolymerization increases the melt viscosity and decreases water resistance and adhesion. Water-borne polyesters which are of the acrylics-grafted type form stable aqueous dispersion. They consist of core-shell particles with a core of high molecular weight
polyester. Small particle diameters were obtained by use of polyesters having the
largest amount of unsaturated bonds unless gelation occurs [2430]. Thermosetting
water based polyester resin coating composition prepared from polyalkadienediol
may be directly applied to wet electrodeposited coating [31].
Composition of primer
Primers are highly pigmented systems, containing titanium dioxide in combination
with extender pigments such as silicates or barium sulfate, carefully selected to improve the paint attributes (leveling, sanding, humidity resistance). UV absorbers and
HALS stabilizers can be added to improve UV resistance. The pH of the system is
maintained between 7 and 8.
Application and testing
Primer coating are spray applied onto the electrocoated substrate. Typical wet phase
testing includes seed check, gloss, weight per gallon, viscosity, appearance, humidity
sensitivity, settling , impact resistance, topcoat adhesion, solvent resistance, filterability and sand scratch telegraph. For the anti-chip-appearance, weight per gallon,
viscosity, solids, sag and solvent pop and gravelometer-chip resistance test are
used.
7.2.4
Basecoat
Basecoat is the layer which contains the color pigments. This layer is covered by the
transparent coating (clearcoat).
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174
Basecoats along with the clearcoat also called the topcoat system form protective layers over the car body surface and are very important as decoration. They have
the characteristics of:
full and deep gloss
highly brilliant solid or metallic color effects
long-lasting resistance against weather and chemical influences
easy to repair and polish
In terms of appearance, a significant trend in automotive original equipment finishes has been influenced the dramatic growth in the use of basecoat-clearcoat finishes to replace single-stage pigmented topcoats. Basecoat-clearcoat finishes provide
a wet appearance, previously associated with European vehicles, in that the appearance of the basecoat is enhanced by the transparent clearcoat. Because of the
smoothness of the surface and clarity of the film of the clearcoats, the gloss and distinctness of the image of these multi-stage finishes has been widely accepted as the
standard of appearance in both the automotive original equipment and refinish coatings markets.
The basecoat/clearcoat system consists of a colored layer (basecoat) which is
overcoated after a brief flash off time with a protective layer of clearcoat. Both layers
are cured together at about 120140 C. The basecoat contains pigments which provide solid (straight) shades or metallic finishes. In order to reduce the emissions of
VOC, water-borne basecoats have been developed, which may contain only up to
20 % co-solvents.
Composition of basecoat
The pH of the system is maintained between 7.0 and 8.0. Approximately 1015 % by
weight is comprised of solvents. The trend nowadays is to go with HAPS (Hazardous
Air PollutantS) compliant solvents like monoethers of propylene glycol. Solvents
help in achieving good flow and leveling of the coating after it is sprayed. They also
help in proper alignment of the metal flakes of a metallic coating. A UV absorber in
the top coat that strongly absorbs UV in the wavelength range of 290380 nm also
helps to protect the primer from degradation. HALS stabilizers are added to improve
UV resistance. Water-borne basecoats contain crosslinker building a polymer network and ensuring film stability and durability. Water-borne basecoats also contain
rheology modifiers e.g. polyurethane thickeners [32], polyacrylic acids [33] and pigment like additives (metasilicates, colloidal silicon dioxide).
Metallic pigments are frequently incorporated into the basecoat to provide the appearance phenomenon known as the geometric metamerism or color-travel. Coatings with geometric metamerism display different hue and brightness when viewed
at different angles. This effect is used by automotive stylists who specify metallic
basecoatclearcoat finishes to draw viewers eye the subtle contrast in hue and brightness found in styling lines and curvatures in the vehicle.
Even though, water-borne coatings have been the most popular approach to VOC
reduction and there has been a substantial reduction of solvents on going from
solvent-borne systems to water-borne systems, the trend now is to eliminate solvents
Solvent-borne basecoats
Water-borne basecoats
Resin 22%
Resins 23%
Pigment
2%
Pigment 2%
Organic
Solvent 12%
Water 63%
Organic Solvent 76%
Fig. 7-3
Solvent and water-borne basecoat compositions.
almost completely. Fig. 7-3 shows the differences in composition between solventborne basecoats and water-borne basecoats.
Binders used
Anionic coatings systems for water-borne topcoats are emulsion polymers,
miniemulsion polymers, polyurethane dispersions, different types of dispersions of
acrylic resins in water and amino resins, water-borne polyesters, polyurethanes.
Many of the polymers are hydroxyl containing and cured with various melamines
and blocked isocyanates. The polymers are mainly stabilized in the water phase by
neutralization of anionic groups with volatile amines (2-amino-2-methyl-1-propanol).
Cross-linkers like aminoplast resins, alkoxy silanes, blocked epoxy resins, carbodiimides can be used.
Application and testing
Typically, line speeds for spray application of basecoats are lower in Europe compared to United States. Furthermore, turbine pumps are used for circulation of water-borne basecoats in United States, while piston pumps are used in Europe.
The main tests for basecoats paints are: solids content, viscosity, stability at room
temperature/hot box 43 C/56 C. Basecoatclearcoat testing depends strongly upon
customer requirements, e.g. film failures (popping, cratering, seeding), flow and leveling, color matching, gloss and effect (in case of metallic systems). There are different stability tests: mechanical stability (hardness and flexibility) and stability against
environmental influences (rain, humidity, light, higher temperature). To test the stability of topcoats against the effects of weather (mainly sunlight, humidity, temperature and fallout against pollution) coated panels are exposed for several years in special places (Florida, Arizona, Okinava, a southern Japanese isle and Alunga in northern Australia). For trials, there is the possibility to run shorter test times in accelerated weather machines (weather-o-meter) which try to model the natural conditions.
There are many other requirements including: resistance to car brushes, bird drop-
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176
pings, acid rain, sudden thunder showers on a car that has been sitting in the hot
sun, the impact of pieces of gravel striking the car, gasoline spillage and so on.
7.3
Properties of Water-borne Binders used for Automotive Coatings

7.3.1
Emulsion Polymers
Emulsion polymers are binders of choice for automotive water-borne basecoats applications, because of their low cost and processing requirements. A particularly
valuable element of acrylic emulsion polymer chemistry is the ability to incorporate
a broad range of functional chemical groups into the polymer chain via ester, amide
carbamate, derivatives of acrylic or methacrylic acid. These functional groups can
provide sites for crosslinking, adhesion, compatibility with other polymers, postpolymerization reactions, biochemical activity, etc. Acrylic latexes are increasingly
becoming popular for basecoat automotive applications, because of their resistance
to photodegradation and low cost, in addition to their well-known features including
safe handling, low toxicity, low odor, and easy clean-up. A number of patents exist in
the literature, wherein core shell polymers have been suggested to be used for waterborne basecoats. To achieve good flow properties, a low minimum film-forming
temperature, good stability to agitation and good adhesion to other coating layers,
multiphase emulsion polymers are used, where the latex particles are small in size,
the core material is hard and the shell is soft and the latter is made of strongly hydrophobic monomers and a relatively large proportion of monomers carrying carboxyl groups [3436].
Acrylic core-shell polymers have been used as principal polymers for aqueous metallic basecoat paints [3740]. The anionic shell allows pseudoplastic flow behavior
which ensures parallel orientation of the aluminium pigments in the wet paint film.
This orientation and the low solids content are responsible for the metallic gloss and
high color flop (change in color observed on varying the viewing angle) of the basecoats.
For thermoset automotive coatings cross-linkable polymer dispersions are
used [4147]. Compositions containing methylol(meth)acrylamide can be used for
very low VOC water-borne coatings. Relatively low-Tg polymers that coalesce well
without coalescing solvents are applied and subsequent crosslinking will give the required film properties. Water-soluble or a water-dispersible alkylated melamine
formaldehyde crosslinking agent or a polymeric partially methylated melamine
formaldehyde resin having a degree of polymerization of approximately 13 are used
frequently. Such compositions have been used for automotive quality clear coat
and/or pigmented color coat for automobiles and for an automotive quality primer
composition [48]. Functionalized latexes in baked coatings can be crosslinked with
aminoplast resins, alkoxy silanes, blocked isocyanates, epoxy resins and many other
cross-linkers.
7.3 Properties of Water-borne Binders used for Automotive Coatings
To improve the water resistance, branched vinyl esters with long hydrophobic
chains can be used [49].
Emulsion polymerization is carried out as a semi-continuous batch process [50].
The polymer particle size is between 50 and 500 nm.
7.3.2
Microgels
Microgels are used as rheology control agents (RCA) for solvent-borne basecoats and
clearcoats. They are crosslinked microparticles made by emulsion polymerization
using monomers like ethylene glycol dimethacrylate, allyl methacrylate or divinylbenzene. They are insoluble in the aqueous medium and are stable towards gross
flocculation. The chemical composition and degree of crosslinking of the microparticle may be such that it has a Tg below room temperature in which case the microparticles will be rubbery in nature, alternatively, it may be such that the Tg is
above room temperature, that is to say the particles will be hard and glassy. The polymer micro-particles can be dispersed in the basecoat composition in a state in which,
even at low solids contents, the dispersion contains a few if any multi-particle aggregates. The presence of the crosslinked polymer microparticles in the basecoat composition, confers upon the film derived from the latter, the desired ability to withstand subsequent application of the topcoat composition without disturbance of the
film or of the pigmentation, in particular metallic pigmentation, which it contains
and without which, therefore a successful basecoat/clearcoat system cannot be
achieved. Microgel dispersions having a pseudoplastic or thixotropic character have
been used for formulating metallic pigments in the basecoat composition. This gives
the advantage of the flip tone effect as well as the gloss to produce the ever popular
metallic finishes for the automotive industry [51].
7.3.3
Miniemulsions
Significant advances have been made in recent years in applying miniemulsions for
making water-borne polymers for the coating industry. Since the introduction of
miniemulsion polymerization in the early 1970s [52] many investigators have studied the subject and have used many different methods to prepare miniemulsions [5357]. Miniemulsions are routinely prepared using some kind of high shear
device, in most cases this being an ultrasonifier or a microfluidizer [58].
Shork et al. have shown that incorporation of polyester into each acrylic latex particle, prepared via miniemulsion polymerization, leads to an effective in situ grafting
of the acrylic and polyester systems [59]. The hydrophobic nature of the polyester
resin makes it impossible to be accommodated by traditional emulsion polymerization due to mass-transfer limitations in crossing the aqueous phase to micellar nucleation sites. Thus, stable water-based latex coatings can be prepared that also have
the ability to cure (by crosslinking).The above hybrid miniemulsion polymerization
was successfully used to incorporate an oil modified polyurethane in the acrylic
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178
droplets to give stable miniemulsions which were polymerized to give hybrid latexes [60, 61]. The hybrid polyurethane modified miniemulsion latexes have been successfully used in formulating coatings for basecoats [6264].
Additionally, miniemulsions made using a mixture of polyurethane and acrylic
monomers were used to make latexes using a semi-continuous feed. This technique
was successfully used to core-shell polymers for use in making water-borne
basecoats [64, 65]. Stable aqueous dispersion of polymeric microparticles containing
cellulose ester, and an acrylic polymer and a surfactant has been used for coating
compositions. These coating compositions have good leveling and flow characteristics and exhibit good humidity resistance, appearance, adhesion and chip resistance
when used in a low bake repair process as well as a good automotive quality finish [66]. These dispersions of microparticles are produced by high stress dispersion
followed by polymerization of the vinyl monomers in the presence of cellulose ester
within the micro-particles.
7.3.4
Selection of Monomers, Initiators, and Surfactants
Glass transition temperature is usually the first design property considered for the
application. Hydrophilicity, hydrophobicity, acid-base properties, crosslinking ability
are other properties [67, 68]. Acrylic acid (AA) or the somewhat less water-soluble
methacrylic aid (MAA) are used in the order of 12 % (w/w) of the monomer charge.
The effects of acid monomers on stability and viscosity are maximized when they are
incorporated in the last part of the monomer feed and the polymerization medium is
acidic. Sometimes di- or tri-functional cross-linking monomers are included. To improve acid rain etch resistance, carbamate functional monomers are included,
wherein the carbamate groups crosslink with melamine, used for clearcoats. The
aminoplast cured coating system combines acid resistance with excellent coating
properties providing protection against etching by acid rain [69].
The most common initiators are peroxydisulfate salts, especially ammonium peroxydisulfate. Thermal initiation is preferred to redox initiation. Whitening of films
may occur sometimes due to the hydrophilicity of the salts like ferrous thiosulfate. A
water soluble azo initiator 4,4-azo-bis(cyanovaleric acid) has also been used for making acrylic latexes [70].
Chain transfer agents are sometimes added to control the molecular weights and
the distribution. Latexes and coatings are stabilized by biocides or water-miscible solvents to prevent microbiological contamination and deterioration [71]. Choice of surfactants are critical for automotive paint application due to their foaming tendency,
ability to impart water sensitivity to paint films and change gloss characteristics. Typically a low particle size in the range of 50300 nm is preferred, so in general anionic surfactants are used at levels of 0.52 % (w/w) based on polymer. Nonionic surfactants may be added in stabilizing the latex against coagulation during freeze-thaw
cycling making it less sensitive to coagulation by salts, less sensitive to changes in
pH. Choice of surfactant can also affect film formation temperature, since some
nonionic surfactants plasticize the latex polymer, leading to lower Tg and hence, a
7.3 Properties of Water-borne Binders used for Automotive Coatings
lower temperature for coalescence. For example, nonylphenylethoxylate nonionic

surfactants with less than nine ethoxy units reduce film formation temperature as
compared to 20 to 40 ethoxylate units, but the higher ethoxylated surfactants are
more effective latex stabilizers [72].
7.3.5
Secondary Acrylic Dispersions
Automotive coatings containing acrylic resins as binders are well known. Organic
solvents used are generally alcohols, glycol ethers and other oxygen-containing
solvents that are soluble or miscible with water. Acrylic resins made in solvents (e.g.
1-(n-propoxy)-2-propanol, 2-butoxyethanol, butyl alcohols) are polymerized by freeradical mechanisms. Typical monomers used are MMA/BA/BMA. Azo initiators are
typically used. Hydroxy monomers like HEMA, HEA are used, while acrylic acid
monomers are used to impart water solubility. After polymerization the carboxylic
acid groups are neutralized. Typically, these resins have acid numbers of 4060 (acid
number is determined by titration and is defined as mg of KOH required to neutralize 1 g of resin solids, equivalent weight equals 56 100/acid number). In the low-molecular-mass range (<6000 g mol1), the Tg depends on the molecular mass. Subsequent cross-linking leads to an increase of Tg which is dependant on the cross-linking density.
The choice of amine is crucial. 2-(dimethylamino)ethanol is widely used [73]. Thermoplastic latexes are of higher Tg (upwards of 60 C) are used for higher toughness,
mar and chemical resistance, since heat is available for film formation. The hydroxylic monomers can be incorporated for cure with melamine and isocyanate resins,
the carboxyl monomers can provide cure with epoxies, aziridines and carbodiimides.
7.3.6
Secondary Polyurethane Dispersions
Another important class of materials used for OEM coatings are aqueous
polyurethanes due to their versatility in their properties [7480]. Since the introduction of polyurethane dispersions in 1960s, they have enjoyed considerable interest
and commercial acceptance. Polyurethane dispersions can be classified into three
main groups:
non-ionic type;
ionic type; and
dispersions containing both the non-ionic and the ionic groups.
Anionic PU dispersions
In the first step of the synthesis, a conventional polyether- or polyester-based isocyanate-terminated prepolymer is obtained by condensation polymerization of a diol
and a diol containing a carboxyl function, preferably reacting the hydroxyl groups of
dimethylol propionic acid with isocyanate groups. In the next step, the carboxyl
groups are neutralized with an amine which is subsequently dispersed in water and
179
180
chain extended in order to obtain high-molecular-weight materials by reacting with a

diamine in further steps. Aliphatic isocyanates are preferred, because beside conferring good durability, they show lower reactivity with water and carboxylic groups.
Further aliphatic isocyanates favor very rapid reaction with diamines in the chain extension step. As neutralizing bases, tertiary amines are preferred compared to other
amines to prevent unwanted side reactions with isocyanates. A number of diols, isocyanates and amine raw materials can be used to adjust the mechanical properties,
glass transition temperature and durability.
Non-ionic Dispersions
In the non-ionic types, the hydrophilic centers comprise of polyether chain segments [75, 81]. The different morphology exhibited by aqueous polyurethanes and
acrylics explains why the minimum film forming temperatures of polyurethane dispersions (PUD) are lower than that of acrylics with equal hardness [82]. Polyurethane
particles can exhibit core-shell morphology with the shell having higher molecular
weight and higher urea functionality than the core. This effect was found to be quite
pronounced with isophorone diisocyanate-based polyurethane dispersions [83]. A
two coat one bake coating process which does not give environmental problems has
been developed using aqueous PUD [84, 85].
Water-borne basecoats containing polyurethanes have been produced with a formulation containing less than three pounds per gallon and lower temperatures than
solvent-borne systems [86]. Rapid-drying polyurethanes have been used for industrial finishing and automotive refinish with a well-balanced range of properties at low
VOC level. High-performance OEM-clearcoats have been produced with good chemical resistance with excellent mar resistance. Some limitations of using anionic water-borne polyurethanes are, volatile amines used to salt these carboxylic acid-functional resins, which leaves during baking, thereby hindering the cure of the strong
acid-catalyzed acrylic-melamine clearcoats, resulting in wrinkled finish and loss of
DOI (Distinctness of image), and the limited rheological stability with metallic formulations which contain certain rheology control agents. In certain formulations,
anionic PU resins have generally not given satisfactory application properties and
paint stability. In response to these limitations, nonionic polyurethane dispersions
were developed [87, 88].
Hybrid systems
The blending of resins is a simple and useful technique for improving paint properties. While water-borne acrylic resins and polyurethanes have been widely used as
polymers for automotive coatings, both water-borne resins are inferior to corresponding solvent based counterparts because of hydrophilic functional groups or surfactants which are introduced to impart dispersion stability to these resins. Table 7-6
shows some of the advantages and disadvantages of polyurethane and acrylic resins.
The most widely utilized technique for making hybrids is to free radically polymerize a combination of monomers in the presence of a pre-formed polymer which
may or may not be intrinsically dispersible. If the preformed polymer is water dispersible, it can be used directly as a seed for subsequent free radical polymerization.
7.4 Rheology
Advantages and disadvantages of polyurethane and
acrylic resins.
Tab. 7-6
Acrylics
Polyurethanes
Advantages
Disadvantages
Hardness
Weatherability
Chemical resistance
Gloss
Affinity for pigments
Cost
Mar resistance
Elongation
Softness and adhesion
Toughness
Mar resistance
Elongation
Cost
Urethane acrylic aqueous dispersions prepared by an acrylic polymerization in the

presence of an aqueous polyurethane can possess a range of advantages over the corresponding blends, e.g. reduced water sensitivity, ability to prepare in the cosolvent
form. Since polyurethanes are generally more hydrophilic than the acrylic copolymer, the polyurethane concentrates at the particle surface. In a well designed system,
the particles coalesce on film formation to give a film with a continuous polyurethane phase. Hybrid acrylic-urethane latexes have been made by simultaneous
polymerization of acrylic monomers and chain extension of urethane prepolymers
giving structures similar to interpenetrating network polymers, with mechanical
properties exceeding those, if blended [89].
Combination of special emulsions, microgels and water-soluble resins have yielded excellent aqueous binders for various coatings [25].
7.4
Rheology
A major concern in developing water-borne automotive coatings is to achieve a distinct rheology profile providing good sprayability, sag resistance and leveling properties, simultaneously. In low solids solvent-borne systems, controlling the rate of solvent loss controls viscosity and sagging and metal flake orientation. In water-borne
systems rheology control agents (RCA) are added to control sag and flake orientation.
The viscosity of the paint must be very low at the spray gun in order to ensure a
good and uniform atomization. After the paint meets the car body, however its viscosity needs to be very high so as to prevent sagging on vertical surfaces and clouding. The flow behavior of the aqueous basecoat therefore has to be adjusted by including a rheology additive, the thickener, in the formulation. The paint must have a
good intrinsic viscosity, i.e. the viscosity must depend on the shear rate. With a high
shear force, such as is present at the nozzle during the spraying process, the viscosity needs to be very low. If the paint then meets the car body, it is virtually unaffected
181
by the shear strength and the viscosity must rise to very high values with almost the
same solids content so that the paint does not sag and the aluminum platelets do not
lose their alignment. A pseudoplastic (shear thinning) behavior is ideal for coating
materials. Viscosity is fairly high at low shear rates which avoids settling in the can
and gives good anti-sag properties. At higher shear rates, the viscosity is reduced
which allows easy handling and application of materials.
Interactions between thickener and latex particles in water-borne automotive coatings and the corresponding microstructures were investigated using dynamic mechanical spectroscopy, cryo-replication, TEM and analytical ultracentrifuge techniques [90].
Attempts to correlate various rheological parameters to good metallic appearance
have not been found to be successful [91]. However, in the case of four samples with
varying metallic flop index values, it has been observed that higher degree of pseudoplasticity led to a better flake orientation when compared to samples with lower
metallic flop index values. (Fig. 7-4)
Steady Shear Viscosity Profile
10000
Sample A
Viscosity [mPas]
182
Sample B
Sample C
1000
Sample D
100
Viscosity versus shear rate, metallic

flop index values: sam1000 ple A 62, sample B 57,
sample C 58, sample
D 49.
Fig. 7-4
10
1
10
100
Shear Rate [1/s]
A Zeiss multiangle goniospectrophotometer MMK-111 with 45 illumination angle was used to measure the lightness values of the basecoat/clearcoat film at different angles. The degree of travel was estimated using the following mathematical
calculation [92]:
Metallic flop (MF) index = 50(L25 L70)/L70
where L25 and L70 is the lightness value at 25 and 70 off of specular reflectance.
Specular reflectance is the reflectance of the incident light. When incident light falls
on the coating surface. Values of this parameter for basecoat/clearcoat typically
range from 45 for a coating with poor travel to 70 for a coating with very good metallic flake orientation.
When light strikes a surface, some of the light penetrates where it can then be absorbed, scattered, or even transmitted if the layer is sufficiently thin. Nevertheless,
because of the change in refractive index between air and most substances, a certain
7.5 Crosslinking
proportion of the incident light is reflected directly from the surface. The angular
distribution of this light depends upon the nature of the surface but light that is reflected at the opposite angle to the incident light is called specular reflectance. Light
that is reflected by the substance itself is called body reflectance. Instead of examining the energy that passes through the sample, specular reflectance measures the energy that is reflected off the surface of a sample or its refractive index. By examining
the frequency bands in which the rate of change in the refractive index is high, users
can make assumptions regarding the absorbency of the sample.
Acrylic microgels have been developed that impart thixotropic flow using swollen
gel particles [52, 9396]. Thixotropic agents are added to increase the viscosity at low
shear rates to minimize sagging [97, 98]. In the final film, the index of refraction of
the polymer from the microgel is nearly identical with that of the crosslinked acrylic
binder polymer so that light scattering does not interfere with color flop. The effect
of the gel particles depends on the interaction with the low molecular weight resin.
The rheological properties of the systems are discussed elsewhere [99].
7.5
Crosslinking
Thermoset coatings (chemically crosslinked film) play a very important role in the
automotive coatings industry. All coating layers uses resins which need to be
crosslinked. By crosslinking the resin used in the coating, many properties can be
greatly improved, such as hardness, mar resistance and solvent resistance.
Crosslinking reactions became important in the 1950s with the introduction of
acrylic resins in the automotive sector. A further impetus was given by increasingly
stringent environmental legislation. Lower solvent content and the replacement of
conventional solvent-borne paints by water-based paints meant that the molecular
mass of the binders had to be lowered to a range where the required paint properties
(film formation, hardness and flexibility) no longer exist. These properties therefore
had to be obtained by increasing the molecular mass by crosslinking after application. Furthermore, the glass transition temperature and film hardness are increased,
the chemical reaction after application also provides advantages of high molecular
mass dispersions.
A widely used method of cross-linking paint films consists of reacting of hydroxyl
containing acrylates or carbamate containing acrylates with melamine-formaldehyde
resins or urea-formaldehyde resins [100102]. Crosslinking is carried out at
ca.130 C and is effected by acid catalysis (Fig. 7-5). The paints exhibit outstanding
gloss and durability [103].
The possibility of making cross-linkable latexes by emulsion polymerization in the
presence of etherified melamine-formaldehyde resins has been demonstrated by
Jones et al. [104]. Dynamic mechanical measurements showed that films from
slightly or moderately cross-linked particles behave like homogeneous networks in
the linear viscoelastic range [105]. Melamine formaldehyde cross-linkers have been
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184
used with water-reducible acrylics, water-reducible polyesterpolyurethanes and

acrylic latexes [106109] in automotive water-borne basecoats.
A practical and effective crosslinking mechanism in cathodic electrocoating is
done with polyfunctional blocked isocyanates. The mechanism involves the reaction
of an isocyanate group (NCO) with the hydroxy group of the epoxy backbone and liberation of the blocking group. Other crosslinking mechanisms that have been studied are use of addition polymers, Mannich bases, Michael adducts [110] sulfonium
stabilized polymers, transesterification reaction of hydroxy, alkoxy, amido and ester
systems with hydroxy functional cathodic backbone (Fig. 7-5) [111114].
Melamine-Hydroxyl reaction
R'
N
OR
HO
OR
R'
ROH
N
OR
H+
R'
N
R'
Alkoxylated
Melamine
Hydroxyl-functional
Acrylic
Melamine Ether
Isocyanate-Hydroxyl reaction
R NCO
HO
O
O
Hydroxyl-functional
Acrylic
Isocyanate
Urethane
Melamine-Carbamate reaction
OCNH2
OCNH2
O
OR
N
N
N
250 F
N
N
OR
N
N
N
N
N
Fig. 7-5
OH
Crosslink reactions.
C O
N
H
OR
7.6 Application Properties
7.6
Application Properties
Water-borne coatings initially presented a number of difficulties. Water-borne viscosity characteristics are distinctly different and application, film formation and drying behavior are dependant on humidity and phase distribution of solvents as well as
the usual factors of solids, temperature and air flow. Water-borne coatings themselves vary depending whether they are latexes, dispersion (semi-soluble) resins or a
combination of the two. On account of the viscosity anomaly, water-borne paints
based on water-soluble binders have a relatively low solids content (ca.3040 %) and
require relatively large amounts of organic solvents (up to 15 %) to ensure water solubility and film formation. They also have the advantage of a broad drying spectrum
(physical, oven drying).
As a result of the particulate nature of the acrylic latex polymers, only low gloss
and, in some cases, only limited corrosion protection can be obtained. Water-borne
coatings based on dispersions can be applied by spraying, however they are of only
limited use for electrostatic coating and dipping applications due to their rapid drying properties. Aqueous dispersions generally contain a few per cent of high boiling
solvents which act as temporary plasticizers and lower the minimum film-forming
temperature, thus allowing film formation to occur. A film of sufficient hardness is
obtained only after complete evaporation of solvent, which may take up to several
days. The film may, however be somewhat hydrophilic due to the presence of carboxyl groups and emulsifier residues, this reduces its water resistance, gloss and
gloss retention.
Coating films formed from some water-soluble binders tend to be water-sensitive
because of their hydrophilic solubilizing groups. They can be formulated to have a
high gloss due to their good pigment wetting and stabilization. They can also have a
high level of corrosion protection, which depends on the corrosion-inhibiting pigments used and the chemical nature of the binder. The latter determines adhesion to
the substrate and diffusion of water and oxygen through the paint film. In the case of
paints made from emulsion polymers, the required application viscosity of waterborne emulsion paints is generally obtained by adding a small volume of water. The
evaporation behavior of polymer dispersions is similar to that of conventional solvent-based paints.
In the production and application of water-borne paints, water is used as the solvent or diluent. The physical properties of water and organic solvents differ. Some of
these properties have to be taken into account when water is used as a paint solvent.
The water molecules have a high dipole moment and associate with one another.
This means that water has a high boiling point and high latent heat of evaporation
despite its low molecular mass. This in turn results in fairly long evaporations or in
the need to supply energy in the form of heat to evaporate the water and dry the paint
film. The high dipole moment of water is also responsible for its high surface tension. With substrates having a low critical surface tension (e.g. plastics or unsatisfactorily greased metals) this leads to inadequate wetting, unsatisfactory edge covering,
and crater formation. Critical surface tension (at 20 C) of water is 72.5 mN m1.
185
186
Circulation studies of water-borne metallic basecoats demonstrate a few reasons

why specular reflectance is lost during circulation. The flow induced stress of circulation reduces flake size and produces cycles in liquid surface tension. Surface tension in turn controls amount of picture framing and film thickness. If rust is present
in the circulation system, it can react with the paint resins, creating gel lumps which
under circulation trap the metal flake hindering flake alignment. Smaller flakes,
thicker film thickness and poor aluminium alignment all reduce specular reflectance within the sprayed basecoat paint film [109115].
7.6.1
Metallic Effect
Typically in solvent-borne systems, the basecoat requires high solvent or low solids
content in order to achieve perfect orientation of aluminium flakes, which results in
the so-called flip effect. The key factor is the rapid rise in viscosity on the car which
results in the aluminum flakes effectively frozen in an orientation parallel to the surface. The slower rate of evaporation of water means that a water-borne basecoat cannot rely upon water evaporation to achieve his rapid viscosity rise. ICI, through its
patented microgel technology has managed to stimulate the rapid viscosity rise. The
microgel pseudoplastic rheology means that the paint at the spray gun tip behaves
like a thin liquid while the paint on the car panel is highly viscous. The microgel particles are acrylic-based and swell rapidly in the presence of small amounts of organic
co-solvents such as butyl cellusolve in alkaline solution e.g. pH 7.6. These are supplied to the European and world automotive industry for production line applications. These basecoats are cured at 130140 C [116]. The lower film thickness of the
basecoat and the flash-off time required before applying the clear top coat reduces
the popping problem. Control of sagging during application requires that the waterborne basecoat is shear thinning, which also reduces surface distortion during subsequent application of the clear coat [117].
7.7
Environmental Aspects and Future Trends
Water-borne coatings for automotive applications have a broad application spectrum. The prospects for the increasing use of automotive water-borne coatings lies in
their economic advantages and in the possibility of reducing solvent emissions during application to comply with legal requirements. Savings in organic solvents as
diluents, savings in insurance premiums, lower energy consumption in spray cabins, ventilation zones, and drying ovens, all contribute to the overall economy of water-borne coating materials. Water-borne coatings can generally be classed as less
toxicologically harmful than corresponding solvent-based paints. Nevertheless, lungpenetrating paint mists (aerosols) of water-based paints present a health hazard and
appropriate protective measures (e.g. use of respirators) must be taken depending on
the workplace concentration. The main problems arise due to the relatively high
7.7 Environmental Aspects and Future Trends
freezing point, high surface tension and low evaporation rates of water compared to
organic solvents. Moreover the presence of water causes rusting problems of ferrous
substrates and also make the water-borne systems very prone to attach by microorganisms. Although water-borne systems are not considered toxic, they require careful selection of resin/binders and additives such as biocides, cosolvents, coalescing
agents, etc., in order to avoid toxicity caused by these components. Future approaches will encompass improvements in scratch and environmental etch resistance, better color options, better performance features all at a lower cost to the manufacturer.
Acknowledgment
The author wish to thank BASF Coatings Division for their support in writing this
chapter.
References
General
M. S. El-Aasser, P. A. Lovell (eds)
Emulsion polymerization and Emulsion
Polymers, Wiley, New York, 1997.
D. C. Blackley, Emulsion polymerization,
Theory and Practice, Wiley, New York,
1975.
J. W. Vanderhoff, J. Polym. Sci.: Polym.
Symp. 1985, 72, 161198.
G. Fettis, Automotive Paints and Coatings,
VCH, Weinheim, 1995.
D. Stoye, W. Freitag, Paints, Coatings and
Solvents, 2nd edn, Wiley-VCH, 1998.
Z. W. Wicks, Jr, F. N. Jones, S. Peter
Pappas, Organic Coatings Science and
Technology, 2nd edn, 1998.
1
C. C. Esposito, Coatings World,

March 2001, 38.
9 B. M. Perfetti, Metal Surface Character-
10
11
12
13
14
15
16
17
18
19
20
21
2 A. H. Tullo, Chem. Eng. News, October 9,
2000, 19.
22
3 http://www.protectall.com/Paint.htm
4 http://www.asashop.org/autoinc/
may2001/paint.htm
23
5 K. Weigel: Elektrophorese-Lacke, Wis-
senschaftl. Verlagsgesellschaft, Stuttgart

1967.
6 M. E. Rosenberger, Automotive Coatings,
International Sterling Publications,
2001, p. 91.
7 J. Woltering, Paint and Coatings Industry
Magazine, September 2000, 108.
8 M. Greissel, Industrial Paint and Powder,
October 2000, 22.
24
25
26
istics Affecting Coatings, Federation of

Societies for Coatings Technology,
Blue Bell, PA, 1994.
J. J. Wojtkowiak, H. S. Bender, J. Coat.
Technol. 1978, 50 (642), 86.
S. Maeda, J. Coat. Technol. 1983, 55
(707), 43.
J. C. Padget, J. Coat. Technol. 1994, 66,
839, 89.
US Pat. 4419467.
US Pat. 4170579.
US Pat. 4423166.
US Pat. 4104174 assigned to PPG.
US Pat. 4177124 assigned to Dupont.
US Pat. 4698141 assigned to Dow.
US Pat. 4113682 assigned to Nippon.
US Pat. 4139510 assigned to Celanese.
D. Dietrich, Prog. Org. Coatings 1981,
9(3), 281.
K. Horibe; H. Haneishi, ; M. Mitsuji,
M. Yabuta, Y. Okumura (Kansai Paint
Co) EP 785034 (July 23 1997).
B. Vogt-Birnbrich, A. Gobel, (Herberts
GmbH) Eur. Pat. Appl. EP 798323 (October 1, 1997).
G. Fettis Automotive Paints and Coatings, 1995, 37.
Yasuhara Nakayama, Prog. Org. Coatings, 1998 33, 108116.
T. Shimizu, A. Nagara, A. Kaji, S. Higashiura, M. Ohguchi J. Appl. Polym.
Sci. 2000, 78 (2), 392.
187
188
References
27 T. Shimizu, S. Higashiura, M. Ohguchi
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
J. Appl. Polym. Sci. 2000, 76 (3), 350.

T. Shimizu, S. Higashiura, M. Ohguchi
J. Appl. Polym. Sci. 2000, 75 (9), 1149.
T. Shimizu, S. Higashiura, M. Ohguchi
H. Murase, Y. Akitomo, Polym. Adv.
Technol. 1999, 10 (7), 446.
T. Shimizu, S. Higashiura, M. Ohguchi,
J. Appl. Polym. Sci. 1999, 72 (14),
18171825.
T. Nishi, T. Takagi, Y. Okude, Eur. Pat.
Appl. EP 849341 A2 (June 24 1998).
DE 3606513, BASF L+F (1986); EP
0260430, AKZO (1987).
DE 3630356, Asahi Glass (1986).
S. C. Wieditz, J. Niemann, A. Dobbelstein (BASF), US Pat. 5635564 (Jun. 3,
1997).
W. Jouck, B. Mayer, S. C. Wieditz,
US Pat. 5322715 (Jun 21, 1994).
A. J. Backhouse (ICI), US Pat. 4403003
(Sep 6, 1983).
A. J. Backhouse, Eur. Pat. B-0015035
(1979).
R. Buter, Eur. Pat. A 0238108 (1986).
R. Buter, Eur. Pat. A-0273530 (1986).
R. Buter, Eur. Pat. A-0287144 (1987).
B. G. Bufkin, J. R. Grawe, J. Coat.
Technol. 1978, 50 (641), 41.
Technol. 1978, 50 (643), 67.
Technol. 1978, 50 (644), 83.
Technol. 1978, 50 (645), 70.
Technol. 1978, 50 (647), 65.
Technol. 1979, 51 (649), 34.
E. S. Daniels, A. Klein, Prog. Org. Coat.
1991, 19, 359.
S. K. Nickle; E. R. Werner, Jr. (E. I. Du
Pont de Nemours) US Pat. 5314945
(May 24, 1994).
D. R. Bassett J. Coat. Technol. 2001, 73,
912, 65.
Anon., Emulsion Polymerization of
Acrylic monomers, Tech Bull. CM-104
A/cf, Rohm and Haas, Philadelphia.
R. M. Christenson, T. R. Sullivan, S. K.
Das, R. Dowbenko, J. W. Du, R. L. Pelegrinelli (PPG) US Pat. 4055607 (Oct 25
1977).
52 J. Ugelstad, M. S. El-Aasser, J. W. Van-
derhoff, Polym. Lett. 1973, 11, 503.

53 J. Ugelstad, F. K. Hansen, S. Lange,
Makromol. Chem. 1974, 175, 507.

54 J. Ugelstad, M. S. El-Aasser, J. W. Van-
derhoff, Polym. Lett. 1973, 11, 503.

55 F. K. Hansen, J. Ugelstad, J. Polym. Sci.
Polym. Chem. Educ. 1979, 17, 3069.

56 B. J. Chamberlain, D. H. Napper, R. G.
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
Gilbert, J. Chem. Soc. Faraday Trans. 1

1982, 78, 591.
J. Delgado, M. S. El-Aasser, J. W. Vanderhoff J. Polym. Sci. Polym. Chem.
Educ. 1986, 24, 861.
Technical Bulletin on Microfluidizer,
Microfluidics Corporation, Newton,
MA, 1989.
J. Tsavalas, J. W. Gooch, F. J. Schork,
J. Appl. Polym. Sci. 2000, 75, 916.
S. T. Wang, F. J. Schork, G. W.
Poehlein, J. W. Gooch J. Appl. Polym.
Sci. 1996, 60, 2069.
W. Gooch, H. Dong, F. J. Schork, J.
Appl. Polym. Sci. 2000, 76, 105.
R. L. Martin, B. G. Piccirilli, D. L. Faler
(PPG) US Pat. 5071904 (Dec 10, 1991).
H. J. Drexler, F. Ebner, H. D. Hille,
U. Roth (BASF Farben & Fasern AG)
US Pat. 4489135 (1984).
S. Grandhee (BASF) US Pat. 5569715
(Oct 29, 1996).
S. Grandhee (BASF) US Pat. 5786420
(Jul 28, 1998).
S. K. Das, S. Kilic, R. E. McMillan,
(PPG) WO 9749739 (1998).
M. K. Yousuf, Mod. Paint Coat. 1989,
79, 48.
K. OHara, J. Oil. Colour Chem. Assoc.
1988, 71, 413.
S. Swarup, D. L. Singer, G. J. McCollum, K. G. Olson, S. T. Stefko, R. J.
Sadvary, R E. McMillan, M. A. Mayo,
WO 9410212.
M. Nair, Prog. Org. Coat. 1992, 20, 53.
J. Gillatt, Pitture Vernici Eur. 1991,
67(11), 9.
G. A. Vandezande, A. Rudin, J. Coat.
Technol. 1996, 68 (860), 63.
Z. Z. Jin, Y. Hu, Y. Zhu J. Coat.
Technol. 1988, 60 (757), 31.
J. W. Rosthauser, K. Nachtkamp,
Water-borne Polyurethanes in:
Advances in Urethane Science and
Technology, K. C. Frisch, D. Klempner
References
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
(eds), Technomic, Westport, CT 10,

1987, 121.
R. Arnoldus, Surf. Coat. 3 (Waterborne
Coat.). Wilson (ed.) Elsevier, London,
1990, 179.
R. Arnoldus, J. Polym. Paint Colour 1991,
178, 4226, 860.
D. Dietrich, Adv. Org. Coatings, Sci. Technol. Ser. 1979, 1, 55.
D. Dietrich, Prog. Org. Coatings 1981,
9(3), 281.
S. Paul, Surface Coatings: Science and
Technology, John Wiley, Chichester,
1985.
W. D. Davies, in: Additives for Waterbased Coatings, D. R. Karsa (ed.) Royal
Society of Chemistry, 1990, p. 181.
R. E. Tirpak, P. H. Markusch J. Coat.
Technol. 1987, 58, 49.
R. Satguru, J. McMohan, J. C. Padget, R.
G. Coogan, J. Coat. Technol. 1994, 66
830, 4755.
H. T. Lee, Y. T. Hwang, N. S. Chang, C.
C. T. Huang, H. C. Li, Proc. twenty second
Interaction Waterborne, High-Solids and
Powder Coating Symp., University of
Southern Mississippi 22nd 1995,
224233.
U. Akimitsu, K. Teruaki (Nippon Paint
Co. Ltd) Eur. Pat. EP 602497 (July 7,
1997).
P. B. Jacobs, P. C. Yu, J Coat. Technol.
1993, 65 822, 4550.
R. R. Roesler, R. W. Rumer, WaterBorne, Higher-Solids and Powder Coatings
Symp., Feb 1991, pp. 309331.
T. G. Savino, T. C. Balch, A. L. Steinmetz, S. E. Balatin, N. Caiozzo, US Pat.
4794147 (Dec 27, 1988).
T. G. Savino, T. C. Balch, A. L. Steinmetz, S. E. Balatin, N. Caiozzo, US Pat.
4946910 (Aug 7, 1990).
P. Walstra, Principles of Emulsion Formation, Conf. Preparation of Dispersions,
J. Laven, H. N. Stein (eds) Veldhoven,
The Netherlands, 1991, 7792.
N. Willenbacher, T. Frechen, H. Schuch,
B. Lettmann, J. Eur. Coat. 1997, 9, 810.
L. J. Boggs, H. Taniguchi, Int. Waterborne, High-Solids and Powder Coating
Symp., Feb. 1998, pp. 3039.
D. Schmittmann, BASF internal
communication.
93 J. M. Maklouf, S. Porter, US Pat.
4147688 (April 03, 1979).

94 M. S. Andrews, A. J. Backhouse,
US Pat. 4180619 (1979).

95 A. J. Backhouse (ICI), US Pat. 4268547
(1981).
96 H. J. Wright, D. P. Leonard, R. E.
Etzell, US Pat. 4290932 (1981).

97 D. R. Bauer, L. M. Briggs, R. A. Dickie,
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
Ind. Eng. Chem. Prod. Res. Dev. 1985,

21, 686.
L. G. Boggs, M. Rivers, S. G. Bike,
J. Coat. Technol. 1988, 60 (766), 27.
S. Ishikura, K. Ishii, R. Midzuguchi
Prog. Org. Coat. 1988, 15, 373.
W. S. Zimmt, Chemtech 1981, 11, 681.
D, R, Bauer, R. A. Dickie J. Coat
Technol. 1986, 58, 41.
G. Y. Tilak, Prog. Org. Coat. 1985, 13,
333.
L. W. Hill, A. Kaul, K. Kozlowski, J. O.
Suter, Polym. Mater. Sci. Eng. 1988, 59,
283.
Y. Huang, F. N. Jones Prog. Org. Coat.
1996, 28, 133.
A. Zosel, G. Ley, Macromolecules 1993,
26(9), 2222.
C. B. Fox, Proc. ESD/ASM Adv. Coat.
Technol. Conf. 1991, 1991, 161.
A. J. Backhouse, J. Coat. Technol. 3, 54
693 (1982) 83.
Z. Vachlas, J. Oil. Color. Chem. Assoc.
1989, 72, 139.
I. Wagstaff, Proc. ESD/ASM Adv. Coat.
Technol. Conf. 1991 (1991) 43.
S. L. Buchwalter, R. D. Jerabek, L. H.
Chou, R. M. Christenson (PPG)
US Pat. 4198331 (1978).
J. T. Valko (PPG) US Pat. 4423167
(1981).
(1981).
(1981).
P. E. Kordemenos, J. D. Nordstrom,
J. Coat. Technol. 1982, 54 (686) 3341.
J. Meister, Polym. Prepr. (Am. Chem.
Soc., Div. Polym. Chem.) 1997, 38(2),
638639.
C. B. Fox, Proc. ESD/ASM Adv. Coat.
Technol. Conf. 1991 (1991) 161.
Z. Vachlas, J. Oil Colour. Chem. Assoc.
72 (1989) 139.
189
Applications in the Adhesives and Construction Industries

Dieter Urban and Luke Egan
8.1
Introduction
Adhesives are high-molecular-weight substances which bond materials to one another without significantly changing their structure. The action of adhesives is based
on two key properties: they must firstly wet solid surfaces and adhere to them, and
secondly, they must be cohesive, i.e. have internal strength.
Adhesives of natural origin were mainly used prior to the beginning of the 20th
century and by early civilizations as long ago as 2000 BC. These included animal
glue, casein, natural rubber and starches. Today, specially developed adhesives based
on semi- or fully synthetic products are used for a wide variety of bonding applications (Fig. 8-1).
The development of synthetic adhesives paralleled the development of plastics
which began in 1845 with the nitration of cellulose to give cellulose nitrate, the first
semi-synthetic plastic, whose ethereal solution was used by the shoe industry in 1910
for bonding leather. The products discovered in 1872 by Adolf Baeyer by polycondensation of phenol with formaldehyde were the basis for the first fully synthetic
plastic, Bakelite, which was obtained by Bakeland in 1909 by thermally curing reactive phenolic pre-condensates. But it was not until 1930 that phenol-formaldehydes
and urea-formaldehyde condensates developed by C. Goldschmidt in 1896 (Kaurit)
were used widely as adhesives.
Polymerization processes discovered in the 1920s resulted in a large number of
new thermoplastics and elastomers, of which, in particular, polychloroprene, and
polyisobutylene were used as the basis for new adhesive technologies. Polyurethanes
and epoxies developed in the mid-1930s further broadened the range of adhesive
raw materials.
Thermally stable plastics were more recently developed which enable adhesive
bonds that withstand temperatures up to 350 C. Concurrent development of new
bonding technologies (e.g. sandwich construction) now makes it possible to adhere a
multitude of various materials to one another. As such, classical connection meth-
191
192
8 Applications in the Adhesives and Construction Industries

Natural adhesives
Animal glue
Gluten (hide glue, bone glue)
Casein
Blood albumin
Vegetable glue
Albumin, wheat, pectin
Starches, artificial gum
Natural gum, gum arabic, tragacanth
Natural rubber, gum rosin, natural resins (colophony)
Synthetic adhesives
Physical binders
Bonding by evaporation (water- and solvent-borne adhesives)
Cellulose ester, cellulose ether
Synthetic rubber (polychloroprene, copolymers of butadiene with acrylonitrile or
styrene)
Copolymers of acrylics, vinyl esters, vinyl ethers
Derivatives of natural rubber (chlorinated or cyclized rubber)
Polyurethane elastomers
Bonding by cooling (hot melt)
Ethylene copolymers
Polyalkylene terephthalate
Polyamide
Butadiene or isoprene based block copolymers
Chemical reacting adhesives
Urethanes, epoxides, silicones
Urea, melamine, and phenolic resins
Cyanoacrylate, (meth)acrylates
Fig. 8-1
Synthetic and natural adhesive raw materials.
ods, such as welding, riveting, screwing, sewing, etc., continue to be replaced by adhesive bonding techniques.
Adhesive bonding has now become a routine joining method in a host of various
industries including automobile, furniture, shoe, construction and packaging. A
particularly impressive example of new adhesive technology is in aircraft and rocket
construction, where supporting structures are adhesively bonded on assembly
lines [19].
In Western Europe, about 1.5 million tons of adhesives (dry weight) were used in
1996 [10] compared to 2.3 million tons in North America [11]. The world market in
1996 for adhesives and sealants was about US$ 21 billion compared to approximately US$ 6.4 billion in North America [11].
8.2 Pressure-sensitive Adhesives
8.2
Pressure-sensitive Adhesives
Pressure sensitive adhesives (PSA) are highly viscous, viscoelastic liquids which adhere to virtually all surfaces when pressed down gently. They are used in manufacturing easy to apply self-adhesive products, such as labels and tapes. Pressure sensitive adhesives typically have permanent tack and adequate cohesion, so that further
curing operations after applying the tape or label are generally unnecessary.
The first self-adhesive products were adhesive plasters [12], which were developed
in the USA in 1845 by the medical doctor H.H. Day [13] and in Germany in 1882 by
P. Beiersdorf [14]. The use of self-adhesive tapes for industrial purposes marked the
beginning of dry-adhesion technology. A new branch of industry began to coat various support materials with pressure sensitive adhesives and to make self-adhesive
products from them. In 1935, R.S. Avery [15] invented a coating unit for self-adhesive paper labels using a wooden cigar box filled with an adhesive solution. The adhesive dripped through holes cut in the bottom, on to a roll of paper that ran below.
This was probably the first curtain coating process.
Until the beginning of the 1970s, pressure sensitive articles were produced
mainly by coating from organic solutions. Solvent-based rubber/resin mixtures and
comparatively smaller amounts of acrylate solutions were processed almost exclusively.
The first water-based acrylate dispersions were developed as long ago as the 1930s.
They were produced on an industrial scale for the first time at the beginning of the
1940s. However, acrylate dispersions for pressure sensitive adhesives were not introduced into the market until the beginning of the 1950s. The first areas of application
were self-adhesive book binding and map protection films. It was then possible for
the first time to make flexible PVC films self-adhesive without the need for a primer.
This excellent property also made it possible to use dispersions for electrical insulation tapes. The use of self-adhesive films in advertising applications (e.g. promotional graphics, signs) began at virtually the same time. Furthermore, acrylate dispersions satisfied the demand for removability without leaving a residue.
A continuous increase in pressure sensitive adhesive dispersion production occurred throughout 1960s. The rapid development of a number of new applications
accelerated this process. The crucial factor was the ground-breaking, systematic
work in the 1970s on high speed coatings technologies [16]. The development of new
application equipment and corresponding high-solids dispersions has enabled coating rates to be increased from less than 60 m min1 to as high as 6001000 m min1
today.
As so often it occurs in new technical developments, completely unexpected
advantages became evident with newly developed acrylic dispersions. The inherent
properties of polyacrylates made by emulsion polymerization enabled hitherto
unknown speeds during down-stream converting operations (i.e. slitting, die cutting
and stripping). It was also found that existing solvent coating units could be modified to permit economical processing of aqueous dispersions. This increased efforts
to use aqueous polyacrylate dispersions as pressure sensitive adhesives.
193
194
The total market demands for pressure sensitive adhesives (tapes and labels) is
about 300 000 tons of polymer in North America and about 200 000 tons in Europe.
Aqueous polymer dispersions have a share of about 30 % in North America and 40 %
in Europe. About 30 % in North America and 45 % in Europe are applied from
organic solution while hot melts have a share of 40 % in North America and 15 % in
Europe [17, 18].
8.2.1
Self-adhesive Labels
Self-adhesive labels (and decals) are pieces of paper, plastic film or metal foil coated
with pressure sensitive adhesives which adhere to any solid surfaces after removal
from a release liner. They are typically used to convey various kinds of information
for example, product or package contents, barcodes, price stickers, instructions, and
technical data.
The most important adhesive raw material compositions for adhesive labels are
polyacrylate dispersions, styrene-butadiene rubber solutions, and styrene-butadienestyrene (SBS) and styrene-isoprene-styrene (SIS) hot-melt adhesives. Permanent and
removable UV-cross-linkable acrylic hot-melt adhesives have recently also been introduced [1922].
In the 1970s, Japanese paper label manufacturers started converting from rubber
solutions to water-borne systems because of very strict environmental protection regulations, resulting in acrylic dispersions becoming the most important group of PSA
raw materials in Japan. In North America, 85 % of the PSA label market was solvent
born in 1975 [23] but in 1991 approximately two-thirds of the market was waterborne [24].
In Europe, the conversion was carried out in the 1980s and now the use of acrylic
dispersions in self-adhesive products is widespread and well advanced. The importance of acrylic dispersions continues to increase for reasons of environmental protection (nonflammable, no hazardous solvents), high solids contents, good aging resistance, and excellent coating and processing properties.
About 2.9 billion m2 of self-adhesive labels were produced in Europe in 1996,
corresponding to 35 % of world production. At average application rates of 24 g m2,
this corresponds to a demand for adhesives of 70 000 dry tons year1 in Europe.
In North America 3.5 billion m2 of self adhesive labels were produced in 1999. Assuming the same coating weight, the adhesive demand in North America was 84 000
dry tons year1.
Polyacrylate dispersions
Adhesion and cohesion of polyacrylate dispersions can be varied over a broad range
and matched to many applications through the type and combination of low Tg (soft)
and high Tg (hard) monomers, the choice of auxiliaries, and the control of the
molecular weight and process parameters [2629]. Some examples are given below.
The influence of glass transition temperature (Tg) of acrylic homopolymers on tack
(according to A. Zosel [30, 31]) at various temperatures is shown in Fig. 8-2.
Tack of polyacrylates as a function of composition and

temperature.
Fig. 8-2
It can be seen that tack is greatest at temperatures 5080 C above the Tg of the
homopolymers. In addition, the tack increases with increasing hydrocarbon chain
length of the acrylic monomer. For use at room temperature, polyethylhexyl and
polybutyl acrylate have the greatest tack [27].
Besides polymer composition, the molecular weight of the polymer also affects adhesion properties. A practical measure for assessing the average degree of polymerization, in particular for process control, is Fikentschers K-value, which is obtained
by measuring the relative viscosity of a dilute polymer solution [32]. This characteristic constant, which can be determined quickly and simply at a single concentration,
enables a rough estimate of the intrinsic viscosity and molecular weight [27].
The following measures may be used for varying degree of polymerization:
addition of a chain transfer agent, crosslinking additives, mixing high-molecularweight with low-molecular-weight components, and variation of the polymerization
process [27].
The following example is intended to clarify the effect of molecular weight. Acrylic
dispersions of identical composition, but of different K-value, varied through different amounts of a chain-transfer agent, were investigated (Fig. 8-3) [27]. The peel
strength is low at very low K-values and high at a K-value of 50 (cohesive fracture). At
K-values above 50, the failure mechanism changes from cohesive into adhesive, and
the peel strength drops to a low value. If the K-value is increased further, the peel
strength drops slightly.
Substrate wetting and polymer cohesion strength are responsible for these results.
Although wetting is good at low K-values, the cohesion of the film is very low. The
higher the K-value, the higher the internal strength of the film and the worse the wetting, i.e. the lower the tack or adhesion.
195
196
peel strength in N / 2 cm
peel rate 300 mm / min
20
cohesion failure
adhesion failure
15
10
0
20
50
80
K-value
Fig. 8-3 Peel strength as a function of molecular weight (K-value),

according to W. Druschke [27].
However, adhesion is not affected by the average molecular weight alone, but also
by the molecular weight distribution. This can be seen in Fig. 8-4, which shows the
peel rate 300 mm / min
20
cohesion failure
adhesion failure
15
10
0
10:0
8:2
6:4
4:6
2:8
0:10
lower/higher molecular weight component

Peel strength as a function of the content of high-molecularweight component, according to W. Druschke [27].
Fig. 8-4
peel strength of various mixtures of relatively high molecular weight acrylic polymer
(K-value ca. 90) with low molecular weight material having the same composition
(K-value ca. 55). With increasing content of high-molecular-weight component,
i.e. an increase in the average degree of polymerization, the transition from cohesive
to adhesive fracture occurs again with a sudden drop in the measured peel values.
The maximum peel strength is obtained at a high molecular weight component content of 80 % [27].
When an acrylic dispersion with good low temperature peel strength (A) is mixed
with one having high cohesive strength (B), the actual performance of the mixtures
can deviate strongly from a linear mixing relationship. As Fig. 8-5 shows, the shear
values are significantly reduced by small amounts of dispersion A and low temperature peel strength drops to zero at only 20 % of component B.
Shear values at 20 C and low temperature peel strength at

23 C depending on the mixing ratio of a high peel dispersion A and
a high shear dispersion B [33]
Fig. 8-5
Interestingly, copolymerized functional monomers like acrylic acid, for example,

results in an increase in cohesion (Fig. 8-6) and produces a significant increase in the
shear strength.
The two contradictory requirements for high tack and needed internal strength
can be best achieved in polyacrylate dispersions when adhesive and cohesive components are produced stepwise during the emulsion polymerization. The transfer of
free radicals to pre-formed polymer chains results in the formation of branches,
which crosslink on recombination. Crosslinking affects the viscoelastic behavior in
two ways: by slightly raising the glass transition temperature and by increasing the
modulus level above the glass transition region. It also reduces the mobility of the
crosslinked polymer chains. This behavior is pronounced in polyacrylates and can be
197
198
shear in min
1/2 inch x 1/2 inch, 500g
1 500
Shear strength as a
function of copolymerized
acrylic acid.
Fig. 8-6
1 000
500
0
0
2
acrylic acid in pphm
used to improve cohesion. Adhesion can be improved using a chain transfer agent,
which suppresses crosslinking and produces lower molecular weights.
Figure 8-7 shows that even small amounts of chain transfer agent cause a significant reduction in cohesion. The maximum peel strength is achieved at 0.2 pphm and
the maximum quick-stick (or loop tack) at 0.3 pphm of chain transfer agent. An optipeel (Cr)
[N/inch]
300 mm/min
quick-stick (Cr)
[N/inch]
300 mm/min
cohesion
[min]
1/2 x 1/2 inch, 500 g
peel strength in N / inch

20
time in min
100
80
15
60
10
40
5
20
0
0
0,1
0,2
0,3
0,4
chain transfer agent in pphm
0,5
Effect of the chain transfer agent on the adhesive properties of an

acrylic dispersion.
Fig. 8-7
mum balance between plasticity and bond strength is clearly achieved at a certain
degree of crosslinking.
The polyacrylate dispersions optimized in this way for pressure sensitive adhesives are produced and supplied with solids contents between 50 % and 70 %.
Average particle sizes are typically between 100 nm and 1000 nm. However, dispersions with a high solids content (> 60 %) and low viscosity (<500 mPa s) need to have
a bimodal or multimodal particle size distributions. The viscosities of most commercial products are generally between 10 and 1000 mPa s but high-viscosity dispersions
greater than 10 000 mPa s are also used in certain packaging applications. Polymers used in pressure sensitive applications have glass transition temperatures of
between 60 and 20 C.
Formulation modifications
Acrylate dispersions can be used directly in only a small number of applications.
Technical or economic considerations often make modification necessary [34]:
optimization and refinement of the adhesion properties;
production of a large number of self-adhesive products using a small number of
starting materials;
optimization of the formulation from a commercial point of view; and
matching of the viscosity, rheology and wetting behavior of the adhesive to the proposed coating method and substrate.
This is generally done by mixing acrylic dispersions with one another, and adding
tackifying resins and plasticizers. Wetting agents, defoamers and thickeners are
added to adapt the adhesive to the prevailing coating conditions. Fillers or pigments
are used to color the adhesive material (e.g. brown adhesive tapes for packaging) or
to achieve special effects (e.g. zinc oxide in medical tapes).
Dispersion mixtures
In some self-adhesive products (for example, protective films), the goal is a weak tack
which does not increase after extended bonding times. These products are based on
special self-crosslinking acrylics. In order to improve the tack, cohesive products
with good tack are admixed. In certain applications requiring chemical resistance
(e.g. against plasticizers), a dispersion with superior resistance can be mixed in certain proportions to increase the overall formulation performance. In wet labeling applications (e.g. bottles), which previously used natural adhesives such as casein, a
blend of acrylic dispersions, natural latex, and wax dispersion have been employed.
Note that blends of acrylics and styrene-butadiene latex (SBR), for example, produce
dry films which are opaque because of differences in refractive index. The formulator can take advantage of this effect to impart opacity to a substrate. But it is important to note that when blending acrylics and SBR, water resistance of the dried
films can be affected in unexpected ways (Fig. 8-8).
199

70
60
Water Update (%, after 24hrs)
200
50
40
30
20
10
0
100/0
80/20
50/50
20/80
0/100
PSA Blend Ratio (Acrylate / SBR)
Water resistance of dried PSA films depending on the blend ratio

acrylic/styrene-butadiene latex.
Fig. 8-8
Addition of tackifying resins

Resins are used to improve the tack of pressure sensitive adhesives. They must be
compatible with the polymer (i.e. mixture has a single Tg) and modify its viscoelastic
properties resulting in improved polymer flow characteristics, substrate wetting, and
adhesive bond formation.
The most suitable products for improving the tack of polyacrylates are modified
natural resins, such as dimerized or hydrogenated gum rosins and esterified abietic
acids. With resins whose softening points are about 70 C, pressure sensitive adhesives with high shear strength but relatively low tack are obtained. If these resins are
combined with softer resins, the tack is significantly increased. Besides the general
increase in tack, addition of resin also specifically increases the adhesion to polyolefin surfaces. However, the addition of resin may impair the aging resistance of
the adhesive. Preferred applications for acrylateresin combinations are paper labels
and double-sided adhesive tapes (for example, carpet laying tapes). Hydrocarbon
resins based on petroleum oil derivatives are preferred for tackifying styrenebutadiene dispersions [24, 35].
To retain the advantage of the solvent-free feature offered by polymer dispersions, resin dispersions should be used instead of resin solutions. Resin dispersions
are available, for example, from Akzo Nobel/EKA Chemicals (Netherlands, USA),
DRT/ND Dispersions (France, USA), and Hercules (Germany, USA). However, it
should be noted that a resin dispersion generally reduces cohesion to a greater extent
than does a resin solution because of the surfactants present. In addition, the water
resistance, evident from blushing, is often reduced. Polymeric tackifier has been reported to increase the elastic properties of a pressure sensitive adhesive resulting in
improved peel strengths, especially at high peel rates [36].
Addition of plasticizers
Plasticizers increase the flow properties of the adhesive film. This results in faster
wetting of the substrate surface to be bonded and consequently increases the initial
peel strength. This naturally occurs at the expense of cohesion and heat resistance.
In contrast to resins, which normally increase the Tg of the adhesive polymer, plasticizers decrease the Tg and make the polymer softer. The tack-increasing effect of
resins can be augmented by addition of small amounts of plasticizers. Particularly in
the case of resins with high softening point that have a deadening action on the
adhesive, addition of a small amount of plasticizer results in a lowering of the softening point. A resin-plasticizer combination consequently increases the tack very
effectively. Small amounts of plasticizer (25 %) are frequently added to the acrylic
dispersions in order to obtain gentler removal.
The main plasticizers used are the classical plasticizers (i.e. phthalates such as
DOP, DBP and DIDP). Adipates are also suitable as polymeric plasticizers, but are
rarely used owing to price reasons and their somewhat lower compatibility. A special
polymeric plasticizer polypropylene glycol alkyl phenyl ether (Plastilit 3060) from
BASF, has extremely good compatibility with acrylate polymers and does not migrate. This product has now proven highly successful in a number of applications
(including pressure sensitive adhesives, acrylic sealants and paints).
Thickening of pressure sensitive adhesive dispersions
Suitable protective colloids and thickeners include animal glues, gelatin, casein, vegetable gum, dextrins, enzymatically digested starches, alginates, cellulose derivatives
(methyl-, carboxymethyl- and hydroxyethylcellulose), polyvinyl alcohols, polyacrylic
acids, polyacrylamides and polyvinylpyrrolidones, amongst others. They increase the
viscosity and water retention, modify the rheology for optimum coatability and
speed, and in addition generally also improve the mechanical stability and compatibility of the dispersions with electrolytes and fillers. In order to achieve optimum results, precise metering and suitable selection and combination of the protective colloids and thickeners are necessary. Since the water resistance of polymer films from
dispersion decreases with increasing addition of thickener, the proportion of thickener should always be minimized.
Addition of wetting agents
Thickened dispersions generally have little problem wetting various surfaces. Even
surfaces with extremely low surface tension, such as silicone paper and corona treated polyolefin film, can be wetted under the uniform pressure imparted by the liquid
adhesive on to the substrate during the coating operation. A high resistance to flow
(i.e. high viscosity) prevents subsequent dewetting and minimizes the occurrence of
coating flaws (e.g. fish eyes).
The situation is quite different, however, in high speed, low viscosity coating systems such as modern vario-gravure where the dispersion film, which is initially uniformly distributed on the surface, re-coalesces relatively quickly if its surface tension
is excessively high. In this case, the surface tension of the pressure sensitive adhesive dispersion must be matched to that of the substrate to be coated (film or silicone
201
202
paper). This is achieved by adding corresponding surfactants, so-called wetting

agents. These surfactants naturally increase the risk of foaming and in some cases
increase the water sensitivity of the adhesive film. The amount added should again
be kept as low as possible. The sodium salt of a sulfosuccinic acid ester (Lumiten I-SC,
BASF, Aerosol OT70-PG, Cytec) is a relatively low-foaming surfactant whose particular effectiveness as wetting agent arises due to its tendency to migrate to newly
formed surfaces very quickly.
Addition of antifoams
Surfactants (emulsifiers and wetting agents) often cause foaming, which results in
coating defects particularly when operating at high speeds. This is prevented by addition of antifoams. The effectiveness of antifoams, for example higher alcohols,
non-ionogenic acetylenic compounds, or aliphatic hydrocarbons with non-ionogenic
constituents, varies depending on the other auxiliaries present in the formulation
and in addition can drop with increasing storage time. The antifoam may float, settle
or diffuse into the polymer and thus, is no longer available at the liquidair interface
where it is needed. It is therefore recommended that the dilute antifoam only be
added immediately before processing or, even better, sprayed directly on to the foam
surface by means of an atomizer if needed.
It should be noted that excessive amounts can impair flow of the dispersion,
which rapidly results in flaws (pinholes, fisheyes) in the coating. A general rule of
thumb is that the amount of antifoam in initial experiments is 10 % of the amount of
wetting agent, i.e., for example, one part of wetting agent and 0.1 part of antifoam
per 100 parts of dispersion. Owing to interaction with the auxiliaries in the dispersion, the most effective antifoam for each adhesive must be determined experimentally.
Companies which offer suitable antifoams include: Air Products and Chemicals
Inc., Allentown PA (USA); BASF AG/Corporation, Ludwigshafen/Mount Olive
(Germany/USA); Ashland Chemical Co., Drew Industrial Division, Boonton, NJ
(USA), or Drew Ameroid Europe, Ultra Additives Inc, Patterson, NJ (USA); Henkel
AG, Dsseldorf (Germany); ICI Surfactants, Middlesbrough (England), Muenzig
Chemie, Heibronn (Germany).
Addition of fillers or pigments
Fillers cause significant deadening of the adhesive, which can be compensated again
by a slightly increased amount of tackifier. In labels made from relatively thin paper,
small amounts of fillers or pigments can be added in order to increase the hiding
power.
Zinc oxide has proven successful as an antiseptic, moisture-absorbent filler in rubber-based medical adhesive tapes. In contrast, modern medical adhesive tapes with
non-woven or woven fabric as support material use polyacrylates owing to their lower skin irritation action. These contain virtually no filler. If necessary, white coloration is produced using TiO2.
Fine sand (SiO2) also has a very strong deadening action. Even on addition of only
10 %, the tack can no longer be measured. Calcium carbonate filler exhibits much
better behavior. The smallest reduction in tack is caused by titanium dioxide, but this
is relatively expensive.
For homogeneous incorporation of fillers or pigments, it is advantageous to prepare a paste with a little water. Additives to the water, such as ammonia, polyacrylic
acid salts and polyphosphates, aid in dispersing and also prevent the filler particles
from subsequently re-agglomerating. A wetting fluid comprising one part of ammonia, one part of Pigment Dispersant A (BASF), one part of Calgon N (sodium
polyphosphate, Benkiser, Ladenburg) and 97 parts of water, to which the pigments
are mixed to yield a paste, has proven successful.
Protection against microorganisms
The risk of bacterial, yeast or fungal contamination is naturally the greatest in the
neutral or weakly basic pH range. This pH range is in most cases established during
modification as it also provides the best compatibility of the dispersion with formulation additives. Preservatives used include formols, benzisothiazolinones (Proxel,
Avecia, Wilmington, DE, USA and Manchester, UK), isothiazolones (Kathon , Rohm
and Haas, Philadelphia, PA, USA, Rohm and Haas France SA, Valboonne-Cedex,
France). Other preservative suppliers include Riedel-de Han AG (Germany), Troy
Corporation, Florham Park, NJ (USA) and Arch Chemicals (Paris, France and
Cheshire, Connecticut, USA).
General notes on modification
The following is a suitable compounding procedure: the pH of the starting dispersion is firstly increased in order to improve compatibility. Secondary acrylate dispersions are then added, followed by resin solution or resin dispersion, other tackifiers,
plasticizers and, if used, a pigment and/or filler paste. The final step is adjustment to
the processing solids content and viscosity by thickening, dilution and addition of
wetting agent.
Guiding formulations
1. Acrylic permanent paper label (resin tackified)
Polymer dispersion
Tackifier dispersion
Defoamer
Wetting agent
Neutralizing agent
Water
Rheology modifier
Application rate: 20 g solid m2
Acrylic dispersion, 6070 %

Tacolyn 1070, 55 %*
or Snowtack 880G, 57 %
Drewplus L-108
Lumiten I-SC
Ammonia (10 %) to pH 7.58.5
As required to max. 65 % solids
As needed for coating head
Suppliers: *Hercules, Wilmington, DE, USA; Akzo Nobel, Toronto, Ontario, Canada;
Ashland/Drew Chemical; BASF, Charlotte, NC, USA
Wet wt.
116
36.4
0.10.5
0.51.5
02
02
203
204
2. All-temperature paper label (non-tackified)

Polymer dispersion
Acrylic dispersion
Neutralizing agent
Ammonia (10 %) to pH 7.58.5
Wetting agent
Aerosol OT70-PG#
Rheology modifier
As needed for coating head
Water
To maximum 65 % solids
100
35
0.51
02
Suppliers: #Cytec
Styrene-butadiene dispersions
In North America approximately 510 % of the dispersions used for labels are based
on styrene-butadiene rubber (SBR) [24]. SBR used in pressure sensitive adhesives
are produced by emulsion polymerization with butadiene contents typically between
25 and 45 %. With careful control of process conditions (temperature, styrene
and butadiene feed rates) and ingredient feed levels (chain transfer agent, initiator,
monomers), intermediate molecular weight, lightly cross-linked elastomers having
an excellent balance of cohesive and adhesive properties can be obtained.
SBR based systems are primarily used in cost-sensitive paper label applications;
they are not used, when clear films with long-term UV or heat aging resistance are
required. While the hydrophobic nature of SBR promotes superior initial tack and
adhesion to low energy substrates, this feature also makes them susceptible to plasticizer attack.
Compared to tackified acrylic PSA, styrene-butadiene based systems normally require significantly increased tackifier contents (up to 2 times) to achieve desired tack
and peels levels. SBR are compatible with both commercial rosin and hydrocarbon
based tackifying resins. Differences in chemical composition, softening point, and
surfactant stabilizers in tackifier dispersions can have a significant impact on the
peel-shear balance of the formulated product [26]. Since commercial SBR are available at relatively low solids contents (ca. 5055 %), the formulated adhesives have
higher water contents compared to those based on acrylics. This subsequently translates into slower line speeds and/or higher energy demand during the drying operation. An antioxidant would be recommended for SBR applications requiring extended stability against heat exposure or oxygen attack.
Guiding formulation
SBR permanent paper label (resin tackified)
Polymer dispersion
Butonal NS 166, 51 %*
Tackifier dispersion
Aquatack 6085, 60 %
Defoamer, wetting agent, and rheology modifiers added as needed.
Wet wt.
63.8
36.2
Suppliers: *BASF Corporation, Charlotte, NC, USA; Arizona Chemical, Panama City, FL, USA
Coating
Self-adhesive labels and films are produced by coating support materials such as silicone release liner, paper stock, and film webs with pressure sensitive adhesives
(Fig. 8-9). Various coating methods are used to ensure the correct amount of adhesive is applied per unit area of substrate [3740]. High viscosity adhesives can be applied using a knife-over-roll coater. In reverse-roll coating, the adhesive is transferred
to the substrate web after being taken up by an application roll rotating in a direction
opposite to that of the web. Knife coaters and reverse roll coaters are traditional systems originally developed for coating solvent-based adhesives. But with aqueous dispersions, coating speeds of only 100120 m min1 are possible with these coating
methods at application rates of about 20 g m2. For higher production speeds,
Meyer rod (150250 m min1), reverse gravure (300 m min1), vario gravure
(600+ m min1), and slot die technologies are available. These systems require lowviscosity dispersions and their development in the 1960s paved the way for a major
breakthrough by acrylate dispersions for mass-produced pressure sensitive articles
in Europe. Improvements in coating speeds, reliability, coating consistency, and
product quality led to lower production costs and continuation of the trend to waterbased emulsion coating technologies.
Coating head
Steam
Dryer
Laminating
station
Release
liner
Schematic representation
of PSA label coater.
Fig. 8-9
Unwind
Backing
Rewind
Reverse gravure was introduced by BASF at the beginning of the 1980s for pressure sensitive adhesive processing and basically consists of a blade pressed on to a
gravure cylinder rotating in a pan of wet adhesive in a direction opposite to that of
the web. Adhesive is transferred from the pan into the recesses of the gravure roll
and then on to the web. The blade and roll assembly are primarily responsible for
metering on the correct quantity of wet adhesive and establishing a consistent, defect
free adhesive coating. Gravure rolls (Fig. 8-10) with 14 to 18 lines cm1 give a dry
coating weight of about 20 g m2. A gravure roll with 36 lines cm1 gives, for example, about 10 g m2 (in each case with an approximately 50 % solids adhesive). If desired, the coating weight can be varied slightly by adjusting the blade position and by
modifying the viscosity of the adhesive. For significant changes, a roll with a different grid must be used.
When high reverse-gravure coating speeds (600+ m min1) are attempted, coating
weight is found to drop off drastically above about 300 m min1. This behavior occurs
at high speeds because of the shorter residence time of the gravure roll in the dispersion reservoir i.e., so short that the gravure line cells are no longer completely
205
206
Fig. 8-10 Portion of a gravure roll (left), cross-sectional schematic (right).

(a) 1020 m chrome layer, (b) 1015 m nickel layer, (c) 70250 m
copper layer, (d) steel base roll.
filled and too little dispersion is applied to the web. However, if the dispersion is
forced into the engraving under pressure, it is possible to vary coating weight over a
broader range, even with a constant number of lines. For example, application rates
from 15 to 30 g m2 can be achieved at 600 m min1 with an 18 lines cm1 gravure roll
and from 20 to 40 g m2 with a 14 lines cm1 gravure roll.
Vario gravure is a substantial refinement of the standard reverse gravure method
(Fig. 8-11). The side seal consists of two polyethylene margin wipes pressed
against the polished ends of the gravure roll. Two grooves, providing pressure release and lubrication, are incorporated into each margin wipe. Rubber parts are also
built into the margin wipes to seal the side edges of the coating blade the entire
casting box assembly is sealed by a lateral force applied on to the sides of two margin wipes. The upper blade is additionally pressed against the gravure roll surface,
which simultaneously prevents air being drawn in and results in very low air entrainment (i.e. low foaming).
substrate
adhesive
blade adjustment
margin wipe
out
blade adjustment
Fig. 8-11
Vario gravure coating head.
in
PSA dispersion
Coating weight is controlled mainly via the pump pressure, designed to operate
without pulsation (Mohno pump). Due to the excess pressure prevailing in the casting box (0.20.6 bar), not only are the recesses of the gravure roll surface filled, but a
film, i.e. an excess, is also applied on to the roll. This is the only way that a coating
weight of 20 g m2 can be maintained at higher speeds (400600+ m min1). The flow
rate of wet adhesive through the pump can also be coupled to the web speed in order
to keep coating weight constant during speed changes.
Water based pessure sensitive adhesives can also be directly applied on to the substrate web using a slot die coater (Fig. 8-12). Die coating is widespread in the USA
(est. 6070 % of total label production), but is only used occasionally in Europe.
adhesive
substrate
width adjustment of slot die opening
die
die lip offset adjustment
Fig. 8-12
Slot-die coating head.
PSA dispersion
feed line
Coating weight can be easily varied over a broad range at different web speeds.
Uniform distribution of medium-viscosity adhesive over the web width is achieved
with a special die geometry where the outlet aperture is larger at the web edges than
in the center. This method provides an impressive final coating characterized by
unusual levelness.
8.2.2
Self-adhesive Tapes
Self-adhesive tapes are flexible substrates coated with pressure sensitive adhesives
which are wound up in roll form and cut to different widths.
About 4.3 billion m2 of adhesive tapes were produced in Europe in 1996 [41]. Seventy percent of these are packaging tapes, while the remainder are double-sided adhesive tapes, masking tapes and other adhesive tapes (medical tapes, electrical insulation tapes, household tapes, office tapes and protective films). Solvent-based, resinmodified rubber solutions, used mainly for packaging adhesive tapes, are still dominant in this segment. The stringent requirements on tack and cohesion for tapes
207
208
have still not been achieved by any other adhesive system in such a balanced way.
The proportion of water-borne adhesives used in the European tape market is about
14 % [19]. Water-borne adhesives are mainly used for double-sided adhesive tapes
and electrical insulation tapes.
In North America, about 4.5 billion m2 of adhesive tapes were produced in 1999.
Assuming an average coating weight of 40 g m2, this corresponds to a polymer demand of 180 000 tons year1. About 70 % are used for industrial and packaging tapes,
the rest is used for consumer, surgical, electrical and masking tapes [18]. Waterborne systems are used mainly to produce carton-sealing tapes.
Packaging tapes
Packaging tapes are required to form the contact points necessary for box or carton
closure (typically corrugated), even on gentle pressure. This means that the adhesive
must have high tack and good adhesion. In Europe, natural rubber is predominately
used to meet these requirements. Although acrylate dispersions have better aging
resistance, they have lower tack at the high cohesion levels needed.
Experiments have shown that the lower tack values can be fully compensated
through increased positioning or application pressure. In North America, carton
sealing tapes made from oriented polypropylene and water-borne acrylic PSA are
also produced. Anchoring of the dispersion adhesive to the polypropylene film is
achieved by corona pretreatment. A release coating is not necessary. The main requirements for this application are withstanding the continuous shear and low-angle
peel forces transmitted to the tape at the carton closure. Coating weights of about
1535 g dry adhesive m2 are typically used. Paper backed tapes, such as masking
tapes, require coating weights in the 3060 g m2 range.
Foil duct tapes
Foil duct tapes, used in North America for heating, ventilation and air conditioning
systems, are constructed of 50 m aluminum foil coated with 50100 m of an
acrylic dispersion PSA to provide high adhesion and functionality at extreme use
temperatures. Once coated, the adhesive is covered with a release liner to prevent adhesion to the top side of the foil and subsequent blocking of the tape roll. Some foil
tapes use strands of fiber reinforcement laminated between foil and kraft paper layers to improve tensile strength [24].
Electrical tapes
Flexible PVC tapes of various types are predominately used for electrical insulation
purposes and to a lesser extent, for pipe insulation. In Europe, acrylate dispersions
have been used in the manufacture of electrical tapes for more than four decades.
Coating weights of ca. 25 g dry adhesive m2 are typically used. Their advantage is
that they can be coated on to flexible PVC films without a primer. However, the use
of dispersions requires a high level of knowledge of the compositions and interactions between particular flexible PVC substrates and acrylic adhesives. As a result,
suitable dispersions must be carefully selected and in many cases, it is necessary to
use more than one dispersion type to achieve required performance levels. Of prime
importance are plasticizer resistance screening tests on the adhesive, carried out in
order to examine for undesired changes in adhesive properties due to plasticizer migration from the PVC film.
Masking tapes
This term covers tapes for protecting surfaces during painting, sand blasting, etc.
The support material used is crepe paper of various quality and extensibility with natural rubber predominately used in the adhesive. Nonetheless, adhesives made from
mixtures of certain acrylate dispersions are highly suitable for painters-grade
masking tapes. Key requirements of masking tapes include adequate adhesion and
then easy removability without leaving a residue even after extended storage times
or after exposure at high ambient temperatures. Coating weights of ca. 45 g m2 dry
adhesive are used.
Double-sided adhesive tapes
Double-sided adhesive tapes or mounting tapes have been used to replace conventional attachment methods in a range of different end-use applications. They are
used on a wide variety of surfaces, for example, as an assembly aid in the automotive
industry, in graphic arts for plate mounting and in home and office uses that previously required mechanical fasteners (e.g. nails and screws). The central support substrate used includes non-wovens, textile fabrics, foams and other materials and in
some cases, support-free mounting tapes are also available. Foam mounting tapes
are especially useful because the foam provides stress distribution for increased
shear strengths.
While acrylate dispersions are often used, the most demanding applications employ solvent based acrylates that are subsequently crosslinked chemically or thermally to achieve performance requirements. In applications requiring exceptionally high
adhesive coating weights (up to 100 g dry adhesive m2), dispersions having high
solids contents have been advantageous to increase drying rates during the coating
operation.
Protective films
Protective films are used to protect high-value items like painted or polished metal
surfaces (e.g. automobile paint finish), anodized aluminum, acrylic sheets, lacquered furniture surfaces and automotive carpets from scratching, soiling and marring during manufacture, shipping and installation. A range of support substrates
are used, including paper, flexible PVC, PE-, PP- and polyester films [24]. Here too,
acrylate dispersions are being used instead of the cross-linkable acrylate solutions
used in the past. In particular, self-crosslinking emulsion adhesives providing crucial cohesion and anchoring to PE films have been developed especially for protective
films [24, 42]. Coating weights of about 5 g dry adhesive m2 are employed.
209
210
8.2.3
Test Methods
Tack, adhesion and cohesion are the three main properties required of a pressure
sensitive adhesive.
The tack is the ability of a pressure sensitive adhesive to adhere immediately to a
surface. A pressure sensitive adhesive with good tack forms the contact points necessary for adhesion of the tape or label after only brief contact with a substrate. Solvent based rubber adhesives can have very good tack, depending on the formulation.
Acrylate solutions and dispersions, as well as hot-melt contact adhesives, meet the
usual demands.
The peel strength (adhesion) is a measure of the separating force necessary to peel a
label or tape off from the surface to which it was applied. The term describes the
strength of adhesion or grab to a surface. Acrylate compositions require a few
hours before achieving full adhesion. Rubber adhesives and hot-melt contact adhesives exhibit high peel values after only a relatively short contact time.
The shear strength (cohesion) is the ability of a pressure sensitive adhesive to withstand applied forces or loads. Good shear strength is required when labels are stuck
to curved surfaces and for processing purposes, i.e. die-cuttability, slitting and to
minimize edge-ooze of roll products. When assessing shear strength, a distinction
must be made between the performance at room temperature and at elevated temperatures. Pressure sensitive adhesives designed having adequate room temperature
shear strengths should also be formulated to resist failure at higher service temperatures. While acrylic dispersions exhibit only a slight change in shear strength at elevated temperatures (due to internal gel structure), hot-melt adhesives tend to soften
and the shear strength drops significantly.
Depending on the use, different requirements are made of pressure sensitive adhesives with respect to adhesion and cohesion (Fig. 8-13).
adhesion
permanent
labels
packaging
tapes
removable
labels
protective
films
cohesion
Fig. 8-13
Adhesion level of self-adhesive articles.
A protective film must be removable without leaving a residue, i.e. must have very
low adhesion, even after long bonding times, in conjunction with high cohesive
strength. By contrast, a packaging tape must stick immediately and durably, i.e.
must have both very high adhesion, even after brief contact, and high cohesion. In
paper labels for permanent bonding, high adhesion is needed in order to ensure rapid bonding to the various surfaces, while the cohesion need only be sufficiently high
to avoid formation of adhesive filaments during label stamping and stripping operations. Removable labels have low adhesion and sufficient cohesion for removal.
Numerous methods are available for quantifying these different property profiles.
For better comparison of the properties of pressure sensitive adhesives, standardized
test methods have been developed by various organizations, including:
FINAT Fdration Internationale des Fabricants et Transformateurs dAdhsifs
et Thermocollants sur Papiers et autres Supports
PSTC Pressure Sensitive Tape Council.
These and other PSA test methods were compared in a review article by R.P.
Muny [43]. One common feature of these established test methods is that they are all
destructive measurements. In the first phase of the test, a bond is formed on contact
of pressure sensitive adhesive with the substrate. Initially, depending on the applied
pressure, only individual, small points of adhesion form, whose number and size increase during the contact phase due to elastic deformation, viscous flow and wetting
of the substrate with the adhesive. Contact formation is, therefore, determined by
mechanical behavior and surface properties, such as surface tension, roughness, and
adsorbate layers. Other important influencing factors are contact time, contact pressure and temperature. During the second phase, the bond is separated under the action of a tensile force, with the bond being deformed. Both processes, i.e. contact formation and separation, are influenced by the test conditions, which are different in
each measurement method [27, 30, 44].
It is conceivable to carry out nondestructive measurement of an adhesive joint using nuclear magnetic resonance methods (NMR imaging). However, such methods
are still under development [45].
Peel strength
The most common adhesion test is peel strength testing [27], in which the force
which occurs on peeling the adhesive layer off from a substrate is measured.
Conditioned test strips with a certain width are rolled on to test panels using a
roller with a defined weight. Stainless steel with a surface of defined roughness is
used in method PSTC-1 while glass is employed in the FINAT method. But in both
cases, after a certain dwell or bonding time, the peel measurement is carried out in a
mechanical testing machine at constant peel rate and at a peel angle of either 180 as
in Fig. 8-14, or alternatively at 90. There are various standards for the peel strength
test which differ essentially through the type of cleaning of the test panels and the
bonding times. For example, the bonding time is a maximum of 1 min in the PSTC
test, and 20 min and 24 h in the FINAT method. Since the dwell time has a significant effect on the level of adhesion, different values are obtained by the two methods
mentioned [27].
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212
clamp
support substrate (paper, film)
test substrate
(steel, glass,
polyolefin)
adhesive
method
A.F.E.R.A. 4001
PSTC-1
dwell time
max. 10 min
max. 1 min
FINAT
20 min
24 h
clamp
Fig. 8-14
Peel strength at 180 [27].
Even after a bonding time of 1 h, the wetting process is not complete in all cases
(Fig. 8-15). Besides the immediate value, a measurement is therefore often taken after, for example, a bonding time of 24 h, corresponding to FINAT test method 1 [27].
Besides numerous other authors [4649], the main contributor to understanding
of the very complex peel mechanism in self-adhesive tapes is Kaelble [50, 51]. He has
shown that the peel strength is dependent on the moduli of elasticity and the thicknesses of both the adhesive and the support, on the peel angle, and the interaction
forces at the adhesive-substrate interface [27]. Peel strength also depends on temperature and peel rate. At a given temperature, the peel strength increases with increasing peel rate. At low peel rates the viscous properties are dominant, polymer moledwell time
10 min
4,0
30 min
4,6
1h
5,3
3h
5,5
24 h
8,0
Fig. 8-15 Peel strength of an acrylic pressure sensitive adhesive depending on the dwell time, according to W. Druschke [27].
cules have time to slide past one another, to disentangle and to dissipate energy. At
high peel rates the elastic properties of the polymer network predominate, the polymer molecules are not able to disentangle, and so the polymer modulus or stiffness increases. Since the mobility of polymer chains increase with increasing temperature, the peel strength will decrease as well at a constant peel rate [52].
Tack
Tack is defined as the limiting value of the adhesion as the contact time approaches
zero. Targets for tack measurements are shortest possible contact time and lowest
possible contact pressure. With this aim, a number of methods have been developed [53, 54]. The best known tack measurement methods are quick-stick, probe
tack, Zosel tack and rolling ball [27]. All these methods are ultimately a refinement of
the subjective finger test, which still plays significant role in forming a qualitative
practical opinion [27].
In the quick-stick method corresponding to FINAT test method No. 9, a test strip
is formed into a loop, brought into contact with a glass plate and then immediately
peeled off again, as shown in Fig. 8-16.
clamp
support substrate
adhesive
clamp
support substrate
adhesive
test plate
(steel, glass, polyolefin)
Fig. 8-16
Quick-stick tack measurement [27].
This FINAT method differs from the PSTC (PSTC-5) quick-stick method, in which
peeling is carried out at an angle of 90 without formation of a loop [55]. The Tag and
Label Manufacturers Institute (TLMI, Iowa City, IA 319-337-8247) specifies a loop
tack test and within their manual, includes a host of useful TAPPI and ASTM methods for testing paper and plastic film substrates used in pressure sensitive labels, respectively.
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214
The advantage of the quick-stick methods compared with other tack measurement
methods is that the test can be carried out in any mechanical test machine with only
minimal contact pressures. Disadvantages of the method include a relatively long
contact time, different contact times within a test area and different contact areas.
Moreover, the peel angle is not constant in the FINAT method.
A widespread tack measurement method is the probe tack method proposed by
Wetzel [56] and refined by Hammond [57]. In this method, known as the Polyken
probe tack method (Fig. 8-17), a cylindrical ram with a diameter of 0.5 cm is pressed
from below against the adhesive layer at a defined pressure and speed and removed
again at a defined speed after a certain contact time (see ASTM D2979-71).
substrate
adhesive
weight
weight
support
support
piston
Fig. 8-17
Polyken Probe Tack method [27].
Contact times in the region of 0.1 s are possible using this method. The fact that
the measurements can be carried out simply and quickly and the conditions varied
easily and widely is advantageous. However, a very complex instrument is necessary.
In addition, the very small ram contact area of only 0.2 cm2 means that only small areas of the adhesive layer are measured. Air inclusions in the adhesive layer can result
in incomplete wetting of the piston surface [27].
An instrument developed at BASF by A. Zosel [3031] for fundamental studies [5863] on the theory of adhesion operates on a similar principle to the probe tack
method (Fig. 8-18).
The polymer to be tested is applied to a flat steel plate in a defined layer thickness
and dried. With the aid of an electric motor, the sample platform within the test
chamber is moved against the piston and then away again in the opposite direction
after contact. The shortest contact time that can be set is 0.01 s. The piston is connected to a piezoelectric force transducer. Variable parameters are the piston area,
contact force, contact time and approach speed of the tack experiment. The instrument allows measurements from 50 C to 200 C. This method also allows basic
studies with variation of other key parameters, such as separation speed, surface tension of the test piston, and composition of the adhesive layer [64, 65].
force transducer
rod
test chamber
sample
steel support
electrical motor raises

and lowers test chamber
Fig. 8-18
Zosel tack measurement.
For adhesive layers whose tack is not too low, the rolling ball tack method may be
used [66]. In accordance with PSTC-6, a steel ball of defined diameter is rolled down
an inclined plane at a certain tilt angle on to the adhesive test strip, as shown in
Fig. 8-19. The distance traveled before the ball stops is a measure of the tack.
Fig. 8-19 Rolling ball

method [27].
In contrast to the other tack measurement methods mentioned above, the rolling
ball test requires simple equipment and is easy to carry out. The main difference to
the other tack measurement methods is the fact that the rolling ball method does not
measure force. The meaningfulness of the method is also impaired by the following
characteristics:
The surface of the ball can change its nature even during the first rotation, because
of transfer of traces of adhesive ball contamination.
The adhesive values are relatively dependent on the viscosity and on the thickness
of the adhesive layer [27].
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216
Reproducibility of adhesion measurements

Figure 8-20 shows a statistical evaluation of tests on a commercially available adhesive tape.
Test
Number
of samples
Mean
Standard
deviation
Coefficient of
variation (%)
Peel strength after 10 min

Peel strength after 24 h
Quick-stick
Sample tack
Zosel tack
Rolling ball tack
25
42
50
43
25
50
3.8 N/2 cm
9.3 N/2 cm
10.2 N/2 cm
11.3 N cm12
13.9 J m2
3.9 cm
0.31 N/2 cm
0.54 N/2 cm
0.34 N/2 cm
1.24 N cm12
4.67 J m2
1.46 cm
8
5
3
11
34
38
Fig. 8-20
Statistical evaluation of the test results [27].
The scatter in the values after exclusion of outliers is 338 % of the mean, depending on the test. Apart from the very low scatter in the quick-stick method, the scatter
is lower for methods with longer contact times. Prerequisites for such results are
very uniformly defined test specimens and exact compliance with defined test conditions [27].
Shear strength
The cohesive properties of a pressure sensitive adhesive are generally determined by
measuring the shear strength.
Corresponding to FINAT test method No. 8, the shear strength is the time required for a certain area (25 mm 25 mm) of a self-adhesive material to slide off a
standard surface in the parallel direction to the surface with a load of 1 kg (Fig. 8-21).
The standard surface used is glass. In PSTC-7, a 12.5 12.5 mm adhesive contact
area on corrugated or stainless steel is subjected to a 1 kg load and the time to adhesive failure is recorded.
Fig. 8-21 Shear strength

measurement.
8.3 Laminating Adhesives
8.3
Laminating Adhesives
Laminating adhesives are used to permanently bond various types of substrate webs
together in industrial manufacturing processes. The term lamination has gained
general acceptance for this industrial process. These multi-layer laminated products
are generally known as laminates and can consist of three, and in many cases more,
distinct layers in the total construction. Depending on the sector of industry and
product class, a distinction is made below between film-to-film lamination for flexible packaging, glossy film lamination and technical lamination applications such as
furniture assembly.
8.3.1
Flexible Packaging
The process of laminating single-layer web materials to give flexible multilayer film
structures has been an established method for many years. Alternate production
techniques include extrusion coating and co-extrusion, where plastics are melted
and extruded in thin layers through an extrusion die.
A wide variety of flexible laminates can be produced on fast, high-performance
laminating machines using suitable adhesives. Materials with specific properties are
utilized in each layer which altogether impart the performance attributes needed for
the particular application. The multilayer film for vacuum-packed coffee, for example, consists of polyethylene so that the pack is heat-sealable, an aluminum foil layer
for aroma retention and light barrier, and a polyester film for mechanical strength
and good printability. Multilayer structures are widely used in packaging of foods,
such as cheeses, snack foods (potato chips), bacon, juice pouches and boil-in-bag
meals where oxygen barrier, water and heat resistance, and oil or fat barrier characteristics are required.
Common laminating adhesives include solvent containing and solvent free,
crosslinking polyurethanes, and two-component, water-based polyurethanes the
latter have been increasing in importance in recent years because of environmental
pressures. The choice of adhesive depends on the type of film to be bonded and on
the end use application. In food packaging, for example, food regulations and the resistance of the adhesive (e.g. to boiling water) are also important.
Polymer dispersions
The prime advantage of aqueous polyurethane and polyacrylate dispersions over solvent-containing systems is that recovery or disposal of significant amounts of solvent
is unnecessary. In the packaging industry, potential for residual solvent traces in the
adhesive and subsequent migration into food are also major concerns. Therefore,
solvent-containing adhesives have already been replaced by environmentally friendly
water-borne adhesives in a number of applications.
Film laminates are produced by coating adhesive on to one side of the primary
film, drying, and then laminating a second film on to the dried adhesive layer under
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218
heat and pressure. Multiple layer structures are typically built up by applying further
adhesive and film layers at subsequent coating and laminating stations. Application
rates between 1 and 3.5 g dry adhesive m2 are typical, depending on the film or web
type the adhesive used. Adhesive purchases into flexible packaging applications (including paper and plastic laminates) totaled in USA approximately 150 million dollars in 1997 [67].
In low-performance laminates, dispersions are employed as the only adhesive
component. If additional boiling resistance or sterilization capability is required,
from 3 to 5 % of a suitable curing agent should be added e.g., water-dispersible
polyisocyanates. The water-dispersible polyisocyanate does not just act as crosslinking agent yielding increased heat resistance, but also significantly increases adhesion to most films [68]. Figure 8-22 shows the reaction of a trifunctional polyisocyanate with an acrylate polymer and the OH groups of a corona-pretreated film.
Fig. 8-22 Reaction of a two-component aqueous lamination adhesive

(acrylate dispersion + water-dispersible triisocyanate) with corona-pretreated films.
Addition of curative of this type results in a significant increase in adhesive

strength; however, covalent reaction occurs to a small extent owing to steric factors.
The majority of the adhesion increase is attributable to the formation of hydrogen
bonds predominantly formed between OH and NH groups and polar groups of the
individual substrate.
A mixture of polymer dispersion and polyisocyanate has a maximum processing
time of about 57 h. If this time is exceeded, the laminate adhesion and hence peel
strength drops. Additionally, pH must be maintained between 3 and 4, higher pH result in shorter pot-lives.
Polyurethane dispersions adhere strongly to a broad range of corona-pretreated
plastic films. Achievable adhesion levels with PU dispersions are in many cases
higher than with acrylates. As mentioned above, PU can be crosslinked for use in
higher-end applications, or used alone to produce medium-performance laminates.

In either case, low initial green-strengths after forming the laminate bond are common. Moreover, it can take as many as seven days to achieve final laminate peel
strengths (by chemical reaction of isocyanates with hydroxyl groups), making it necessary to store laminate rolls temporarily prior to downstream converting.
A specially designed high performance acrylic dispersion that does not require addition of crosslinking agent and which yields excellent green strengths has been developed [69]. Due to the rapid development of peel strengths, laminates can be used
immediately after production thus, eliminating the need for inventory storage.
Moreover, adhesive pot-life issues are eliminated because of the absence of a reactive
second component.
Guiding formulation
Two-component polyurethane laminating adhesive
Wet parts
Dispersion
Crosslinking agent
Polyurethane dispersion (40 %) anionically

stabilized
Water-dispersible, aliphatic
polyisocyanate, NCO content approximately 18 %
100
35
Test methods
With film laminates made by adhesive bonding, the aim is to form the strongest possible laminate, thus, peel strength (i.e. laminate adhesion) is typically measured. The
test is usually carried out with 15 mm wide test strips where the film layers are
peeled apart using a tensile tester. The peel strength is specified in N/15 mm. The
test report should furthermore indicate the failure mode; possibilities include film
tear, cohesive failure, and adhesive failure to either of the film surfaces involved (including printed layers). The peel strength in the region of a heat-sealed seam is
known as the seal seam strength.
8.3.2
Glossy Film Lamination
Glossy film lamination involves the covering of printed paper or board products with
an optically clear, high-gloss plastic film. The process improves the brightness of the
printing inks and protects the printed material from external influences (e.g. scratching, bleaching and moisture). Examples include book covers, advertising and packaging materials. Other methods besides film lamination are used to finish print
products, including both physically and chemically cured coating systems. Glossy
film lamination is used to a large extent in Europe but in North America, a special
form of film lamination, predominates, called thermo-lamination [70]. In thermolamination, oriented polypropylene (OPP) films with a pre-applied heat-sealable adhesive layer are thermally bonded to the substrate, therefore, eliminating the need
for additional adhesive.
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220
High-gloss film laminates have been available in Europe since the 1960s. Lamination is frequently still carried out using solvent-containing adhesives. Embossable
paper board laminates were only made possible by high adhesion, two-part solventcontaining polyurethanes with crosslinking agents. However, the limited pot lives of
two-component systems require increased care from the processor.
Efforts to eliminate solvents to comply with more stringent emission regulations
likewise here resulted in the use of aqueous polymer dispersions. One-component,
self-crosslinking dispersions with shelf lives equal to those of standard polymer dispersions were developed, solving the pot life problem.
Wetting and flow of the adhesive on the film are the main prerequisites for high
clarity lamination. This requires the polymer dispersion adhesive layer to be as plastic and film-forming as possible during the lamination process. However, such adhesive films would then be too soft and would result in partial separation between
film and board during subsequent bending and embossing operations. A considerable advance was made, however, with the development of aqueous acrylate-based
polymer dispersions which crosslink after evaporation of the water, after the film has
formed. Crosslinking takes place at room temperature using a reactive ketone-dihydrazide chemistry designed into the polymer dispersion (Fig. 8-23).
Fig. 8-23
Chemical crosslinking reaction of a one-component acrylic adhesive.
The polymer particles contain co-polymerized carbonyl groups which, on film formation, react with hydrazide groups of the water-soluble acid dihydrazide to form
hydrazone. Increased cohesion strength results due to both inter-particle and intraparticle crosslinking reactions. A similar process also occurs between corona-pretreated polypropylene film and the emulsion adhesive thereby significantly increas-

Fig. 8-24 Infrared
spectrum of polyethylene films, according
to W.-D. Domke and
H. Steinke [71].
absorption
0,8
C=O
COOH
0,6
0,4
corona treated PE film

unteated PE film
(according to W.-D. Domke u. H. Steinke)
0,2
1900
1800
1700
1600
1500
wave number in cm-1
ing the adhesion strength of the laminate. As shown in the IR spectra for the PE films
in Fig. 8-24, additional carbonyl and carboxyl groups are observed on the film surface
after pretreatment [71], which can then react with the dihydrazide crosslinking agent.
The measurement of peel strengths after drying shows that significant crosslinking occurs after only approximately 2 h and is complete after about 48 h. In practice,
this means that bending and embossing of freshly produced board laminates should
only be carried out after this time period, in order to maintain film-to-film bonding [72].
Test methods
Drying
The progress of crosslinking over time can be recorded by measuring the surface
tack. This can be carried out using the Zosel tack measurement tester described in
Sect. 8.2.3 (Fig. 8-18). This enables measurement of the separation work of adhesive
layers throughout the course of drying.
Resistance to Delamination
After allowing sufficient crosslinking time, the lamination is formed, embossed and
evaluated after certain time intervals. Formed and embossed laminates are classified
as failures if the film is observed to have delaminated in the high-stress zones, as
evidenced by pale strips or spots in the otherwise high-gloss, if possible dark, lamination.
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222
Yellowing
High-quality, durable laminates are expected to maintain print color and gloss levels
even after prolonged light exposure. In addition to adhesive, the behavior of the top
film layer and underlying paper and printing should also be evaluated by including
appropriate control samples light exposure tests. Accelerated tests can be carried out,
for example, using a Q-UV type exposure instrument with a radiation spectrum and
intensity matched to that of natural sunlight. One-component acrylic adhesives perform very well in this respect, while conventional solvent-containing two-component
polyurethane adhesives yellow after a relatively short exposure time.
Gloss
No reliable test methods for measuring the surface gloss of film laminates have, so
far, been established. As such, the assessment of surface film gloss is best carried
out visually. Evident graying is an indication of tiny air bubbles between board and
film. These may be caused by inadequate application of adhesives, insufficient drying, or coalescence of the adhesive during lamination. Optical microscopy has also
proven useful in confirming defect types in laminates.
8.3.3
Furniture and Automotive
Solvent based, hot-melt, and water-based dispersion adhesives are typically used in
producing technical laminates for the furniture and automotive industries. The market share for aqueous dispersions is about 40 %. The main products are heat-activatable polyurethane dispersions, which provide excellent adhesion and extremely
high bond strengths to a range of substrates. Important applications are furniture
lamination (lamination of medium density fiberboard to decorative sheeting) and
the lamination of moldings for interior automotive parts (e.g. dashboards, door interior panels) [73]. In North America, the total automotive adhesive market is estimated to be roughly $ 200 million (in 1997) [74].
Polyurethane dispersions are secondary dispersions typically produced by polymerization of isocyanates and diols in organic solvent. After polymerization water is
added followed by solvent removal. The polyesterpolyol component can be designed
to form crystalline structures (Fig. 8-25), which make a significant contribution to
the internal strength.
The cohesive polyester-polyol crystals of commercially available PU adhesives melt
at about 50 C the lamination adhesive is thermally activated and becomes soft and
capable of heat-sealing (Fig. 8-26). During cooling, the polyesterpolyol segments recrystallize, resulting in a rapid increase in the internal strength of the adhesive film.
This effect is utilized in furniture lamination, in which the polyurethane dispersion is usually mixed with a reactive crosslinking agent. The polyurethane adhesive
is applied using a spray gun. After the adhesive has dried, a blocking-resistant film
forms, and the fiberboard elements can be stacked. They are then pressed with the
decorative sheet at 6080 C, for example in a membrane press. On cooling, recrystallization produces a rapid increase in strength. This is necessary to counter the re-
Fig. 8-25
Crystalline structures of a polyurethane adhesive.
Fig. 8-26
Differential heat flow measurement of a water-borne PU adhesive.
covery forces in the thermoformed decorative sheet which are effective in the first
minutes after pressing. The increase in cohesion due to the crosslinking reaction of
water-dispersible isocyanate is, by contrast, a slower process, with the final strength
only being achieved after days.
The reversible melting of the polyester-polyol segments is the physical basis for
the thermal activation ability. The possibility of heat activation is a very important ad-
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224
vantage of polyurethane adhesives. It is also an example of switchable properties of

polymers, where heat is the switch.
Formulation modifications
The addition of suitable resin dispersions and small amounts of plasticizer enables
the thermal activation temperature to be reduced, although this also results in a reduction in heat resistance. In contrast, the addition of crosslinking agents improves
adhesion and water resistance and increases the heat resistance. The crosslinking
agents used are water-dispersible triisocyanates, carbodiimides and polyaziridines.
The reactivity of the crosslinking agents is reduced by various methods so that an adequate processing time is available. Mixing with other acrylic dispersions allows the
properties to be modified and the costs of the adhesive to be reduced.
Guiding formulation
Two-component polyurethane dispersion for furniture lamination
Dispersion
Crosslinking agent
Luphen D 200 A, 40 %,* or Dispercoll U 53

Water-dispersible polyisocyanate
Wet parts
100
5
Suppliers: *BASF AG, Ludwigshafen, Germany; Bayer AG, Leverkusen, Germany
Test methods
The static peel strength of the laminate made from PVC furniture sheet and MDF is
assessed visually for delamination after storage at elevated temperature.
8.4
Construction adhesives
8.4.1
Floor-covering Adhesives
The term floor-covering adhesives denotes all materials for laying flexible floor-coverings. These include secondary and unitary backed carpets, felt backed vinyl, vinyl
composition tile (VCT), homogeneous vinyl sheet, rubber, and various vinyl and
polyurethane backed carpet tile products. Rigid coverings, such as natural stone, ceramic and parquet, are not included here.
The main driving force for the development of modern floor-covering adhesives is
the need for reduced volatile organic content (VOC). Though there are regional differences, reducing emissions of organic solvents is a worldwide consumer driven
trend based on environmental and health concerns (sick building syndrome).
In Europe at the beginning of the 1960s, flexible floor-coverings (such as linoleum)
were bonded using alcohol-soluble resin adhesives. However, these were unsuitable
for the new PVC floor-coverings on the market, for which solvent-containing polychloroprene adhesives consisting of 75 % of organic solvents and 25 % of polychloroprene and resins were used. These contact adhesives had to be applied to both
8.4 Construction adhesives
sides, i.e. to the back of the floor-covering and to the floor. A precise laying technique
was vital as the floor-coverings, which were laid after the solvent had evaporated,
could not be corrected once laid. This technique was soon also used for bonding
high-quality carpeting.
A severe disadvantage of contact adhesives with a solvent content of 50 to 70 % was
the emission of large amounts of solvents. Poor ventilation and the presence of an
ignition source resulted in explosions, burns and even fatalities.
The first polyacrylate dispersion for the production of aqueous floor-covering adhesives became available in Europe in the mid 1960s. The adhesive consisted of
40 parts of Acronal 80 D (50 %), 40 parts of chalk and to improve the wet tack
20 parts of balsam resin solution (70 % in toluene). The solvent content was only
6 %, and the bond strengths which could be achieved for PVC floor-coverings corresponded to the level of polychloroprene contact adhesives. In addition to significantly reducing the risk of accident, further advantages of the new type of adhesive were:
application of adhesive to one side only
the floor-coverings could be corrected
good aging resistance
fresh adhesive residues could be removed from the floor-covering and tools using
water
Solvent based polychloroprene adhesives have a different setting mechanism
compared to water based flooring adhesives. Polychloroprene adhesives develop
their bond strength through recrystallization of the elastomer from solution. In the
case of emulsion adhesives, the polymer particles are initially swollen by the resin
solution. During evaporation of the water, a film-formation phase occurs in which
the polymer film, due to the residual solvent, has particularly high tack and low
cohesion. The final strength is then achieved by two processes occurring in parallel:
Firstly, post-flow of the polymers on to the substrate surfaces results in an increased contact area and consequently in an increase in adhesive strength; secondly,
evaporation of the residual solvent and recrystallization of the small and rigid abietic
acid molecules increase the cohesion of the polymer film to its final strength.
At the beginning of the 1970s, rapid growth commenced for back-coated textile
floor-coverings, which were also bonded using one-side adhesives. At the end of the
1980s, solvent-free floor-covering adhesives were produced for the first time with
Acronal A 323 in combination with a plasticizer. In these, the tackifying resin solution was replaced by a resin melt. Adhesives formulated in this way have proven adhesive properties and are solvent-free substitutes as defined in the Technical Rules
for Hazardous Materials, TRGS 610 [75].
The next generation of floor-covering adhesives was developed in 1994. In these,
solvents, plasticizers and resins were deliberately omitted. Although plasticizers are
not solvents in the sense of TRGS 610, they are nevertheless low-molecular-weight
substances with a certain vapor pressure and are consequently a source of emissions.
Resins were omitted because the usual abietic acid derivatives are odor carriers. The
absence of the action of these two proven starting materials was compensated by a
larger proportion of the softer and tackier acrylate dispersion Acronal A 200 or Primal CA-187 (see guide formulation 2) [76].
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226
The adhesive formulated in this way has very low emissions as defined in the requirements published by the Association of Emission-Controlled Laying Materials
(Gemeinschaft Emissionskontrollierter Verlegewerkstoffe, founded in Germany) at
the beginning of 1997. These requirements have no legal foundation, but are based
on a voluntary self-commitment by the member companies for processor and consumer protection. The emissions are measured using a chamber test method (see
Test Methods), which enables firstly, volatile carcinogenic (suspected or proven) constituents to be identified and measured after 24 h (processor protection) and secondly, the long-term total emissions of volatile organic compounds (TVOC) to be determined after 240 h (consumer protection). Corresponding to the TVOC after 240 h,
three emission classes are defined: EC 1 very low emissions (TVOC <500 g m3),
EC 2 low emissions (500 to 1500 g m3) and EC 3 not low emissions (TVOC
>1500 g m3). For all classes the maximum emission of carcinogenic compounds
after 24 hours has to be less than 10 g m3.
In North America reductions in solvent levels in floor-covering adhesives have
been essentially driven by environmental and VOC concerns. In March 2001, the
California South Coast Air Quality Management District (SCAQMD) approved a proposal, Rule 1168, to reduce solvent levels, specifically non-exempt VOC, in floor-covering adhesives from approximately 150200 g L1 to approximately 5070 g L1. Other state agencies are expected to implement similar solvent and VOC criteria in years
to come. These regulatory changes necessitate a further shift from solvent-rich adhesive systems towards water-based adhesive technology.
Total North American carpet consumption in 1999 was approximately 1.6 billion
square meters, split between two main sectors, residential (75 %) and commercial
(25 %). Residential carpets are typically installed using glue-less installation techniques (e.g. tack-strip). However, carpets in commercial installations including
schools, retail establishments, hospitals, workplaces and hospitality facilities are installed employing specially designed or multipurpose adhesive systems. These adhesives are typically formulated employing non-carboxylated, high-solids, styrene-butadiene lattices (SBR HSL), hydrocarbon resin-oil blends, and fillers as the primary
components. In the past, such adhesives were formulated with resin solutions based
on hydrocarbon solvents (e.g. mineral spirits) and/or plasticizers. Environmental
pressures led to near elimination of solvents and plasticizers in the 1990s and introduction of increasingly lower VOC adhesives made with increasingly higher viscosity naphthenic oils.
Flooring mastics based on non-carboxylated SBR HSL are employed primarily in
carpet and mineral fiber or felt-backed vinyl glue-down applications over most common sub-floor surfaces. Such SBR based adhesives are not recommended for unbacked vinyl (PVC) applications due to plasticizer migration from PVC to the adhesive and bond loss issues. Conventional felt backings provide an effective barrier to
plasticizer migration. In contrast, acrylic copolymer based floor-covering adhesives are
employed in direct vinyl contact applications where plasticizer resistance is required.
The main constituents of the SBR HSL based flooring adhesive are the resinoil
blend, surfactant, latex and filler (see guiding formulation 1). Carefully selected
resinoil systems are employed for both cost and property reasons (early wet tack
development, legging or webbing, initial or green strength, final bond strength,

aging resistance and low VOC). Webbing and bond strength are also sensitive to formulation latex content, typically in the order of 1015 %. The rosin acid and non-ionic surfactants in this formulation serve to stabilize the oil in water emulsion during
compounding and to provide end-product in-can stability. Urea can be employed to
achieve freeze-thaw resistance (low molecular weight alcohols and/or glycols can
also be considered). Caustic solution (e.g. 20 % KOH) is added to neutralize the rosin
acid and to achieve sufficiently high pH so that when the non-carboxylated HSL is
added, pH shocking effects with coagulation are avoided. Clay is added for reinforcement purposes and for costperformance optimization. Alkali sensitive emulsions
(e.g. Latekoll D) are added for thickening purposes.
The key parameters to control are formulation water content, clay/latex ratio and
resin/latex ratio, depending on the desired adhesive cost structure. Not surprisingly,
too much filler or too little resin and/or oil will result in inferior properties. Excess
water will result in slower drying, and probably the need for more water sensitive
thickeners. Like many other SBR based adhesives, HSL based flooring mastics include in-can and dry-film preservatives as well as an antioxidant package to ensure
long-term performance.
The total volatile organic content (TVOC) is a key property of floor-covering adhesives. In the mid 1990s, the Carpet and Rug Institute (CRI) introduced a voluntary
TVOC specification for floor-covering adhesives, defined as the Green Label Program in North America. The method employs a small chamber test apparatus
described in ASTM D-5116. For CRI Green Label certification, 24-h emission rates
from adhesives must be <10 mg m2 h1 for TVOC, <3 mg m2 h1 of 2-ethylhexyl
alcohol, and <0.05 mg m2 h1 for formaldehyde. TVOC and formaldehyde are
quantitated employing thermal desorption GCMS and HPLC techniques, respectively.
In North America, formulation technology based on high solids content styrene
butadiene lattices and naphthenic oils are widely used in the market place. Low
TVOC products have evolved to meet the CRI Green Label requirements and to provide cost-effective, high performance adhesives for carpet and felt-back vinyl floorcoverings.
Floor-covering adhesives made from water-based polymer emulsions contain approximately 1020 % dry polymer in both European and North American systems.
Floor-coverings are bonded using an application rate of about 250500 g m2.
1. High solids content styrene butadiene (HSL) and naphthenic oil based flooring
adhesive for carpet and felt backed vinyl floor-coverings with emissions satisfying
CRI Green Label TVOC requirements. Such adhesives are not recommended for
homogeneous or solid vinyl sheet goods where plasticizer migration is a concern.
227
228
Wet parts
9.7
Hydrocarbon resin Neville LX 1200*
Rosin acid
Melhi
2.2
12.0
Naphthenic oil
Tufflo 1200
0.2
Surfactant
Igepal CO-897 (70 %)
Surfactant
Igepal CO-530
0.1
Anti freeze
Urea (50 %)
1.4
Neutralizing agent Potassium hydroxide (2.5 %)
8.7
41.4
Filler
Huber 95 (70 % clay slurry)#
20.4
HSL dispersion
Butonal NS 104 (71 % s.c.)**
3.9
Thickener
Latekoll D (pH adjusted 8 % solution)**
Total
100
Procedure: Add resins to oil at 140150 C, stir until homogeneous, then cool to
9598 C. Surfactant, urea and KOH solution are slowly added under mild agitation
to form an emulsion. The clay, SBR, and thickener are then added to the resin emulsion in the order indicated above.
2. Very low emissions corresponding to the requirements of the German association
of Emission-Controlled Laying Materials (GEV)
Wet parts
Dispersion
Acrylic dispersion
24.4
2.0
Plastiziser
Plastilit 3431**
0.2
Antifoam
Agitan 282
0.5
Dispersant
Pigment dispersant NL**
42.0
Chalk
Ulmer white XM
10.9
Thickener
Latekoll D 2 %**
Resin melt
Gum resin WW: Plastilit 3431 = 8:2
16.0
4.0
Resin
Poli melt 15
Total
100
Suppliers: *Neville Chemical Company, Pittsburgh, PA, USA; Hercules Incorporated, Wilmington,
DE, USA; Lyondell Lubricants, Houston, TX, USA; Rhone-Poulenc, Cranbury, NJ, USA;
#
J.M. Huber Corp., Wrens, GA, USA; **BASF, Charlotte, NC, USA; Ludwigshafen,
Germany; Mnzing Chemie, Heilbronn, Germany; Omya, Cologne, Germany;
Erbsloeh, Krefeld, Germany
Test methods
North American industry standard test methods for floor-covering adhesives are currently not available. However, methods are under development by ASTM committee
D14.70.12, Carpet Adhesives. As a guiding method for evaluating carpet to plywood
peel strength the adhesive is troweled on to plywood (application weight ca.
300 g m2), after 20 min the carpet or vinyl is laid and pressed down at room temperature, and, after a certain curing time at room temperature or 60 C, the floor-covering is peeled off at 90 angle using a tensile tester.
Drafts of European test standards for measuring peel and shear strengths of floor
and wall coverings were submitted for approvals in early 1999 by Technical Committee CEN/TC193. These methods, referred to as prEN 1372 and prEN 1373 respectively, are fundamentally quite similar to methods developed in Germany through a
collaboration between floor-covering manufacturers, official test institutes, and adhesive and raw material producers. German test standards and specifications for
peel and shear strength discussed below are summarized in DIN 16860 for PVC
floor-coverings and in DIN 53269 for textile floor-coverings.
Peel resistance
The peel resistance is the force, per unit width of floor-covering, which results when
peeling-off a bonded sample perpendicular to the original adhesive bond line. According to regional requirements, the adhesive is applied to plywood, cement board
or other substrate using a trowel spreader and, after a certain open or evaporation
time, a 5 cm 30 cm floor-covering strip is laid on to the adhesive bed and pressed
down, preferably using a fixed weight roller (e.g. 5 kg). After a storage time under defined standard laboratory conditions, the floor-covering strip is peeled perpendicular
to the adhesive join at a certain speed using a tensile testing machine (Fig. 8.27). The
peel forces which occur during this operation are measured and specified in
N mm1. According to DIN 16860, the average peel strength must have a certain
minimum value (e.g. 1 N mm1). Other factors such as early bond strength development, water resistance, and accelerated oven aging (e.g. 50 C) can also be evaluated
using variations of this general method.
Fig. 8-27
Measurement of peel resistance.
Shear strength
The shear strength is the force per unit area which results in fracture of bonded samples parallel to the bond joint. Adhesive areas of 1000 mm2 (ca. 2.5 cm 5 cm) are
produced on plywood or other cementitious substrates using a template and trowel,
then the floor-covering is laid on to the adhesive area and pressed down. After a storage time under standard laboratory conditions, the floor-covering is removed parallel
to the adhesive join at a defined speed using a tensile testing machine. The shear
229
230
forces which occur during this operation are measured and specified in N mm2 .
According to DIN 16860, the mean of the shear strength must have a certain minimum value (e.g. 0.3 N mm2) to be considered passing.
The curing of water-based adhesives is typically dependent on temperature and
humidity conditions. For this reason, it has proven useful in the development of water-based adhesives for carpets and other floor-coverings to also test peel strength as
a function of time. There are two additional test methods for this:
Green strength development
The 5 cm wide floor-covering strip is laid in the wet emulsion adhesive after a
1020 min drying time, and then pressed down. Floor-covering specimens are
peeled off at a certain speed perpendicular to the adhesive join after a further 10, 20,
30, and 60 min. The peel forces, which occur during this operation are measured and
specified in N/5 cm strip. Depending on drying conditions and adhesive composition, peel strengths on the order of 1015N/5 cm strip should be expected within
1530 min after applying the floor-covering strip. When peel testing SBR HSL based
mastics in particular, it is equally important to also report the degree of web or leg
development as a function of time. While not necessarily correlated with final adhesive bond strength, installers nevertheless commonly look for early web development as an indication of adhesive quality.
Open time
Open time represents the maximum recommended time after troweling that the
floor-covering should be laid into the adhesive. To quantify this parameter, a 5 cm
wide floor-covering specimen is placed in the partially dried emulsion adhesive after
30, 45, 60 and 90 min airing times and pressed down. The floor-covering is immediately peeled off at a certain speed perpendicular to the adhesive join. The peel forces,
which occur during this operation are measured and specified in N/5 cm. After exceeding the open time, unacceptably low peel strengths and poor adhesive grab on to
the floor-covering substrate are observed. As with green strength development, temperature and humidity conditions also have a significant impact on the open time actually found under installation conditions. Typically, longer open times and delayed
green strength development are expected at higher humidity and lower installation
temperatures (i.e. because of slower water evaporation from the adhesive itself).
These two methods have a reproducibility of 20 %.
Chamber method for emission measurement
North American CRI Green Label and European chamber TVOC methods for
flooring adhesives are fundamentally similar. In both cases, the adhesive sample is
applied to a stainless steel or glass plate and immediately sealed in a stainless-steel
test chamber carefully maintained under well defined temperature and humidity
conditions (e.g. 23 C, 50 % rel. humidity). VOC are collected onto adsorption tubes
containing suitable adsorbents after flowing purified air through the chamber at a
controlled rate. The CRI Green Label method requires volatile and formaldehyde
samples be collected at the 24 h point. However, the German Association of Emis-
sion-Controlled Laying Materials specifies that substances known or suspected of

being carcinogenic must be determined at the 24 h point (in accordance with
Hazardous Materials Regulation/TRGS 905), but also that long-term emissions be
determined after 10 days. After desorption, the emitted substances are determined
by gas chromatography (GC-MS coupling) or liquid chromatography. The long term
emissions are quantified using toluene as standard substance for volatile substances
in low concentration. Loading of the chamber should be at 0.4 m2 m3 and the air
exchange rate at 0.5 chamber volumes per hour (1.0 air exchanges per hour in the
ASTM protocol).
8.4.2
Sub-floor and Wall Mastics
Sub-floor and wall mastics are employed in a host of building and home construction applications. Sub-floor type mastics are typically used for fixing plywood subflooring to lumber floor joists and more recently applied to secure plywood roof
sheathing to roof rafters and trusses of existing roofs. In both of these applications,
nails are also used to hold the plywood in place, but the adhesive greatly augments
the structural strength. For example, in wind exposure tests [77], adhesives were
found to increase resistance to wind uplift forces by factors of 23 compared to traditional nail down methods, important for homes and buildings in areas prone to tornadoes and hurricanes. Plywood-lumber sub-floor mastics are employed in quality
construction systems to eliminate nail pops and floor squeaking. Improved mastic
systems are required which are compatible with commercial oriented strand boards
(OSB) used increasingly in place of standard plywood in both sub-floor and roofing
constructions.
Sub-floor mastics are generally supplied in cartridge form (310 cm3 and 860 cm3
tubes) and applied as a 6 mm bead using standard caulk gun applicators. Overall
market in North America for this class of adhesive is approximately $35 million
year1 with 3 % growth per annum. The market consists predominately of formulated solvent based styrenebutadiene polymers, moisture-cure polyurethanes, and
high performance water based acrylic systems. Increasing VOC concerns coupled
with lower solvent threshold limits in California [78] are driving the eventual movement to environmentally friendly, low VOC water-based mastics.
An estimated 75 % of the mastic products sold in North America indicate compliance to stringent AFG-01 (i.e. Adhesives for Field Gluing) requirements. ASTM D
3498 is quite similar to the AFG-01 standard originally written by the American Plywood Association. These methods define a series of six test specifications (Fig. 8-28),
five of which involve shearing plywood to lumber wood block specimens in compression mode after various carefully controlled material conditioning and specimen
curing protocols (Fig. 8-29).
The sixth test, called oxidation resistance, is a mandrel flexibility check on films of
dried mastic after exposure to oxygen at high temperature in an oxygen bomb apparatus. Water based mastics formulated with acrylics or styrene-acrylic polymer dispersions typically pass oxidation resistance requirements. The most challenging pa-
231
232

Fig. 8-28
Force
Plywood on lumber shear test
(AFG-01).
Adhesive
Bond Line
Plywood
Lumber
Conditioning
of materials
Assembly curing
Test specifications
Dry lumber
Wet lumber
48 h, 37 C/30 % rh
48 h soak lumber;
48 h, 37 C/90 rh
for Plywood
28 days, 37 C/30 % rh
28 days, 37 C/90 % rh
Shear >1000 N
Shear >1000 N
Frozen lumber
48 h soak lumber
48 h; 14 C for lumber
and plywood
5 days, 14 C
21 days, 4 C/50 % rh
7 days recovery
Shear >667 N
Moisture
resistance
48 h, standard
conditions
28 days, 22 C/50 % rh
3 cycles of 4 h H2O/o.n.
dry 37 C
7 day recovery
Shear >1000 N;
<10 % bond failure
Gap filling
48 h, standard
conditions
28 days, 22 C/50 % rh
(16 gauge wire)
Shear >667 N
3 days, 22 C/50 % rh;

2 days, 48 C/50 % rh;
500 h, 70 C/20bar O2
bend over 6 mm
Mandrel: no cracking
Oxidation
resistance
Fig. 8-29 Performance specifications for Adhesives for Field Gluing Plywood to
wood framing (AFG-01) rh relative humidity, o.v. over night, 1 N = 0.2248 lbf.
rameters to balance, however, involve moisture resistance and frozen lumber.

Frozen lumber adhesion is promoted through the use a combination of coalescents
and freeze-thaw aids (e.g. glycols, alcohols). Levels of such additives are kept to a
minimum in order maintain maximum resistance to moisture.
The wall mastic market in North America is roughly twice the size of the sub-floor
market mentioned above. Typical wall mastic applications include:
wood bonding to concrete walls and floors
bonding drywall or gypsum board and paneling to studs and framing structures
In concrete bonding applications, use of adhesives eliminate the need for time
consuming drilling operations and prevents damage to the concrete substrate. Drywall
adhesives are used increasingly as builders look for ways to replace time consuming
hammer and nail approaches [79]. Test specifications for drywall adhesives are described in ASTM C-557, Adhesives for Fastening Gypsum Wallboard to Wood Framing.
Like sub-floor mastics, wall mastics are also manufactured in solvent based,
polyurethane and water based formulations. Due to reduced strength requirements
(i.e. relatively low inherent strength of drywall), drywall mastics are typically filled to
a higher degree and thus, are less costly compared to AFG-01 sub-floor mastics.
Guiding formulation
Solvent-free plywood-lumber sub-floor adhesive
Wet parts
56.7
Dispersion
Acronal DS 2159*
0.1
Dispersant
Pigment disperser N*
Dispersant
Sodium tripolyphosphate
0.1
0.05
Defoamer
Nopco NXZ
3.6
Tackifier
Snowtack 301 A
Anti freeze
Ethylene glycol
3.0
2.3
Coalescent
Eastman DBA
11.4
Filler
Duramite
22.7
Filler
Clay
0.3
Thickener
Latekoll D*
Total
100
Ingredients are combined in the order indicated above at room temperature with
high-speed agitation.
Adhesive properties: 70 % solids content, pH 9, 40 % polymer on dry
AFG-01 testing:
Moisture resistance:
3100 N
(>1000 N required)
Frozen lumber:
880 N
(>667 N required)
Bond failure:
None
(<10 % required)
Suppliers: *BASF Corporation, Charlotte, NC, USA; Henkel, Ambler, PA, USA; Akzo Nobel,
Woodstock, CT, USA; Eastman Chemical Company, Kingsport, TN, USA; ECC International, Atlanta, GA, USA
8.4.3
Sealants
Sealants or caulks in accordance with ISO 6927 are materials which remain plastic or
elastic and are used for sealing a joint between two separate construction parts, thus,
eliminating passage of the elements through the joint (i.e. hot or cold air, moisture, insects). While a caulk needs only fulfill the above general purpose, sealants are
considered higher end products that must additionally perform after repeated extension-compression cycles originating from material temperature and humidity fluctuations. Historically, the starting point for sealants was the natural raw material linseed oil, mixed with chalk to give window putty.
233
234
Synthetic polymers suitable as binders for the production of caulks and sealants
include silicones, polyurethanes, polysulfides, and aqueous polymer emulsions. The
importance of these sealants in the construction industry has also increased considerably through the increased use of prefabricated elements. The movement of components must be absorbed and compensated by the joint sealant. These movements
can be expansion, contraction, or shear.
While silicones, polyurethanes and polysulfides set through a chemical reaction,
water based emulsion sealants achieve their functional end state by simple physical
drying, i.e. evaporation of the water. The majority of emulsion sealants are composed of acrylic emulsions and to a lesser extent vinylacrylic and other copolymers.
Polymer emulsion sealants can be used on all sorptive substrates, such as concrete, aerated concrete, cement panels, plaster and wood. They are used for sealing
all types of internal joints, connecting joints (internal and external) and expansion
joints (internal and external) with a movement capability of 1015 %. In Europe, the
joint design is stipulated in the relevant standards, for example DIN 18540.
The total caulk and sealant market in North America is estimated 500 000 tons of
formulated sealants [80], with acrylic emulsion sealants comprising approximately
15 % of the total market, and 23 000 tons dry acrylic resin. Water based sealants, sold
primarily in cartridge tubes, are used predominately in construction applications
whereas reactive urethanes and silicones are used in more demanding construction
and automotive applications.
Formulation ingredients
The properties of an emulsion caulk or sealant are affected by the type of emulsion,
and by the type and amount of the fillers and/or pigments, plasticizers and thickeners [81].
Fillers reinforce and increase the volume of the sealant. Fillers also reduce formulation costs and affect the technical properties of the sealant itself. Common fillers
for sealants are calcium carbonate (chalk), aluminum silicate (clay), barium sulfate
and silicic acids. Finely divided fillers, such as talc and Microdol 1, reduce the surface tack while simultaneously stiffening the film. Thixotropic fillers, for example
fumed silica or SiO2, improve the gunnability and reduce the sag of the compositions. Pigments are used to color sealants; the white pigment used is usually titanium dioxide.
Depending on the degree of compatibility, plasticizers and coalescents reduce
the glass transition temperature of the polymeric component and thereby enhance
low-temperature flexibility and film elongation. While improving formulation cost,
excessive plasticizer detrimentally affects film strength, tack and therefore, dirt pickup resistance. For the production of polymer emulsion sealants, phthalates, dibenzoates, polyisobutenes and Plastilit 3060 have proven successful. With Plastilit 3060
(propylene glycol alkylphenyl ether) as plasticizer, sealants with faster skin formation after application and lower Shore hardness which are particularly elastic at low
temperatures are obtained. Experimental testing to ensure long-term polymer-plasticizer compatibility and minimum tendency to volatilize or migrate to the exposed
surface is always recommended.
Dispersing aids and surfactants improve the incorporation of fillers and pigments
and improve the sealants storage stability. In general, low molecular weight polycarboxylic acid salts are used.
Silane-based coupling agents can be employed to improve adhesion to difficult
substrates (e.g. glass, aluminum). A new class of hydrolysis resistant silanes are now
available [82] which minimize self-crosslinking reactions, improve storage stability
and provide desired enhanced adhesion performance even after extended package
aging. Sealants containing small amounts of silane adhesion promoter are referred
to as siliconized.
Anionic thickeners based on polycarboxylic acids, associative thickeners and
fumed silica are used to adjust the rheological behavior of sealants. Highly disperse
fumed silica with a average particle diameter of from 10 to 30 m is used as
thixotropic agent to ensure that the sealant flows out of the cartridge well even under
gentle pressure, but has low sag after removal of the shear stress.
Addition of suitable antifreeze agents, for example ethylene glycol, protects the
sealants against freezing during storage and transport.
Both wet phase biocides and dry film preservatives should also be added to the
sealants produced using polymer dispersions in order to achieve adequate protection
against microbiological attack. The suitability of these preservatives must be established and monitored experimentally.
The mechanical properties of water-based sealants are essentially determined by
the ambient temperature and atmospheric humidity. Figure 8-30 shows the tensile
stress of a sealant at 50 % elongation as a function of time under various climatic
drying conditions.
Sealant types
Three types of water-based sealant are commercially available; clear, translucent, and
filled sealants. The majority of the market (>75 %) consists of the filled variety. Clear
and translucent sealants are used when a clear or translucent look is desired and in
applications requiring higher adhesion performance, elongation, and dried film
strength. While fillers serve to reduce formulation cost and surface tack, thus, dirt
pickup, they reduce adhesion performance and film elongation.
Clear and translucent sealants consist primarily of polymer dispersion (ca.
7595 % by weight) and various formulation auxiliaries such as plasticizers, defoamers, preservatives, thickeners, and freeze-thaw agents. Since fillers are not used,
formulation solids content is essentially defined by the solids content of the polymer
dispersion used, which for currently available materials, is typically <65 %. Higher
water contents promote slower sealant drying rates. Relatively hard acrylic copolymers (Tg = 10 to +10 C) are needed in clear sealants to minimize surface tack and
subsequent dirt pick-up. Translucent sealants are formulated similarly but with
small amounts of fumed silica thickener to adjust flow properties.
Filled sealants are typically formulated with approximately 2535 wet parts polymer dispersion per 100 parts total formula, with filler to binder ratios in the range
from 2 to 4. With high filler loads, formulation solids contents in the vicinity of 90 %
are possible. Because of the stiffening effect of most fillers, filled sealants are pro-
235
236
Fig. 8-30 Tensile stress values of a dispersion sealant at 50 % elongation

and various climatic influences, r.h. relative humidity.
duced either with lower Tg emulsion polymers (40 to 30 C) and low plasticizer levels or with higher Tg copolymers (<0 C) and higher levels plasticizers which soften
the dried sealant film.
1. Filled sealant with good elasticity (even at low temperatures) and a broad adhesion
spectrum
Wet parts
Dispersion
Acrylic dispersion, pH 8 with NaOH 20 %
31.5
2
Plasticizer
Plastilit 3060*
10
Pigment paste
Plastilit 3060/Kronos 2056 TiO2 (1:1)
0.2
Emulsifier
Lumiten N-OG*
0.1
Dispersant
Pigment dispersant N*
Omya BLP 3
55.5
Filler, CaCO3
0.7
Thixotropic agent
Silicic acid HDK H 20
Total
100
Sealant properties: filler/binder ratio = 2.71, solids content = 89 %
Polymer dispersion properties: 65 % solids, Tg = 30 C
2. High solids, rapid drying, low cost formulation for common gap filling applications; paintable
Wet parts
Dispersion
Acrylic dispersion
23.8
10
Plasticizer
Palatinol N, C-9 phthalate*
0.3
Surfactant
Emulphor OPS 25, non-ionic*
0.6
Dispersant
Pigment disperser N*
Filler
Mikrodol 1, CaCO3
61
Sealant properties: filler/binder ratio = 4.3, solids content = 90 %
Polymer dispersion properties: 60 % solids, Tg = 10 C
Suppliers: *BASF Corporation, Charlotte, NC, USA; Omya GmbH, 50968 Cologne, Germany;
Tipure R901-01 TiO2 also available from Dupont Chemical, Wilmington, DE, USA;
Wacker-Chemie, 81737 Munich, Germany; Aerosil 200 fumed silica also available from
Degussa Corporation, Ridgefield Park, NJ, USA.
Production of sealants
Vacuum planetary mixers have proven particularly successful for the production of
water-based polymer emulsion sealants.
The dispersion is adjusted to pH 8 using 20 % sodium hydroxide solution. Thickener and dispersant are then added, and the mixture is stirred briefly at low speed.
The plasticizer is then added directly.
It has proven favorable in experiments to grind finely divided pigments (for example titanium white and iron oxide black) with the same amount of plasticizer in a roll
mill and to incorporate the resultant pigment paste into the dispersion before the
fillers. This suppresses the formation of pigment particle agglomerates, which can
otherwise easily occur. After a stirring time of about 8 min at 3040 rpm, the fillers
are added in 3 or 4 portions; after each addition, the mixture is stirred for about
5 min until smooth. The speed is then gradually increased to about 80 rpm. After the
final addition of filler, the stirring arms are scraped and stirring is continued for a
further 5 min. The homogeneous mixture is then deaerated for about 5 min under a
vacuum of 900 mbar with stirring at 20 rpm and then packed into polyethylene or
foil carton cartridge tubes. A minimum shelf life of 6 months can be assumed in
properly sealed cartridges.
Test methods
Resistance to flow
The resistance to flow is the property of a sealant to remain in the specified shape
after processing. For testing, a U-profile is filled with sealant (EN 27390, DIN 52454,
ISO 7390, ASTM D-2202).
Elastic recovery
Elastic recovery is the magnitude of the recovery of a sealant after prior elongation
followed by release. For the measurement, two concrete test specimens are joined together, the joint is stretched by 50 %, and after 24 h the separation is measured after
release (EN 27389, DIN 52458, ISO 7389, ASTM C-736).
237
238
Adhesion-elongation test
Two concrete test specimens are joined together and pulled apart in a tensile testing
machine at 6 mm min1 until the breaking point is reached (DIN 52455, EN 28340,
ISO 8339, ASTM C-735).
The mechanical properties of a good emulsion-based sealant should be an elastic
recovery of 6070 %, a tensile stress of 0.10.15 N mm2 and an elongation at break
of 200300 %.
In North America ASTM C-834 and C-920 are used. These are actually umbrella
specifications constructed from a host of individual ASTM test methods [83]. In general, latex sealants are typically unsuitable for sealing joints which are constantly exposed to water or subjected to strong expansion movements. However, sealants can
be developed which satisfy the specifications defined in ASTM C-834 for latex sealing compounds. Higher performance elastomeric joint sealants based on silicone, polyurethane and advanced acrylic emulsion technologies are typically designed to satisfy the ASTM C-920 standard. ASTM C-920 class A sealants are those
that can withstand deformations as high as 50 % while class B sealants tolerate deformations as high as 25 %.
Notes for use
Water-based sealants generally adhere sufficiently well to sorptive substrates without
pre-coating. However, in order to achieve greater reliability, in particular to bind dust
particles, pre-coating of the joint edges with dilute sealant (for example 1 part of
sealant with 3 parts of water) has proven successful in practice.
The sealant is introduced into the joint using a manual or compressed-air caulking
gun. The surface is then smoothed using a wet flat brush.
Jointing should not be carried outside in the rain or at temperatures below +5 C
since the dispersion is still water-sensitive after application. Depending on the temperature and relative atmospheric humidity, it requires 3060 min to form a sufficiently thick skin on the surface. Tools should be cleaned with water immediately
after use as the residues can only be removed mechanically once they have dried.
8.4.4
Ceramic Tile Adhesives
In contrast to the traditional thick-bed method in which tiles are laid in thick layers
of mortar, the thin-bed method involves adhesive bonding. This means that the tiles
are laid into a wet adhesive bed trowel applied on to a substrate. The thickness of the
adhesive bed is variable and depends both on the size of the tiles and on the nature
of the tile undersurface. The greatest advantages of the thin-bed method are the high
application speeds and lower mortar coat or application weights (i.e. cost). However,
the thin-bed method can only be used if the substrate surface is relatively flat. This
prerequisite is achieved in most cases by using appropriate substrate preparation
techniques (e.g. cementitious self-leveling repair underlayments and floor patching
compounds) and industry proven construction materials, such as cementitious
backerboard, gypsum wallboard, underlayment grade plywood or prefabricated con-
crete panels. In thin-bed ceramic tile applications, both cementitious adhesives

(mortar) and non cementitious systems (mastics) are applied.
Ceramic tile mortar adhesives (thinsets)
Thinset mortars are employed in demanding interior and exterior floor and wall applications where there may be standing water or high moisture exposure. Both one
component polymer modified thinsets and two component cementitious adhesives
are used. Ethylene vinyl acetate copolymers (EVA) are the predominant powder polymer base used in one component polymer modified thinsets, they are described in
Chapter 13. Recently styrene acrylics or straight acrylics and styrene butadiene copolymer powders gain an increasing market share. Two component thinsets systems
combine a cementitious powder mix and a separate polymer dispersion admixture.
Polymer modification imparts a wide range of performance improvements to
ceramic tile mortar adhesives, including improved bond strength, water resistance,
flexibility, impact strength, freeze-thaw resistance, improved mix workability. Polymers also aid in promoting adhesion to difficult substrates such as plywood and vitreous tiles (porcelain).
Two component thinset adhesives employ acrylic, styrene-acrylic and SBR polymer emulsions in the admix component. The benefit of a styrene-acrylic polymer
compared to a straight acrylic backbone involves increased hydrophobicity, thus, improved moisture and alkali resistance.
Ceramic tile adhesive mastics
One component, ready to use ceramic tile mastics are used in interior residential and
light commercial applications where only intermittent water exposure is expected.
They are used both for professional tile setting and owing to their simple processing properties in the do it yourself (DIY) market. They have a broad adhesion
spectrum, a long working time and form a flexible adhesive film. Mastics are generally water based and are supplied as a smooth trowelable paste for setting smaller
sized tiles (<15 cm 15 cm).
Guiding formulation
Low emission, ammonia-free, water resistant ceramic tile mastic without film forming aids
Wet parts
Diluent
Water
6.4
0.1
Defoamer
Nopco NXZ*
0.6
Thickener
Natrosol CG 450
Dispersion
Acrylic dispersion
20
Filler
Silica sand (0.16 mm)
39
Filler
Calcium carbonate (23 m)
17.1
Filler
Calcium carbonate (7 m)
17
Total
100
Suppliers: *Henkel Corporation, Ambler, PA, USA; US Silica, Ottawa, IL, USA
239
240
Action of the additives

Cellulosic thickeners (Natrosol) are used to adjust the viscosity and regulate mix consistency, working time and spreadability. Special thickeners (Attagel 50, an attapulgite clay) are used to generate a flow barrier, so that the tiles do not slip under
their own weight. In cementitious systems, cellulosics are used to provide water for
cement hydration over an extended time period due to their natural tendency to
retain water. Surfactants improve the homogeneity and shelf life of adhesives with
high filler content and also have a tendency to extend open time.
Preparation of polymer-emulsion-based CTA mastics
Additives are incorporated into the polymer emulsion in the stated sequence. The
additives are added in portions, and the mixture is stirred after each addition until it
is smooth again. These high-viscosity mastic adhesives (ca. 500 000 mPa s) can in
principle be prepared using any mixing equipment with an appropriate stirrer geometry. Planetary mixers and turbulent mixers are particularly recommended. Preservatives are added to the adhesives to protect them against microbiological attack.
Test methods for assessing tile adhesives
Well defined test methods are available in North America and Europe for evaluating
ceramic tile adhesives. Test methods used in Germany for emulsion-based mastics
are described in DIN EN 1324 (adhesive shear strength) and DIN EN 1346 (correction or adjustment time). Cementbased CTA are tested by DIN EN 1348 (pull of
strength) and again DIN EN 1346 (open time). Classification is determined for both
types of adhesives by prDIN EN 12004. North American test methods and specifications for tile adhesives are described in the following American National Standards
Institute (ANSI) standards:
One-component CTA mastics with glazed wall tiles
ANSI 136.1
Latex-Portland cement mortar with glazed wall tile, quarry tile
and porcelain and/or mosaic tile
ANSI 118.4
Latex-Portland cement mortar with quarry tile on plywood
ANSI 118.11
DIN Methods
In the pull-off strength test performed with cementions CTA, the tile adhesive is first
applied to concrete. After 20 min, earthenware tiles (50 mm 50 mm) are pressed
into the adhesive bed. After a storage time under standard atmospheric conditions,
tension anchors (50 mm 50 mm) are attached to the smooth tile surface using a
two-component adhesive (epoxy). A tensile tester is used to measure the force needed to detach the tile from the concrete; it must be greater than 0.5 N mm2.
To estimate adjustment time, earthenware tiles are laid in the adhesive bed as described above, rotated by 90 after 10 min and then rotated back into the original position. The adhesion pull strength after storage must still be at least 0.5 N mm2.
Also described in DIN 18156 Part 3 is a method for evaluating vertical slip of tiles
under their own weight.
ANSI Methods
The key mechanical tests defined in ANSI 136.1 involves tile-to-tile shear strength
after dry conditioning and after water immersion. In this method, adhesive mastic is
applied to the unglazed back of a 108 mm 108 mm test tile using a specified template to produce a pattern of equally spaced circles of adhesive on the back of the tile.
After 2 min airing time, the unglazed back of a second tile is carefully oriented on to
the adhesive bed tile to tile separation is controlled with the use of spacer rods. Test
assemblies are then subjected to compression under a 6.8 kg load for a period of
3 min. Bonded tile assemblies are then dried for 72 h at 50 % rel. humidity and 22 C
and then further conditioned for 21 days in an air circulating oven set at 49 C. Wet,
type 1 shear strengths are determined by shearing wet test specimens at a defined
rate using a tensile tester, immediately after immersing the bonded test assemblies
in a water bath for 7 days. The minimum ANSI wet, Type 1 shear strength specification for CTA mastics is 3.5 kg cm2 (50 psig). ANSI 118.4 includes a complete series
of methods to evaluate application properties (initial and final set, open time, adjustability, vertical sag) of latexPortland cement mortars and shear strength of
bonded tile assemblies.
8.4.5
Polymer-modified Mortars
Polymer modified Portland cement mortars are used in a range of primary construction and concrete and mortar repair applications (Fig. 8-31) [86, 90].
Damaged
Concrete
Fig. 8-31
Waterproof Membrane
Fine screed
Repair Mortar
Application of repair mortar.
They are applied in bridge decking and airport runway applications, in repair applications, where the mortar layer can be as much as 58 cm thick, in industrial floor
screeds, where up to a 5 cm layer is applied over standard concrete, in fine screeds or
patching compounds, where up to 1.5 cm of repair mortar is applied on floors, in
self-leveling underlayments, where thickness from 23 cm to feather edging are
common.
Fundamentals of concrete and Portland cements, hydration chemistry and classification of admix agents were reviewed by Kosamatka, Panarese and Soroka [84, 85].
Polymers are added to Portland cement based mortar systems for a number of
reasons. Firstly, polymers improve the key properties of the fresh, non hardened
mortar, i.e. adhesion, workability and open time. Polymer additives also tend to have
a plasticizing effect on cementitions mortars, there by reducing the amount of added
water to achieve needed workability and mortar flow properties. Minimizing added
water results in fewer capillary pores, lower porosity and stronger cements. Secondary, the properties of a hardened cement mortar are improved. Properly selected
241
242
polymers, i.e., those with Tg lower than 15 C, form a film within the mortar matrix [86] thereby filling voids, pores and reducing the potential for ingress of water
and dissolved salts. This reduced permeability to salts (e.g. chloride) provides protection against corrosion of underlying steel reinforcing elements. With reduced water
ingress, polymer modification also promotes improved freeze-thaw resistance of the
mortar a feature which is especially important in exterior or cold climate applications.
Improved tensile, compressive and flexural strength are generally realized in polymer modified cement mortars, provided sufficient levels of defoamer are added to
counteract the tendency of emulsion polymer additives to induce excessive foam
generation.
Similarly, concrete used, e.g. in critical bridge decking applications is typically
polymer modified in North America to extend service life and reduce repair costs by
minimizing deterioration caused by exposure to the many forces of nature (Fig. 8-32).
Deterioration of concrete
concrete surface
H 2O
Filler particle
Crack
Steel corrosion - Rust
CaCl
Reinforcing steel
SO2
Pores
Concrete damage
pH = 12 - 13
CO2
Carbonation zone
Fig. 8-32
Deterioration of concrete.
As with ceramic tile thinset mortars, styrene-acrylics, acrylics and SBR polymer
emulsions and their dry polymer analogs, including EVA powders, are employed
across the range of polymer modified cementitious applications. While polymermodified mortars are used widely, for cost reasons, polymer modified concretes are
seldom used with the exception of bridge decks where SBR are almost exclusively
employed. However, in Europe the use of additives in construction concrete is regulated by technical guide lines.
When developing new polymer modified mortars these days, formulators should
also consider the impact of alkali exposure on long-term hydrolytic stability of the
polymer and the subsequent impact of any degradation on application performance
and service life. By their very nature, SBR are inherently resistant to alkali induced
hydrolysis compared to some vinyl acetate containing polymers which, by virture of
the vinyl ester linkage, are more prone to hydrolysis.
Guiding Formulations
Repair mortar
Part A: Liquid Component
Dispersion
Diluent
Part B: Dry Component
Filler
Cement
Filler
Carboxylated SB
Hydration water
Wet parts
54
83
Silica sand
Portland cement
Microsilica
721
273
6
Polymer/cement ratio
Water/cement ratio
Performance after
Flexural strength (bar)
Compressive strength (bar)
0.1
0.4
1 day
60
270
28 days
110
560
Test methods
The test methods are summarized in Chapter 13.
8.4.6
Waterproofing Membranes
Concrete is the most prevalent building material used in the world today [84, 86].
While concrete typically exhibits tremendously high strengths, the fact remains that
it is nevertheless porous in nature and thus, is susceptible to direct moisture penetration and water vapor ingress. Additionally, acids (i.e. CO2, SO2) may penetrate into
the concrete and lower the pH of cementitious materials. Along with migration of
chloride and other salts dissolved in water deep within the concrete, this may cause
severe irreversible damage to steel reinforcements present (i.e. corrosion). Certain
additives can be introduced into the concrete mix to minimize water and salt penetration (e.g. latex admixture, calcium stearate), but due to the costs involved, these
approaches are employed in only the most demanding applications, such as, bridge
decks and parking garages. Moreover, concrete admixtures do not protect the concrete surface layer nor are they able to eliminate moisture penetration in cases where
direct hydrostatic pressure forces exist protective waterproofing membranes are
needed.
A host of different commercial waterproofing systems have been developed to protect against the harmful effects associated with water intrusion into concrete. These
can be broken down into pre-formed membrane sheets and applied coating systems.
243
244
Pre-formed membrane sheets typically consist of rubber modified bitumen supported on a polyethylene web with a release liner to protect the highly adhesive bitumen
layer. These products are available in rolls with total membrane thickness of approximately 12 mm and can be fiberglass-reinforced to provide improved membrane
dimensional stability. The adhesive nature of the rubber-modified bitumen assures
excellent sealing at the roll overlaps. A host of applied coating systems exist based
on rubberized bitumen emulsions, solvent borne synthetic rubber and asphalt
solutions, two-part epoxies, two-part self-curing bitumen-free liquid applied membranes [91], one-component water-based elastic coatings, and flexible one or twocomponent cementitious waterproofing slurries. Water based systems employing
polymer emulsion binders will be discussed further below.
Waterproofing products are used in a wide range of construction and repair applications, applied directly on to pre-formed concrete, concrete blocks, bricks, and stone
products. The most important applications include foundation building walls,
bridges, balconies and terraces, tunnels, basements, planters, silos, and parking
decks. Coating systems are typically applied to uniform thickness (13 mm) using a
brush, roller, trowel or spray system. In all cases, strong adhesion and intimate contact of the waterproofing layer to the underlying substrate, as well as proper waterproof system design, are required to eliminate water seepage through or around the
membrane. Depending on the application, waterproofing membranes should also
exhibit chemical resistance (e.g. to oils and acids), should remain flexible over all potential use temperatures and be capable of resisting hydrostatic pressures, even over
cracks.
Both, one-component, water-based elastic coatings and one or two-component
flexible cementitious waterproofing slurries have the advantage that, by virtue of the
water carrier, they are environmentally friendly and easy to clean after application.
They both yield monolithic, seamless, puncture resistant and watertight layers after
curing but which nevertheless allow water vapor to escape from the inside to the outside. Cementitious systems are particularly ideal on damp substrates because of
hydration reactions which occur in the freshly applied membrane. As they consist of
polymeric binder, sand and Portland cement, through hydration reaction chemistry
they become integrally bonded to and thereby become a part of the underlying concrete. Minor cracks can be bridged at low temperatures, if a sufficiently low Tg, flexible polymer dispersion binder component is selected [87, 93]. Elastic waterproofing
membranes used on the exterior of concrete structures should also exhibit resistance
to the damaging effects of UV radiation, sulfur dioxide and acid rain, carbon dioxide
(carbonation), and repeated freeze-thaw cycles.
Rubber based waterproofing systems are typically based on styrene-butadiene
copolymers and SBS resins while acrylic and styrene-acrylic dispersions are employed in most flexible one-component and two-component cementitious membrane systems.
In Europe, new regulations defined in ZTV-SIB (Additional Technical Contract
Conditions and Regulations for the Protection and Restoration of Concrete Building
Components) specify crack-bridging at 20 C [88]. As a result, lower Tg polymer systems have been developed, which yield membrane flexibility and hairline crack
bridging at lower use temperatures. The industry has moreover shifted to systems
containing, as a rule, higher proportions of polymer binder (0.8 < polymer/cement
ratio < 1) compared with earlier membrane systems.
1. One-component flexible waterproofing membrane (500 m dry film)
Wet parts
Diluent
Water
123.0
5.5
Defoamer
BYK 035*
Freezethaw additive
Propylene glycol
27.1
5.5
Pigment disperser
Pigment disperser NL
1.6
Surfactant
Triton X-405
0.8
Thickener
Natrosol 250 MXR
134.5
White pigment
Kronos 2101 TiO2#
318.2
Filler
Duramite**
16.4
Filler
Atomite**
99.5
Filler
Microtalc MP 10-52
3.3
Biocide
Proxel GXL
Grind until smooth, then add

Polymer binder
Acrylic dispersion
Defoamer
BYK 035*
Thickener
Natrosol 250 MXR
Neutralizing agent
Ammonium hydroxide
Total
Pigment volume concentration: 42.3 %; solids content: 72.8 %
2. Two-component flexible cementitious waterproofing membrane
Dry component
28.0
F-110 Silica sand
27.3
F-95 Silica sand
19.6
Portland cement type I/II##
0.2
Pigment disperser N
Lumiten E-P3108 defoamer
1.6
Styrene acrylic dispersion
Antifoam
Water (to desired flow)
475.7
7.4
2.8
1.8
1223
Wet component
20.6
0.2
0.5
Mix dry and wet components separately, then blend dry mix into the wet phase.
Apply two or three layers of 400600 m each.
Water/cement ratio: 0.45; sand/cement ratio: 2.82; dry polymer/cement ratio: 0.60
245
246
3. Waterproofing membrane
Polymer binder
Defoamer
Thickener
Total
Styrofan D 422
BYK 035*
Rheolate 300***
Wet parts
98.4
0.1
1.5
100
Formulation 3 is intended for sealing interior walls and floors in bathrooms and
other damp areas preventing underlying moisture damage. Compounds based on
Styrofan D 422 can also serve as wet concrete curing compound (by spray application), preventing premature concrete drying during the critical hydration stage.
Suppliers: *BYK Chemie, Wallingford, CT, USA: BASF Corporation, Charlotte, NC, USA;
Union Carbide, Danbury, CT, USA; Aqualon, Wilmington, DE, USA; #Kronos, Houston,
TX, USA; **ECC International, Atlanta, GA, USA; Pfizer, Easton, USA; Zeneca Biocides, Wilmington , DE, USA; US Silica, Ottawa, IL, USA; ##Leghigh Portland Cement Co.,
Allentown, PA, USA; ***Rheox, Hightstown, NJ, USA
Test methods
The ANSI 118.10 test specification describes key test requirements for load bearing,
bonded, waterproof membranes for thinset ceramic tile and dimension stone installation. The standard applies to trowel applied, liquid, and sheet membranes. Requirements include a seam strength evaluation, membrane tensile or breaking
strength, shrinkage or dimensional stability, waterproofness in accordance with
ASTM D 4068, and shear strength of ceramic tile and cement mortar applied on the
waterproofing membrane. Membrane water vapor transmission is typically determined according to ASTM E 96, employing a permeation cup apparatus (Fig. 8-33).
Waterproof membranes in Europe are tested according to [92].
Waterproofness is an indication of a particular membrane materials ability to
withstand a 60 cm hydrostatic pressure head. The apparatus employed in this test is
shown in Fig. 8-34. The membrane film is affixed at the bottom end of the J-tube and
water is then carefully introduced to an overall height of 60 cm above the level of the
membrane.
Fig. 8-33
assembly.
Moisture vapor transmission cup test

Fig. 8-34 J-Tube apparatus for measuring the
hydrostatic pressure resistance of water-proofing membranes.
Fracture of the membrane or evidence of wetness on top of the material (even the
formation of a single droplet) within the first 48 h exposure, are considered as visible
signs of water penetration and require rejection of the material.
The performance of a concrete curing compound is assessed by measuring the water loss of green concrete according to ASTM C 156-94, the water loss after three days
may not be higher than 0.7 kg m2, acievable with SB coatings (Fig. 8-35)
Water loss (kg/m2)
3
without coating
ASTM Spec.
with SB coating
0
Water loss of green concrete
according to ASTM C 156-94.
Fig. 8-35
24
48
72
Time (hours)
247
248
8.4.7
Elastomeric Roof Coatings
Water based elastomeric roof coatings can be described as formulated liquid products, that are applied by spray or roller coating to a sloped roof surface, which have
the ability to form a continuous protective polymer film over the substrate upon
evaporation of the water. Elastomeric roof coatings are used in repair applications to
seal existing roof structures and also in new building construction applications, particularly for protecting polyurethane insulating foam roofs. Elastomeric polymer
films require a proper balance of properties for the film to expand and contract and
return to its original state every time external stress-strain forces have been applied
and removed. Acrylic polymer dispersions are ideal for the manufacture of water
based liquid elastomeric roof coatings.
In particular, white pigmented roof coating membranes are becoming increasingly prevalent as a result of a new EPA program called Energy Star. This program is
aimed at promoting energy efficient buildings and in doing so, reduce building heating and/or cooling costs [89]. The program requires the roof membrane to demonstrate both a minimum initial solar reflectivity and maintenance of that solar reflectance after three years field exposure (by ASTM E 903). Buildings covered with
white coatings, compared to black asphalt type roofs, reflect rather than absorb light
radiation resulting in cooler surface temperatures and reduced cooling demands for
buildings located in hot climates.
While field exposure conditions can vary, the Tg for an elastomeric copolymer
should be lower than the minimum low temperature for a given geographic region
where the roof coating is to be applied (i.e. <20 C). This helps assure that during
cold weather, the membrane will remain flexible and thus, prevent the roof membrane from cracking under contraction stresses.
A typical white roof coating formulation consists of polymer dispersion mixed
with various fillers and pigments and small amounts of additives to provide stability
and to build viscosity to the roof coating mixture. The mixture is applied to a clean
roofing substrate, in two or more coats, and upon drying forms a continuous film or
coating membrane. The polymeric component binds the materials in a monolithic
state and forms the film. This coating membrane must also be sufficiently flexible to
withstand the movement of the substrate due to the diurnal cycle. It also has to provide resistance to water intrusion, cracking, and weathering while maintaining adhesion to the substrate under all exposure conditions.
Low-Tg (20 C) pure acrylic dispersions provide excellent adhesion to polyurethane roofing foam and many other construction substrates. They may contain
internal crosslinking agents that crosslink the polymer film after the water has evaporated. Crosslinking occurs both on the membrane surface and throughout the coating providing required elastomeric film properties with only very slight residual surface tack thereby maximizing dirt pick up resistance and long-term reflectivity.
The demand for dispersions in this market is estimated to be on the order of
20 000 tons wet per annum.
Guiding formulation
Water based elastomeric roof coating
Diluent
Water
Freeze Thaw
Propylene glycol
Dispersing aid
30 % Pigment Disperser NL*
Binder
Acrylic dispersion
Defoamer
BYK 035
Kronos 2101
TiO2 pigment
Filler
Duramite
Filler
Atomite
Filler
Microtalc MP 10-52#
Biocide
Proxel GXL**
Grind, then add Binder Acrylic dispersion
Thickener
Natrosol 250 MXR
Neutralizing agent
Ammonia Solution
Defoamer
BYK 035
Weight % solids = 72; volume % solids = ca. 59
% Pigment volume concentration = ca. 42; viscosity (Krebs) = ca. 105
Wet parts (g)

6.88
2.23
0.45
28.45
0.45
11.17
26.36
1.34
18.27
0.22
12.78
0.34
0.23
0.91
Suppliers: *BASF, Charlotte, NC, USA; BYK-Chemie USA, Wallingford, CT, USA; Kronos, Houston,
TX, USA; ECC International, Roswell, GA, USA; #Pfizer, Easton, PA, USA; **Zeneca
Biocides, Wilmington, DE, USA; Aqualon, A Div. of Hercules, Wilmington, DE, USA
Test methods
In 1997 an American National Standard, ASTM D 6083-97a (Fig. 8-36), was issued
for determining the acceptable performance of liquid acrylic flexible roof coating
mixtures based on laboratory testing. These specifications are based on a somewhat
Film physical property

After 14 days drying at room temperature
Tensile strength D2370
% Elongation at break
After 1000 h aging in a xenon arc weatherometer
% Elongation at break
Accelerated weathering
checking
Low-temperature mandrel flexibility
Adhesion (wet) C 794
Water swelling (%)
Permeance inverted (perms)
Tear resistance (lbf in1)
Fungi resistance (after 28 days)
Fig. 8-36
roofing.
ASTM test
Requirement
200 psig
D2370
100 %
D2370
D4798
100 %
No cracking and
D522
Pass (1/2 in at 15 F)
>2 lb in1
D471
D1653
D624
G21
<20 %
<50
>60 (die C)
Zero observed
Standard specification for liquid applied acrylic coating used in
249
250
broader set of test requirements described in Dade County Florida, Protocol PA 12995 and Protocol PA 143-95.
The standard has minimum specifications, when testing the free film for tensile
strength, elongation at break, water swelling, permeability and tear resistance. These
tests are carried out after a minimum of 14 days drying at standard lab conditions
(22 C and 50 % relative humidity). The coated film must also meet standards for, adhesion to various substrates, tensile strength, elongation at break and mandrel flexibility. These tests are carried out at various specified temperatures, relative humidity
and aging conditions.
Acknowledgments
The authors would like to express their sincere thanks to the following colleagues for
friendly assistance in writing the Applications for Adhesive and Construction Industries chapter and for critical checking of the manuscript: H. Anders, G. Auchter,
O. Aydin, M. Drewery, W. Druschke, P. Fickeisen, P. Fitzgerald, H. J. Fricke, R.
Fl, H. Jger, J. Krobb, U. Licht, W. Mchtle, L. Maempel, H.W.J. Mller, J. Neumann, J. Pakusch, H. Seibert, B. Schuler, K.-H. Schumacher, F. Schwarz, J. TorresLosa, J. Trk, A. Zettl, A. Zosel
251
References
1 D. J. Alner, Aspects of Adhesion, Vols 13,
2
3
4
5
6
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
26
University of London Press, London,

1965, 1966, 1967.
De Bruyne-Houwink, Klebetechnik,
Berliner Union, Stuttgart 1957.
R. Houwink, G. Salomon, Adhesion and
Adhesives, Vols 1 and 2, Elsevier, Amsterdam, 1967.
C. Lttgen, Die Technologie der Klebstoffe,
Wilhelm Pansegrau, Berlin, 1959.
M. Michel, Adhsion und Klebetechnik,
Carl Hanser, Munich, 1969.
R. L. Patrick, Treatise on Adhesion and
Adhesives, Marcel Dekker, New York,
1967.
E. Plath, Taschenbuch der Kitte und Klebstoffe, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1963.
J. Skeist, Handbook of Adhesives, Reinhold, New York, 1977.
P. Weiss, Adhesion and Cohesion, Elsevier, Amsterdam, 1962.
Europischer Klebstoffverband, Kleben
und Dichten Adhsion, 1997, 41, 89.
Chemical Week, March 25, 1997, pp.
2130.
R. Jordan, Adhsion, 1987, 1/2, 1729.
H. H. Day, US Patent 3965, 1845.
P. Beiersdorf, German Patent 20057,
1882.
D. V. Varanese, Adhesives Age, April
2000, p. 22.
H. Jger, Adhsion, 1985, 9, 3239.
M. Kusumgar, Adhes. Sealants Ind.,
Oct/Nov. 2000, 4446.
Schwartz, J., Adhes. Age, April 2000.
Adhsion, 1996, 40, 1011.
G. Auchter, J. Barwich, H. Jger,
G. Rehmer, Adhsion, 1993, 1/2, 1420.
T. Sanborn, J. Barwich, Adhes. Sealants
Ind., August 1997.
K.-H. Schumacher, T. Sanborn, Adhes.
Sealants Ind., June/July, 2001, 4244.
J. W. Hagan, C. B. Mallon, M. R. Rifi,
Adhes. Age, 1979, 3, 29.
D. L. Prentice et al., Adhes. Age 1992, 2,
1826.
D. Satas (ed.), Handbook of Pressure Sensitive Adhesives Technology, Van Nostrand
Reinhold, 1989.
27 W. Druschke, Adhsion, 1987, 5, 2932;
6, 2634.
28 D. Satas, Adhes. Age, October 1972.
29 J. W. Hagan, C. B. Mallon, M. R. Rifi,
Adhes. Age, March 1979.

30 A. Zosel, Colloids Polym. Sci. 1985, 263,
541.
31 A. Zosel, Adhsion 1986, 3, 1424.
32 H. Fikentscher, Cellulose Chem. 1932,
13, 58.
33 L. Varela, T. Sanborn, PSTC Confer-
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
ence, 24th Annual Technical Seminar,

May 2001.
A. Zettl, in: Handbook of Pressure Sensitive Adhesives Technology, D. Satas (ed.),
Van Nostrand Reinhold, 1989.
R. Mildenberg, M. Sander, G. Collin,
Hydrocarbon Resins, VCH, New York,
1997.
S. W. Medina, F. V. DiStefano, Adhes.
Age, February 1989.
R. A. Bafford, Adhes. Age, December
1979.
J. Trk, Papier- und Kunststoff-Verarbeiter, 1985, 5, 40.
J. Trk, Adhsion, 1993, 10, 1720.
I. Benedek, L.J. Heymans, Pressure Sensitive Adhesives Technology, Marcel
Dekker, New York, 1996, Chapter 9.
Exxon Chemicals, Adhes. Update, 1996.
H. Jger, Adhsion, 1985, 9.
R.P. Muny, Adhes. Age, August 1996,
pp. 2024.
K. W. Allen, J. Adhes. 1987, 21(3/4),
261277.
B. Blmich, P. Blmler, A. Guthausen,
C. Flber, G. Eidmann, R. Savelsberg,
Kautschuk Gummi Kunststoffe, 1997,
50(7/8), 560563.
F. S. Chang, Trans. Soc. Rheol. 1960, 4,
75.
J. L. Gardon, J. Appl. Polym. Sci. 1963,
7, 625.
S. Yamamoto, M. Hayashi, T. Inoue,
J. Appl. Polym. Sci. 1975, 19, 2107.
D. Satas, F. Egan, Adhes. Age 1963,
9(8), 22.
D. H. Kaelble, Trans. Soc. Rheol. 1965,
9, 135.
D. H. Kaelble, J. Adhes. 1965, 1, 102.
252
References
52 C. A. Dahlquist, in: Handbook of Pressure
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
Sensitive Adhesives Technology, D. Satas

(ed.), Van Nostrand Reinhold, 1989.
J. Johnston, Adhes. Age 1983, 26(12), 34.
T. H. Hammond, in: Handbook of
Pressure Sensitive Adhesive Technology,
D. Satas (ed.), Van Nostrand Reinhold,
1982, p. 32
F. Chang, L. Rubber, Chem. Techn. 1957,
30, 847.
F. Wetzel, ASTM Bulletin No. 221, 1957,
64.
F. H. Hammond, ASTM Special Technical Publication No. 360, 1963, 123.
A. Zosel, Adhes. Age 1989, 32(11), 42.
A. Zosel, J. Adhes. 1989, 30, 135.
A. Zosel, J. Adhes. 1990, 34, 201.
A. Zosel in: Advances in Pressure Sensitive
Adhesives Technology 1, D. Satas (ed.),
Satas and Associates, Warwick, RI, USA,
1992, p. 92.
A. Zosel, J. Adhes. 1994, 44, 1.
A. Zosel, J. Barwich, Farbe Lack, 1996,
102, 136.
A. Zosel, Adhes. Age Aug 2000, 3439.
A. Zosel, Adhes. Sealants Ind. Oct/Nov,
2000, 3036.
K. Kamagata, J. Adhes. 1970, 2, 279.
Flexible Packaging, July 2000, p. 6.
H. J. Fricke, L. Maempel, Kleben Dichten,
Adhsion, 1994, 11, 1420.
K. H. Schumacher, J. Fricke, M. Gerst,
Adhes. Technol. June 1999, 1214.
www.dkgroup.com/articles.htm
W.-D. Domke, H. Steinke, Poster presentation February 18, 1985, Macromolecular Colloquium Freiburg.
H. J. Fricke, L. Maempel, Adhsion 1990,
7/8, 1319.
L. Maempel, Adhsion 1988, 5, 1418.
Adhes. Sealants Ind. May 1998, p. 30.
P. Fickeisen, R. Fl, R. Hummerich,
J. Neumann, Adhsion, 1988, 1/2, 2429.
76 Rohm and Haas, Kleben und Dichten
Adhsion, 1998, 42(1/2), 2529.

77 Adhes. Age, September 1999, pp. 5ff.
78 California South Coast Air Quality
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
Management District (SCAQMD)Rule

1168.
Adhes. Age March1999, 4.
Adhes. Age May 2000, 44.
J. Krobb, E. Wistuba, Adhsion, 1992, 5,
1420.
OSI Witco, Technical brochure.
V. F. Foster, Caulks and Sealants
Overview, Caulks and Sealants Short
Course, The Adhesives and Sealants
Council, Pittsburgh, March 1997.
S. H. Kosamatka, W. C. Panarese,
Design and Control of Concrete Mixtures,
13th edn, Portland Cement Association, Skokie, Illinois, 1988.
I. Soroka, Portland Cement Paste and
Concrete, Chemical Publishing Co.,
New York, NY, 1979.
S. Chandra, Y. Ohama, Polymers in
Concrete, CRC Press, Boca Raton, 1994.
M. Angel, H-J. Denu, Waterproof Membranes for Concrete Surfaces Protection,
Farbe and Lack, Vol. 103(8), 1997.
http//www.bast.de/htdocs/qualitaet/
dokument/doku.htm
http//www.energystar.gov/
Y. Ohama, Recent progress in
ConcretePolymer Composites, Elsevier,
1997, pp. 3140.
M. T. Pickett, W. R. Grace and Co.
Conn., US Patent 5763014, 1998.
Mineralische Dichtungsschlmme fr
Bauwerksabdichtungen (Prfgrundstze zur Erteilung von allg. neuaufsichtlichen Prfgrundstzen) 02/2001.
J. Pakusch, H.-J. Denn, B. Reck, Polymer Powders with elastic properties,
Farbe + Lack, Vol. 105(12), 1999.
Applications in the Carpet Industry

Peter R. J. Blanpain, Richard L. Scott, Onno Graalmann, and J. Arthur Smith
9.1
Introduction
This chapter covers the use of synthetic polymer dispersions in the carpet industry.
In 1999, carpet accounted for approximately 60 % [1] of the volume of all floor coverings (soft and hard) sold in the USA, with an estimated [2] sales volume and value of
1.6 billion m2 and $11.7 billion respectively. Of this volume, the tufted carpet and
rug segment, the largest user of polymer dispersions, is dominant with an estimated
1.4 billion m2, with broadlooms share accounting for approximately 1.3 billion m2.
Europe and the Asia-Pacific countries produced during the same period an estimated 1.13 billion m2 [3] and 284 million m2 soft floor covering respectively.
Synthetic polymer dispersions have been used as binders for the backing of carpet
since the late nineteen-forties. The function of the polymeric binder in carpet backings is primarily to anchor the pile fibers in place, give improved dimensional stability, hand, and resistance to fraying or tuft loss at cut edges of the carpet.
Carpet backing is the fourth largest user of synthetic dispersions in North America (NA) after paints and coatings, paper, and adhesive applications. During 1999, dispersion consumption in carpet backings was around 490 kt (wet) [4], which represents around 9 % of the estimated 5,300 kt total dispersions (wet) produced in the
USA. In Western Europe and the Asia-Pacific regions, dispersion usage during 1999
has been estimated at respectively 400 kt [3] and 100 kt wet.
9.2
History of Carpet
The history of the manufacturing of rugs and carpets began with weaving. Evidence
obtained from excavations near the Caspian Sea indicates that the spinning and
weaving of sheep and goat wool was practiced as early as 6000 BC. It is known that
the Egyptians of 3000 BC wove linen carpets ornamented by sewn on pieces of colored woolen cloth. A Turkish knotted pile rug, dated back to 500 BC, was found in
253
254
9 Applications in the Carpet Industry
Siberia in the nineteen-fifties. The weaving of hand-knotted rugs spread throughout

the Orient, and Persia (Iran) became the predominant manufacturer.
Oriental rugs were carried to Europe by the Saracen conquerors of Spain, by returning Crusaders, and later Italian merchants. The Spanish in the 13th century,
were the first Europeans to make hand-pile rugs. Moorish weavers were probably
taken from Spain in the 13th century to start the early French carpet weaving industry at Aubusson. Deep-pile rugs, called Savonneries, were first produced in Paris
during the early 17th century. The revocation of the Edict of Nantes in the late 17th
century, that had guaranteed religious and civil freedom to French Protestants, drove
French and Walloon Protestants (the Huguenots) into England, The Netherlands
and Germany, where they made significant contributions to the early development
of the spinning and weaving industries in these countries. The chartering of carpet
weavers in Wilton and Axminster in 1701, and the introduction of carpet production
in Kidderminster around the 1740s, was the beginning of the establishment of England as the worlds major woven carpet producer. This situation continued until the
1960s, when technology developed in America for tufted carpet production was introduced into Europe. This resulted in woven carpet production declining in England by about 70 % by the1970s, and the establishment of Belgium, The Netherlands, Germany, and Great Britain as Europes major tufted carpet manufacturers.
Before the 1790s, the carpet business in the USA was monopolized by expensive
woven imports from The United Kingdom. The US carpet industry had its modest
beginning in 1791 when William Sprague founded the first woven carpet mill in
Philadelphia. During the early 1800s, as carpet became more popular, other factories
were established in New England, New York, and Pennsylvania. Continued domination by British imports, stimulated efforts to improve methods of production, and in
1839 Erastus Bigelows invention of the power loom, which made the mass production
of woven carpet possible, reshaped the industry. This, together with the invention of
the Axminster loom in 1876 to produce woven carpets with a wide range of designs
and colors, increases in loom widths, and other advances in technology, further stimulated the expansion of the US woven carpet industry. The woven carpet industry
continued to thrive until the end of the nineteen-forties and the advent of tufted carpets.
The tufted carpet industry had its beginning in the late 19th century, when a Dalton (Georgia, USA) woman, Catherine Evans Whitener, produced bedspreads by
sewing thick cotton yarns with a running stitch, into an unbleached muslin base
cloth, and cutting the surface loops of the yarn so they would fluff out. After tufting,
the material was washed to cause the muslin to shrink around the tufts to mechanically hold them in place. She sold the first bedspread in 1900, and generated so much
interest that a thriving cottage industry started. Bedspreads led to other small tufted
goods such as toilet covers, robes, and small scatter rugs, and by the 1930s there
were around 10 000 Tufters in the Dalton area.
During the late 1920s and early 1930s, increased costs, and falling prices due to increased competition, resulted in the development of multi-needle tufting machines,
the mechanization of looms, and building of looms of greater width in order to meet
demands for more bedspreads. Tufting machines for producing carpet appeared in
the late nineteen-forties, and by the late nineteen-fifties, carpet affordable to virtually
9.3 Present Day Carpet Business
every home owner in the USA, was being produced in twelve foot widths, using nylon fiber, and jute as the secondary backing cloth. The evolution of the US carpet industry since this time is depicted below in Tab. 9-1.
Tab. 9-1
Evolution of the US carpet industry (in million m2).
Year
Tufted carpet
Woven carpet
Total
1950 [5]
1974 [5]
1992 [6]
1998 [6]
1999 [2]
16
724
1094
1404
1432
65
61
19
30
34
81
785
1113
1434
1466
9.3
Present Day Carpet Business
In 1999 [2], the US carpet industry produced an estimated 1.6 billion square meters
of carpet floor coverings, with a value of $11.7 billion. This represents 45 % of the total world carpet production. The state of Georgia accounts for 74 % of US production
nearly all of which is concentrated in the northwest corner of the state around the
city of Dalton [7]. As shown in Tab. 9-2, tufted carpet is by far the largest carpet type
produced with approximately 90 % of the total carpet volume, with broadloom carpet
representing around 90 % of the tufted volume. Second largest are the carpets
grouped under others (knitted, knotted, needlepunched, etc.) with around 8 % of the
total. Woven carpet has almost disappeared and today only represents around 2 % of
the total carpet manufactured.
Tab. 9-2
1999 US carpet production (in million).
Total Tufted
Woven
Other
Total
m2
US $
1432
34
129
1595
10692
450
548
11690
The situation in Europe, as indicated in Tab. 9-3, is somewhat different in that woven (13 %) and needlepunched (26 %) carpet floor coverings still have an appreciable
share of the total.
In the USA tufted broadloom carpet, the most important segment of the tufted
carpet business with an estimated 1.3 billion m2 in 1999, is constructed for use in
three markets:
consumer residential:
purchases for use in a home by members of a family.
contract residential:
purchases by persons other than the home owner for
new homes, apartments, condominiums, multifamily
units, recreational vehicles, manufactured housing, etc.
255
256

Tab. 9-3
1999 European carpet production (in million).

m2
Tufted
Woven
Needlepunched
Total
682
143
296
1121
I*
6656
1746
441
8843
*Courtesy: GUT e.V., Aachen, Germany
contract commercial:
purchases other than by a home owner for hotels, motels, college dormitories, school rooms, business offices,
banks, institutional buildings and industrial buildings.
In terms of square meters and market share percent, 1999s production forecast
(USA) [1] for the three types of carpet is summarized in Tab. 9-4.
Tab. 9-4
Broadloom carpet by market type (in million).
Type
m2
Consumer residential
Contract residential
Contract commercial
Total broadloom
707
262
339
1308
54
20
26
100
In all three, whilst the binder used for construction may be the same, the type and
formulation of the backing adhesives differ significantly, as each category of carpet
has different performance specifications. The formulations employed, and methods
of adhesive application, for producing the three carpet types will be detailed in sections following, together with insight into their end use property requirements.
9.4
Carpet Backing Binders
During the late nineteen-forties, the starches and natural gums initially used as
binders for improved tuft bind, were largely replaced by rubber dispersions. In the
nineteen-fifties, the major binders were natural latex, cold SB (styrene-butadiene)
and hot SB dispersions, the polymers usually being vulcanized to obtain good
strength. The mid nineteen-fifties saw the introduction of non-cure hot SB dispersions, which began to replace the sulfur cure SB. The late nineteen-fifties saw the
development of carboxylated styrene-butadiene dispersions (XSB) and their introduction as binders for carpet backings. These XSB dispersions, as a result of the
easier and less costly compounding, faster drying rate, and improved performance
in terms of specific adhesion to the fabric substrates, have since become the workhorse of the carpet backing industry. The 70s through to the early nineteen-eighties
was the era of the attached SBR foam cushion backings. Such carpets were con-
9.4 Carpet Backing Binders
structed using a compounded XSB dispersion pre-coat or tie-coat to bind the tufts in
place, followed by the application of a foamed compound of a high solids styrenebutadiene latex (HSL), to provide under foot comfort, and prolong the useful life of
the carpet.
Foam backing is a process in which a high solids SB dispersion, a vulcanizing
agent (suspension of sulfur, zinc oxide, accelerators), chalk and emulsifier together
with air is frothed. The wet foam structure needs to be maintained until vulcanization takes place. This can be achieved by gelling agents which destabilize the polymer particles by smoothly decreasing pH and coagulating the latex within the membranes of the wet foam. Non-gel foam is stabilized with emulsifiers which maintain
the foam structure during the evaporation of water until vulcanization takes place.
Vulcanization is carried out at about 100 C resulting in an elastic polymer network.
The polymer/filler ratio varies from 1:0.5 to 1:2.
In 1975 it was estimated that one third of all the broadloom carpet produced in the
USA had an attached SBR cushion. Unfortunately, the highly competitive situation
prevailing at the time, compelled manufacturers to reduce the cost of the attached
foam by either increasing the level of the cheap calcium carbonate filler and/or reducing foam application weights and density. This inevitably adversely affected the
durability of the foam to such an extent that failure occurred resulting in premature
wear of the carpet. As consequence of the bad name that attached SBR cushions obtained in the eyes of consumers, today HSL foam backed carpet has virtually disappeared in the USA, with the exception of a few specialty floor coverings such as bath
mats.
The situation in Europe is somewhat different to that of the United States of
America. In general the styles of carpet produced in Europe have a much lower face
fiber content, the pile height being much lower and pile density higher. The foam
backing was also generally of higher density therefor thinner for an equivalent
weight. The transfer of heat into the foam product is much easier, and enabled higher production speeds to be achieved than were possible in the USA.
A similar situation to that observed in the USA has been experienced for similar
reasons, but at a much slower speed. The consumption of HSL for foam backing remained fairly static for many years, the growth in the market being almost entirely
restricted to secondary backed products, and the market share of foam backed carpet
being gradually eroded.
In the late nineteen-nineties environmental pressure, particularly in Germany, resulted in a very steep decline in the consumption of HSL for floor coverings. Several
of the ingredients used in the formulations for HSL foam in the floor coverings industry were brought into ecological question. Since 1998, when foam backed carpets
made up approximately 45 % of textile floor coverings in Europe, this has decreased
to approximately 20 % in 2000.
An alternative more ecologically friendly product was required. In Europe this was
achieved by replacing the HSL foam by a needlefelt product which is adhered to the
carpet by means of an XSB latex. In North America carpet underlays made of
polyurethane foam are commonly used to provide the soft comfort of residential
carpets.
257
258
Over the years, it is fair to say that virtually every type of polymer available in dispersion form has been tried for use in the backing compound for tufted carpet. However, because of its versatility and cost-effectiveness, it is the carboxylated styrene-butadiene (XSB) polymer dispersions that hold the major share of this business today
with an estimated 95 % of the volume sold in 1999, the remaining volume being
shared by ethylene-vinyl acetate, polyvinyl chloride and polyurethane dispersions.
During 1999, the US carpet industry consumed approximately 490 kt wet dispersion,
of which 463 kt were XSB [4]. The majority of the XSB is supplied direct to the carpet
mills by the three major dispersion producers BASF, Dow Chemical, Omnova, with
a minor proportion being supplied by so-called re-sellers or compounders such as
General Latex, Polymer Products, Southeastern Latex and Textile Rubber.
The XSB binders of today are considerably different from those at the time of their
introduction into carpet backings. Ongoing advances in polymerization technology
have enabled tailoring of the physical and polymeric properties of dispersions to better meet the evolving demands of present day backing machines and performance
requirements. Whilst the dispersion formulations are the proprietary information of
the producers, some typical characteristics of the dispersions commercially available
today are given below.
Polymer type:
Bound styrene:
Carboxylation:
Carboxylated styrene butadiene dispersion (XSB)

Typically in the range 6067 %
Typically less than 3 % by weight of the polymer. The carboxylic acid may be itaconic acid alone or blends of itaconic
acid with either acrylic acid or methacrylic acid. The actual
type/level of carboxylation is proprietary information to each
producer.
Solids content:
5153 % dry weight
pH:
7.59.0
Particle size:
Up to 10 years ago, 170200 nm used to be the norm. Today, as
consequence of the need to reduce 4-PCH content, particle
sizes are generally within the 140155 nm range.
Volatile organic
Over the last 1012 years, and the advent of Sick Building
components (VOC): Syndrome, the dispersion producers have radically improved
their XSB manufacturing processes to minimize the level of
residual organic compounds. Today, the maximum target values, in ppm on wet dispersion, for the four major VOC are given in Tab. 9-5.
Surfactants:
Type and level is the proprietary information of the individual
producers. They are usually selected not only for good stability
and low foaming during the dispersion manufacturing
process, but also to impart the required foaming properties to
the backing binder formulations during processing in the customers plant.
9.5 Carpet Laminating

Tab. 9-5
Maximum limits (ppm) of volatile organic components.
Styrene
Ethylbenzene
4-Vinylcyclohexene
4-Phenylcyclohexene
Total
North America
Europe*
Denmark
35
10
15
60
200
50
50
200
<400
40
20
10
50
*Defined
by EPDLA (European Polymer Dispersion and Latex Association)

and GuT (Association for environmental friendly carpet)
9.5
Carpet Laminating
9.5.1
Background
Several types of carpets including woven, needlepunch, knitted, and tufted are subjected to the latex laminating procedure [8]. By far the most prevalent carpet construction method is tufting. The first tufting machines were very similar to a giant
sewing machine that uses thousands of threaded needles in a row across the width of
the machine. Todays machines are far more complex and sophisticated, although
they still work in the same basic way. The creel, or rack of yarn cones, are located in
front of the tufter. From the creel, the yarns are passed overhead through guide
tubes to puller rolls. The speed of the puller rolls controls the amount of yarn that is
supplied to the tufter and, with other factors, determines the carpets pile height.
The needles, which number up to 2000 for very fine gauge machines, insert the
yarn into a primary backing supplied from a roll of material located in front of the
machine. Spiked rolls on the front of the tufting machines feed the backing through
the machine.
Below the needle plate are loopers, devices shaped like inverted hockey sticks,
timed with the needles to catch the yarn and hold it to form loops. If a cut pile is
called for, a looper and knife combination is used to cut the loops. For cut-loop combinations, a special looper and conventional cutting knife are used.
Tufting has reached a high degree of specialization utilizing a variety of patterning
devices, many of which are computer-controlled. Stepping, or zigzag moving, needle
bars and individually controlled needles greatly expand patterning possibilities. Such
patterned carpet is frequently referred to as a graphic pattern. Other advanced tufting techniques are loop over loop and loop over cut (LOC) machines.
After completion of tufting, the unfinished tufted carpet will be dyed, if precolored
yarns are not used, followed by a finishing step to add a compound and usually a secondary backing material.
Carpet laminating or backcoating is an essential step in the carpet manufacturing
process. Since the backcoating is hidden from view, the attributes it imparts to the
finished carpet are rarely appreciated. Both the long term performance and the aes-
259
260
thetic value of the installed carpet are vitally dependent upon a correctly formulated
and a properly applied backcoating. Among the most important performance requirements of a backcoating are:
high tuftlock
minimum pilling and fuzzing
adhesion to secondary backing
dimensional stability
bundlewrap
proper hand
durability
water resistance
resistance to heat, light, and atmospheric contaminants
flammability-pill, tunnel, radiant panel, smoke, vertical burn
resistance to edge fraying
odor
9.5.2
Carpet Terminology
Before proceeding further with carpet laminating, a review of carpet terminology

would be useful, since physical properties imparted by the SB latex backcoating relate directly to its construction. Figure 9-1 illustrates a typical cut pile carpet and the
physicals associated with it. A level loop carpet would appear the same but the tops of
the tufts would not be cut. Physicals and terminology for a level loop carpet would be
the same as for cut pile.
Fig. 9-1
Carpet terminology.
Tuft:
Bundle:
Filament:
Primary:
One cut or uncut loop of a pile fabric

A continuous tufted collection of fibers or filaments
A single continuous strand of fiber
Woven or non-woven fabric into which the pile yarn is inserted
by tufting
Secondary:
A woven or non-woven fabric laminated to the tufted primary
to provide dimensional stability
Delamination:
The force expressed in lb/inch required to remove the secondary backing from the primary carpet (ASTM D 3936, ISO
11857).
Tuftbind:
The force expressed in pounds required to remove a single tuft
from its primary backing (ASTM D 1335)
Pill and fuzz:
Hairy effect on the carpet surface caused by slippage of individual filaments or fibers
Bundlewrap:
A subjective rating, usually expressed as a percentage, to indicate the degree of latex encapsulating the yarn
Bundle penetration: A subjective rating, usually expressed as a percentage, to indicate the degree of penetration into the yarn
Hand:
A subjective rating to indicate the stiffness of the finished carpet
9.5.3
Back-coating Applications
Over the last few years, direct coating with scrim lock has replaced pan application as
the preferred method for back-coating carpet. The major advantages associated with
direct coating are:
less waste (mill and disposal savings)
easier clean up
overall ease of operation
uncoated selvages (cost and clean up savings)
uniform weight control side to side
uniform coating side to side
fresh compound always available
less problems with filler fallout
higher compound solids
immediate response to cup weight changes
short lag time for compound changes
elimination of density variations (airing up or collapsing in pans)
thixotropic effects eliminated (troughing, poor pickup)
better visual weight control (puddle gain or loss seen immediately)
faster drying due to lighter densities
Figure 9-2 depicts a typical direct coating unit with scrim coat. This schematic
shows a set up utilizing a bed-plate for the application of the pre-coat and a pan for the
application of the adhesive scrim coat. Variations of this include a roll over roll for
the pre-coat application and a roll over roll or Tillitson application for the adhesive.
261
262
Direct coating with scrim coat.
Fig. 9-2
9.5.4
Back-coating Formulations and Ingredients
Direct coating is used to back-coat both residential and commercial carpets. Backcoating residential carpets involves two latex compounds. One is highly loaded with
filler and is deposited directly onto the tufted primary after having passed through a
mechanical froth machine. The froth machine lowers the density thus allowing for
proper placement and weight control. This compound is usually referred to as the
pre-coat or undercoat. Its primary purpose is to securely lock the tufts into the primary backing. Other properties affected by the pre-coat are pill and fuzzing, hand,
delamination, and flammability.
Along with latex, the pre-coat compound would typically contain water, filler, surfactant, and thickener.
Water is used to adjust the solid content of the compound, aid in the dispersion of
the filler, and extend shelf life.
The filler is almost always calcium carbonate due to its universal availability and
economical price. Its grind and purity are critical for compound stability and runability. Typical pre-coat loadings are between 400 and 600 parts per 100 parts dry
latex. To enhance flame retardant properties, aluminum trihydrate can be substituted for all or part of the filler in the pre-coat.
Surfactants are used to increase stability and frothability of the compound. Sodium lauryl sulfate (SLS) and ammonium lauryl sulfate (ALS), sodium sulfosuccinamate, and combinations of ALS and long chain alcohol are commonly used.
Thickeners are almost always sodium polyacrylates. They impart the proper viscosity and rheology to allow proper placement of the compound. They also help to
suspend the filler in the compound.
Miscellaneous ingredients occasionally will be used, if a back-coating needs a specific appearance or specialized performance property. Miscellaneous ingredients include pigment, penetrant, defoamer, dispersant, chelating agent, anti-blistering
agent, antistatic agent, and stabilizer. A typical pre-coat formulation used in North
America is represented in Tab. 9-6.
Tab. 9-6
Pre-coat formulation (US).
Water
XSB latex
Calcium carbonate
Surfactant
Polyacrylate thickener
Total
Solids content (%)
Dry parts
Wet parts
53
100
35
13
83
100
550
2
1
653
35
188
550
5.7
7.7
786
Solids content of the formulation 83 %; viscosity 1718 Pa s
In Europe a typical pre-coat formulation does not exist due to widely differing
styles and quality requirements. In general they contain more filler (6001000 dry
parts of calcium carbonate), less surfactant (0.20.5 dry parts), and less thickener (0.4
dry parts), and viscosity of 35 Pa s.
The second compound used in residential carpet coating is referred to as the
adhesive scrim or skip coat. It is applied by means of a pan and lick roll directly to the
secondary backing. This coating provides the strength necessary to sufficiently adhere the secondary backing to the primary backing, which in turn imparts dimensional stability to the carpet.
The adhesive scrim coat formulation is similar to the pre-coat with two exceptions.
First, since the compound is not frothed, surfactant is eliminated from the formulation. Secondly, since a stronger compound is required for the adhesive coating, filler
loading is reduced. Loadings between 350 and 400 parts of filler per 100 parts of dry
latex are typical. Table 9-7 is representative of a typical adhesive formulation.
Tab. 9-7
Adhesive scrim coat formulation (US).
Water
XSB latex
Calcium carbonate
Total
Solids content (%)
Dry parts
Wet parts
53
100
13
82
100
375
0.6
475.6
12
188
375
4.6
579.6
In Europe the ingredients for secondary backing compounds are similar but the
filler loads can vary from 0450 parts per hundred part of dry latex. The configuration of the coating machines determines the compound to be used. On average the
viscosity is 5 Pa s.
Since most commercial contract carpets are glued directly to the substrate, the
need for a secondary backing is eliminated. Thus most commercial contract carpets
263
264
are coated with a single high strength compound referred to as a unitary coating. To
meet the enhanced performance requirements of commercial contract carpets a
high density, low filled compound is used. High density is achieved by using low
surfactant levels and lightly frothing the unitary compound. Filler levels are typically
in the range of 150200 parts of filler per 100 dry parts of latex. The two most important properties of a unitary coating are high tuft-bind requirements (1120 lb,
5090 N) and pill and fuzzing. Table 9-8 illustrates a typical North American unitary
formulation.
Tab. 9-8
Unitary backing formulation (US).
XSB latex
Calcium carbonate
Surfactant
Total
Solids content (%)
Dry parts
Wet parts
53
100
35
13
73
100
150
0.5
0.4
250.9
188.6
150
1.4
3.1
343.1
European unitary formulations would be very similar both in ingredients and filler
loads to the above North American formulation. Typical viscosity is 5 to 7 Pa s.
9.5.5
Industry Issues
Although direct coat has been universally accepted as the latex application technique
of choice, there still exist large variations in processing speeds due to a wide range of
dryer configurations and their efficiencies. Current processing speeds for a light
weight carpet can range between 10 to 60 m min1.
As the industry becomes even more competitive, manufacturers will be forced to
continue to reduce fixed and variable costs. More and more high speed dryers will replace slow inefficient ones.
Computerized froth machines will become more common as mills focus on reducing variable costs. Utilizing computerized frothing machines eliminates the need
to sample for density control and allows for a more consistent latex application due
to the consistent froth produced.
Feed forward application systems are beginning to be used by some manufacturers. This system produces a more consistent compound application resulting in enhanced performance.
Electronic monitoring from the compounding area to final inspection is reducing
manpower requirements and increasing dryer efficiency dramatically.
Following is a list of process improvements currently being implemented or anticipated for implementation in the future:
movement toward high efficiency, high speed finishing ovens
increased use of computerized froth machines
feed forward application systems

some carpet producers beginning to question delamination testing as best indicator of fit for use
increased use of polypropylene fibers for commercial carpet resulting in greater
need for latex that has an affinity for polypropylene
greater need for blister resistant latex due to higher heat and more efficient ovens
increased commitments through quality partnerships by both latex producers and
carpet manufacturers in the use of statistical process control
movement towards low/zero ammonia systems to reduce emissions into the workplace
quality issues have replaced VOC issues as the primary concern of carpet manufacturers.
Since 1988 there has been a heightened awareness of volatile organic compounds
(VOC) emitted from carpet. In the early nineteen-nineties allegations stemming
from flawed scientific work arose connecting a chemical (4-PCH) emitted from carpeting to adverse health effects. 4-phenyl cyclohexene or 4-PCH is a byproduct of the
SB latex manufacturing process and has a low odor threshold. It is formed by a DielsAlder reaction of styrene and 1,3-butadiene and is responsible for new carpet odor.
As a result of the allegations the Styrene Butadiene Latex Council (SBLC), the trade
association of US latex producers and the EPA (Environmental Protection Agency)
undertook extensive animal toxicological testing to investigate whether there was a
link between 4-PCH and adverse health effects. After exhaustive testing and numerous reviews, the EPA declared 4-PCH to be an unremarkable chemical [9]. EPA has
repeatedly concluded that valid scientific data showed no link between 4-PCH or any
other carpet VOC emission, and adverse health effects.
Even though carpet emissions have been declared to produce no adverse health effects, the issue of new carpet odor had to be addressed. As a result, the SBLC member companies have reduced VOC emissions by 95 % since 1988. With present low
VOC latex and proper drying technique, carpet manufacturers today can produce
odor free carpet. As well as creating an odor free environment for the carpet consumer by reducing VOCs, the trend toward ammonia free latex is also creating a
more worker friendly environment in the manufacturing site.
Even though alternative backing systems are available, SB latex still accounts for
over 90 % of the carpet back-coating market. Due to its performance, versatility, and
economics, SB latex continues to afford the carpet manufacturer the best value in
back-coating systems today and for the foreseeable future.
265
266
References
1 Floor Covering Weekly, Statistical Report
2
3
4
5
99, 49(19), July 17/24, 2000.

US Department of Commerce, Bureau
of Census, Current Industrial Reports,
Carpet and Rugs, 2000.
Intercontuft, 2000.
American Plastics Council Monthly
Statistical Report, December, 1999.
L. D. Martino, Carpet Backfinishing
Review, Brunswick Corporation, 1975.
6 Carpet and Rug Institute, 1999 Industry
Review, 1999.
7 CRI The Tufted Carpet Industry, The
Pride of Georgia, History and Current

Statistics, 2000.
8 Carpet and Rug Institute, Carpet
Primer, 1997.
9 55 Federal Register 17404, April 24,
1990.
10
Non-wovens Application
Koichi Takamura, Marilyn Wolf, and Jim Tanger
10.1
Introduction
Non-wovens are described as flat, porous sheet or web structures produced by binding and interlocking fibers, yarns, or filaments by mechanical, thermal, chemical, or
solvent means. They are porous sheets that are made directly from separate fibers,
molten plastic or plastic film. They are not made by weaving or knitting and do not
require converting the fibers to yarn.
Non-woven fabrics are engineered fabrics that may be of single-use, limited life, or
very durable. They provide specific functions such as absorbency, liquid repellency,
resilience, stretch, softness, strength, flame retardancy, washability, cushioning, filtering, bacterial barrier and sterility. These properties are often combined to create
fabrics suited for specific jobs, while achieving a good balance between product uselife and cost.
In combination with other materials, non-woven fabrics provide a spectrum of
products with diverse properties, and are used alone or as components of apparel,
home furnishing, health care, engineering, industrial, and consumer goods. They
are categorized according to application as either disposables or durables. Some
familiar products made with non-wovens are listed in Tab. 10-1 [13].
The worldwide production of non-wovens is estimated at 2.7 million tons (or
6.0 billion pounds) in 1999 [46]. Western Europe accounts for approximately 35 %
of the world production of non-woven products, followed by North America (30 %),
China (12 %), Japan (12 %) and others, as shown in Fig. 10-1. The value of nonwoven product shipment in North America reached an all-time high in 1997 with an
approximate value of $2.8 billion [7] and disposables account for nearly 70 % in
value. The non-woven industry in North America is expected to grow at 23 % annually and to be $3.2 billion in 2002.
China and Japan dominate non-wovens production in Asia followed by Taiwan
and Korea as shown in Fig. 10-2. Double-digit growth is expected in these countries,
and production in China and Japan reached to 350 000 tons each in 2000 with an an-
267
268
10 Non-wovens Application
Tab. 10-1
Some familiar products made with non-wovens.
Disposable products
Diapers, sanitary napkins and tampons
Sterile wraps, caps, gowns, masks
Drapings used in the medical field
Household and personal wipes
Filtration media
Laundry aids (fabric-dryer sheets)
Embroidery backing
Durable products
Apparel interlining
Carpet backing and upholstery fabrics, high loft padding and backing
Wall coverings
Agricultural coverings and seed strips
Electronic components (i.e. battery separations, disk liners, insulation liners, polishing cloth, etc.)
Envelopes, tags and labels
Insulation and house wraps
Roofing products
Civil engineering fabrics/geotextiles
Global Production of Nonwovens

W. Europe
Asia
Global non-woven production

reached to 2.7 million tons in 1999. Western
Europe and Asia produced approximately
35 % each.
Fig. 10-1
North America
nual growth rate of 11 % [5, 6]. China non-woven production increased 87 times during the last two decades from 4000 tons in 1980.
The North American market for disposable applications was approximately
$1.9 billion in 1997, and represent roughly 15.5 billion yards (13 billion m2) and
900 million pounds (400 000 tons) of material. As seen in Fig. 10-3, filtration and
medical applications represent nearly 60 % of the dollar value, but fewer than 20 %
Nonwoven Production in Asia
Taiwan
100 kton
Japan
315 kton
China
315 kton
China and Japan are two major

non-woven producers in Asia. They reported
11 % annual growth in 2000.
Fig. 10-2
Korea
100 kton
10.1 Introduction
Total $1.9 billion
Total 15.5 billion yard (13 billion m )
Dryer
Sheets
Wipes
Wipes
Dryer
Sheets
Filtration
Filtration
Medical
Cover
Stock
Cover
Stock
Medical
Fig. 10-3 1997 figures show disposable products account for nearly 70 %
in the dollar value and 85 % in volume in North America.
of disposable square yard volume. Cover stock applications dominate disposable volume, and approximately 80 % of this volume is used for diaper production [7].
The volume for durable non-wovens exceeds that used for disposables in Europe.
Europe has a longer history in the use of durable non-wovens, in particular geotextiles and roofing substrates. This is in contrast to the North American market, where
disposable non-wovens play a stronger role as discussed above.
Electronic, Interlining, and Furniture/Bedding/Home applications account for approximately 55 % of $0.9 billion non-woven materials in durable applications in the
North American market, but furniture, bedding and home furnishing applications
are the largest volume (42 %) of non-wovens in this durable category as shown in
Fig. 10-4.
Total $ 0.9 billion
Total 3.1 billion yard 2 (2.6 billion m2 )
Automotive
Electronic
Construction
Materials
Construction
Materials
Automotive
Electronic
Interlining
Coating/ Laminates
Coating/
Laminates
Interlining
Geotextiles
Geotextiles
Furniture/
Bedding/Home
Furniture/
Bedding/Home
Fig. 10-4 Electronic, interlining and furniture related applications account

for 55 % of $ 0.9 billion in durable applications in North America, but
furniture related applications are the largest in volume.
North American, European and Japanese markets are shown in Fig. 10-5 comparing total weight of products in 1999. Hygiene (cover stock in North America and consumer goods in Japan) medical products and wipes account for greater than 50 % of
269
270
North American Production (800 kton)
European Production (910 kton)
Coaging/
Laminates
Civil
Engineering
Geotextitle
Coating
Substrates
Filtration
Automotive
Carpet Backing
Building
Medical
Furniture/
Bedding/ Home
Hygiene
Construction
Materials
Others
Interlining
Electronic
CoverStock
Garments
Wipes
Dryer Sheets
Footwear/
Leather Goods
Floor
Coverings
Wipes
Upholstery/
Bed Linen
Japanese Production (315 kton)

Others
Medical
Interlinings
Filtration
Consumer
Goods
Industrial
Products
Construction
Medical
Fig. 10-5 Non-woven applications in North America, Europe and Japan

are compared by weight of products in 1999. Hygiene, medical and wipes
account for greater than 50 % in all these continents.
total production in these continents, though consumer goods in Japan appear to include some durable products.
10.2
Manufacturing Systems
Early thrust in non-woven usage emphasized replacing traditional knits and woven
fabrics in low-end applications. During this initial phase, proprietary technology was
used to produce fabric structures that performed not only better than items they
were designed to replace, but often when traditional fabrics could not. As a result,
new applications and markets were established and the industry expanded. Many
non-woven products listed in Fig 10-5 were virtually non-existent a generation ago.
The basic non-woven manufacturing systems have four principal elements or
phases: fiber selection and preparation, web formation, web consolidation, and finishing treatments.
10.2 Manufacturing Systems
10.2.1
Web Formation
Four basic methods are used to form a web, and non-wovens are usually referred to
by one of these methods: dry-laid, spun-laid, wet-laid and other techniques. Carding,
garnetting and air-laying are examples of the dry-laid processes. The dry-laid processes provide maximum product versatility, since most textile fibers and bonding systems can be utilized and conventional textile fiber processing equipment can be
readily adapted with minimum additional investment.
The wet-laid process is similar to paper making, where a dilute slurry of water and
fibers are deposited on a moving wire screen and drained to form a web. A wide
range of natural, mineral, and synthetic fibers of varying length can be used.
In the spun-laid process, polymer granules are melted and molten polymer is extruded through spinnerets. The continuous filaments are cooled and deposited on to
a conveyor to form a uniform web. Even though filaments adhere to one another
during this cooling process, this cannot be regarded as the principal method of bonding. The spun-laid process (also known as spun-bonded) has the advantage of giving
non-wovens greater strength, but raw material flexibility is more restricted.
Other techniques include a group of specialized technologies in which the fiber production, web structure and bonding usually occur at the same time and in the same
place, as melt-blown and flash spun web formation methods.
Detailed description of these technologies can be found elsewhere [1, 4]. As seen in
Fig. 10-6, spun-laid and dry-laid are two preferred processes both in North America
and Europe. The spun-laid process showed the strongest growth during a last
decade [1, 7]. Products produced by the spun-laid technique account for 2025 % of
the market in Japan and China [5, 6].
North American Market by Process
European Market by Process

Wetlaid
Wetlaid
Spunlaid
Spunlaid
Drylaid
Drylaid
Other
Fig. 10-6 Comparison of web formation technologies in North America

and Europe. Spun-laid and dry-laid are two preferred processes both in
North America and Europe.
Other
271
272
10.2.2
Web Consolidation
Webs produced with the above described processed have limited strength in their
unbonded form and need to be consolidated. There are three basic types of bonding;
thermal, mechanical and chemical. The thermal bonding uses the thermoplastic
properties of certain synthetic fibers to form bonds under controlled heating. In
some cases the web fiber itself can be used, but often a low melt fiber or bi-component fiber is introduced at the web formation stage to perform the binding function
later in the process.
In mechanical bonding the strength of the web is obtained through the physical
entanglement of the fibers. Needle punching and hydro-entanglement (also known
as spunlace) are two main mechanical bonding processes. Needle-punching can be
used on most fiber types, whereas hydro-entanglement is mainly applied to carded
or wet-laid webs.
Chemical bonding mainly refers to the application of a latex dispersion based
bonding agent to the web. The major binder application methods include saturation,
printing, spraying, and foaming. Factors to consider when consolidating a web with
binder are the end-use characteristics, the type of web substrate that is used, process
compatibility, line speed, drying capacity and cost [1].
Carded thermally bonded technology is losing significant share in the cover stock
market in North America and spun-bonded non-wovens accounted for 75 % of cover
stock in 1999 (Fig. 10-7). In contrast widely different technologies are utilized to produce non-wovens for wipes. Hydro-entangled products are expected to grow due to
superior strength and softness [7].
Cover Stock
Wipes
Melt Blown
Carded
Thermal
Bounded
Unbounded
Carded
Web
Other
Carded
Thermal
Bounded
Hydroentangled
Unbounded
Carded
Web
Carded
Chemical
Bounded
Wet Laid
Spunbounded
Fig. 10-7 Spun-bonded products dominate the cover stock market in

North America due to better performance and lower cost. Hydro-entangled
products are expected to grow in wipes.
Air Laid
10.3 Polymer Dispersions for Chemical Bonding
10.3
Polymer Dispersions for Chemical Bonding
Most non-wovens use 5 % to 50 % of polymer binder to provide one or more of following characteristics: softness, non-linting, smoothness, stiffness, dry and wet tensile strength, tear resistance, resiliency, flame retardancy, heat sealability, water repellency, absorbency, durability, dry cleanability, abrasion resistance, pilling resistance, color fastness, and bulkiness [1]. An article by Wiaczek [3] estimates that total
latex consumption in the US non-wovens market will reach 160 000 dry tons in 2001.
Latex binders fall into following two categories: those that provide rigidity to a
product and those that render a web soft and drapeable. Acrylics are the predominant binders used in non-wovens as shown in Fig. 10-8 [1, 8]. They are versatile and
offer the ultimate in durability, color stability and dry/wet performance. Ethylene
vinyl acetate binders provide high tensile strength and excellent absorbency. They
are less costly than acrylics. Styrene-butadiene latex offers an excellent combination
of flexibility and toughness. It also provides hydrophobicity and durability to products. Vinyl acetate binders offer good dry strength and toughness but tend to be hydrophilic. Vinyl acrylics are more hydrophobic than vinyl acetate binders, and maintain excellent toughness, flexibility and better color stability. Chlorinated polymers
such as poly(vinyl chloride) and ethylene vinyl polymers promote flame retardancy,
especially together with antimony oxide [11]. Characteristics of these latex binders
and typical applications of non-woven products are summarized in Tab. 10-2.
Vinyl
Acrylic
Vinyl
Chloride/
Others
Vinyl
Acetate
Acrylic
Ethylene
Vinyl
Acetate
Fig. 10-8 Acrylics are the predominant
binders used in non-wovens, but the
vinyl acetate ethylene latex showed
strongest growth during the last decade
StyreneButadiene
For all these latices, monomer compositions are optimized to obtain desired
physicochemical properties, such as glass transition temperature, Tg, molecular
mass, cross-linking density, colloidal stability and specific surface functionality for
post chemical reactions.
273
274
Tab. 10-2
Basic characteristics and typical applications of latex binders used for non-wovens pro-
duction.
Latex binder type
Characteristics
Typical applications
Polyvinyl acetate
Resilient, somewhat stiff,

moderate durability,
limited washability and
dry-cleanability
Highloft webs, filter media,

industrial, home furnishings
Acrylic
Excellent adhesion, stiff to soft,

excellent durability,
launderability, dry-cleanability,
good cross-linking
Coverstock, interlinings medical/

health care, fabric softener, carder,
wet wipes
Vinyl acetateacrylic copolymer
Flexibility, good adhesion,

good solvent resistance
Medical and/or surgical, wipes,

coverstock
Ethylene-vinyl acetate
Good softness, durability

and adhesion
Coverstock, wipes, air-laid pulp
Styrene-butadiene
Good tear and tensile
Filters, wipes, home furnishings
Poly(vinyl chloride)
Stiff to soft, can be plasticized,

heat sealable, low temperature
cure
Scouring pads, filter media,

wall covering
Ethylene-vinyl chloride
Excellent mechanical stability
Underpads, highloft webs
Poly(vinyl alcohol)
Resilient, water absorbent
Filter media, medical
Acrylonitrile-butadiene
copolymer
Resilience, heat sealable,

launderability, dry-cleanability
Synthetic leather
As shown in Fig. 10-7, widely different technologies are utilized to produce wipes.
This is also applicable to the binder application method. The acrylic latex can be
applied through saturation, foam impregnation or print bonding as shown in
Tab. 10-3.
Tab. 10-3
Typical latex-based formulations for wipes with saturation, foam and print bonding methods.
Saturation
Foam Impregnation
Print Bonding
Materials
Weight,
g
Solids,
%
Materials
Weight,
g
Solids,
%
Materials
Weight,
g
Solids,
%
Acrylic latex
Water
Defoamer
Surfactant
100
120450
0.1
01
55
Acrylic latex
Water*
Ammonia*
Surfactants
100
80150
55
100
150450
55
05
50
Acrylic latex
Water1
Dye2
Thickener1
*Adjust to 10-25% solids
100
50
*Adjust to 15-30% solids and pH=8

Typical foam weight of 70150 g/liter
Adjust to 1015% solids and 10Pas

viscosity
Add to the desired color
10.4 Application Test Methods
10.4
Application Test Methods
A series of well-defined standardized test methods have been established through

various trade organizations, government and university research institutes. INDA
(Association of the Non-woven Fabrics Industry) Standard Test [2] and EDANA (European Disposables and Non-wovens Association) Recommended Test Method [4]
are two major standards for non-wovens. International Standardization Organization (ISO) and the American Society for Testing and Materials (ASTM) refine and
approve a wide range of test methods developed by these trade organizations. INDA
Standard Test Methods, and some corresponding EDANA, ASTM and ISO test
methods are listed in Tab. 10-4.
The crosslinking resins such as melamine can be used to enhance wet and dry tensile strength, moisture resistance, heat resistance and solvent resistance (dry-cleanability) of non-woven fabrics. Figure 10-9 illustrates examples of the stiffness improvement of an acrylic latex bonded non-woven sheet as a function of the latex level
in the sheet at two different levels of the melamine resin [12].
Here, the stiffness was measured by the Handle-O-Meter (IST 90.3), where a fabric specimen is pushed through a slot with a blade on an arm at a constant rate and
the resultant force on the center point of the fabric measured. Dent [13] recently reported through theoretical analysis that the initial slope of the load-deflection curve
Handle-O-Meter Reading, mN
250
with 10%
Melamine
200
150
100
with 5% Melamine
50
without Melamine
0
0
20
40
% Acrylic in Sheet
Fig. 10-9 Improvement in the stiffness of an acrylic latex bonded
non-woven sheet as a function of the latex level.
60
275
IST GL non-wovens
IST GL felts
IST 1
IST 10.1
IST 10.2
IST 10.3
IST 20.1
IST 20.2
IST 20.3
IST 20.4
IST 20.5
IST 20.6
IST 30.1
IST 30.2
IST 40.1
IST 40.2
Absorption
Non-woven absorption
Rate of sorption of wiping materials
Demond absorbency
Abrasion resistance
Inflated diaphragm
Flexing and abrasion
Oscillatory cylinder
Rotary platform
Martindale
Uniform abrasion method
Bursting strength
Diaphragm
Non-woven burst
Electrostatic properties
Surface resistivity
Decay
INDA standard
test method
Guideline test methods for evaluating non-woven felt

Non-woven vocabulary
Guideline test methods for non-woven fabrics
Description
Tab. 10-4 INDA Standard Test Methods for non-wovens and the corresponding EDANA, ASTM and ISO tests.
ERT 80.3-99
ERT 230.0-99
ERT 10.3-99
ERT 1.3-99
EDANA recommended
test method
ASTM D3786-87
ASTM D3886-92
ASTM D3885-99
ASTM D4157-92
ASTM D3884-92
ASTM D4966-98
ASTM D4158-92
ASTM D1117-99
ASTM method
ISO 9073-6
ISO 13938-1
ISO 12947-3
ISO 9073.6
ISO
276
IST 50.1
IST 50.2
IST 60.1
IST 60.2
IST 70.1
IST 70.2
IST 70.3
IST 70.4
IST 80.1
IST 80.2
IST 80.3
IST 80.4
IST 80.5
IST 80.6
IST 80.7
IST 80.8
IST 80.9
IST 90.1
IST 90.2
IST 90.3
IST 90.4
Optical properties
Opacity
Brightness
Permeability
Air permeability
Water vapor transmission (multiple tests)
Liquid strike-through time
Water vapor transmission (Mocon)
Repellence
Surface wetting spray test
Penetration by water (rain test)
Penetration by water (spray impact test)
Penetration by water (hydrostatic pressure test)
Penetration by saline solution (automated mason jar test)
Water resistance hydrostatic pressure test)
Penetration by oil (hydrocarbon resistance)
Alcohol repellence of non-woven fabrics
Non-wovens run-off
Stiffness
Cantilever
Gurley
Handle-O-meter
Drape
INDA standard
test method
Binder properties
Resin binder distribution and penetration
Appearance and integrity of highloft batting
Description
ERT 90.4-99
ERT50.5-99
ERT 152.0-99
ERT 120.1-80
ERT 170.0-89
ERT 120.1-80
ERT 150.4-99
ERT 140.1-99
ERT 110.1-78
ERT 100.1-78
EDANA recommended
test method
ASTM D5732-95
ASTM D737-96
ASTM D5908-96
ASTM D4770-00
ASTM method
IS09073-7
ISO 811-1981
ISO 811-1981
ISO 4920-1981 (E)
ISO 9073 8:1995
ISO 2471-198
ISO 2470-1997
ISO

277
Continue.
IST 120.5
IST 130.5
IST 140.1
IST 150.1
IST 150.2
IST 160.1
IST 160.2
IST 160.3
Weight
Non-wovens mass per unit area
Friction
Static arid kinetic
Dry-cleaning
Resistance
Appearance and integrity of highloft batting
Linting
Particulate shedding (dry)
Particulate shedding (wet)
Fibrous debris from non-woven fabrics
IST 120.4
IST 120.1
IST 120.2
IST 120.3
IST 110.1
IST 110.2
IST 110.3
IST 110.4
Tensile
Grab
Seam strength
Internal bond strength
Strip
Thickness
Thickness of non-woven fabrics
Highloft non-wovens
Highloft compression and recovery (measurematic)
Highloft compression and recovery
(plates and weights, room temperature)
Highloft Compression and Recovery
(plates and weights, high temperature, high humidity)
IST 100.1
IST 100.2
IST 100.3
INDA standard
test method
Tear strength
Elmendorf
Trapezoid
Tongue
Description
Tab. 10-4
ERT 220-0-96 & 300-84
ERT 40.3-90
ERT 30.5-99
ERT 20.2-89
ERT 70.4-99
EDANA recommended
test method
ASTM D2724-87
ASTM D5729-97
ASTM D5736-95
ASTM D5035-95
ASTM D5034-95
ASTM D1683-90A
ASTM D5734-95
ASTM D5733-95
ASTM method
ISO 9073-2:1995(E)
ISO 9073-3
ISO 13934-2:1999
ISO 1974-1974(E)
ISO 9073-1997(E)
ISO
278
INDA
IST 10.1-95
According to
ASTM D 1776
In MD direction cut 75 mm
and a length sufficient
so the strip weight
is 5 0.1 g
Wire basket, height 8 cm,

diameter 5 cm,
weight 3 to 8 g,
number 20 to 26 gage B&S
copper wire, 2 cm mesh;
liquid container;
stopwatch
Drop basket from height

of 25 mm into liquid.
Time for specimen to
become completely wet
is measured
Absorbency time in s
Properties
Sample
conditioning
Test specimen
size
Equipment
used
Procedure
Number of tests
Properties
reported
Liquid absorbency
time in s
Drop basket from

height of 25 1 mm
into room temp. liquid.
Record time for the
basket to sink completely
below the surface of the
liquid
Wire basket, height 8 cm,

diameter 5 cm,
weight 3 1 g,
2 cm mesh;
0.5 mm diameter
stainless steel wire;
liquid container;
stopwatch
In MD direction cut
76 1 mm wide and a
length so the strip weight
is 5 0.1 g
Condition test
specimens according
to ERT 60.2-99
EDANA
ERT 10.3-99
Excerpt from 2000 Global Comparison of Test Methods for

non-woven absorption [10]. (Absorption Liquid Absorbency Time)
Tab. 10-5
ASTM
Average, max., and

minimum absorption
time in s, the volume
used, and type of
paper used
10
Drop liquid from

height of at least
10 mm on to the
specimen. 1.0 mL
0.1 mL and 0.01 mL
are the amounts used.
Drop measuring
device. A specimen
support consisting
of a non-absorbent
material 100 100 mm
with a central hole
of approx. 40 mm
diameter
Approximately
100 mm 100 mm
According to
TAPPI T 402
TAPPI
T432 OM-94
ISO
ISO9073-6
Absorbency in s
(of bleached textiles)
Deliver one drop

of water (21 3 C)
1.0 0.1 cm from
hoop. It is important
to condition the
fabric.
Embroidery hoop
15 cm dia. or
more. Burette,
delivering
1525 drops
per mL; stopwatch;
burette stand;
light source
Swatch or skein
to fit tightly over
embroidery hoop
As directed
in EDANA 10.3-99
As directed
in EDANA 10.3-99
As directed
in EDANA 10.3-99
As directed in
EDANA 10.3-99
At moisture
According to
equilibrium
ISO 139
65 2 % RH, 21 1 C
AATCC
79-1995

279
280
gives the fabric stiffness or flexural rigidity, while the ratio of maximum load to initial slope gives the fabric friction or smoothness. Thus, a single measurement can
measure two basic parameters governing the fabric hand or feel.
In addition, TAPPI (Technical Association of the Pulp and Paper Industry) is active in the wet-form non-woven segment of the industry [9]. Some of the standard
test methods established by AATCC (American Association of Textile Chemists and
Colorists) are also applicable to non-wovens. INDA recently published 2000 Global
Comparison of Test Methods [10], which conveniently compares standard test
methods by the above listed organizations. Table 10-5 is an excerpt from the Absorption Liquid Absorbency Time, which demonstrates two different principles used to
quantify similar properties.
Oathout [14] has discussed the water-absorption characteristics of eleven wiping
materials including one 100 % wood pulp with binder, paper making process, six hydro-entangled, two knitted polyester and one woven cotton. In addition to the static
absorption measurements specified by IST 10.1 and 10.2, he describes results of the
dynamic wiping efficiency, or wipe-dry test. In this test, a wiper is affixed to the
bottom side of a 1 kg sled, which is placed on a stainless steel pan. A known amount
of the liquid challenge was placed in front of the sled pulled into and through the
pool at a wiping speed of 25 cm s1. The test tries to simulate manual wiping operations. His results demonstrate that fabrics with bulky character, imparted through
creping or stitch-bonding exhibited superior wipe-dry.
281
References
1 E. A. Vaughn, Non-wovens World
5
6
7
Factbook 1991, ISBN 0-87930-227-5,

Miller Freeman Publications, 1991.
Association for the Non-woven Fabrics
Industry, Cary, North Carolina, USA;
www.INDA.org
P. Wiaczek, Comparison of Trends in
Latex Emulsions for Non-wovens and
Textiles: China and the United States,
International Non-wovens Journal, 1999.
EDANA European Disposables and
Non-wovens Association, Brussels,
Belgium, www.edana.org
All Nippon Non-wovens Association;
www.anna.gr.jp
China Non-woven Technical Association;
www.chinanonwovens.com
Association of the Non-woven Fabrics
Industry, Analysis The Non-woven
Industry in North America, Cary,
North Carolina, USA.
B. M. Koltisko, Vinyl Copolymer Materials, Principles of Non-wovens, 221248,
1992, Association of the Non-woven
Fabrics Industry.
9 1998-1999 TAPPI Test Methods, 1998,
10
11
12
13
14
TAPPI Press, Atlanta, GA;

www.tappi.org
2000 Global Comparison of Test
Methods, Association of the Non-woven
Fabrics Industry, 2000.
E. D. Weil, Flame Retardant Nonwovens, Non-wovens Binders and
Additives Seminar, 53-61, TAPPI
PRESS, 1988.
P. D. Wallace, Crosslinker resins in
non-woven binder systems, Non-wovens
Binders and Additives Seminar,
TAPPI Press, 1988.
R. W. Dent, An analysis of fabric Hand
and Feel, International Non-wovens
Journal, Vol. 9, 2000.
J. M. Oathout, Determining the Dynamic
Efficiency with which Wiping Materials
Remove Liquids from Surface, International Non-wovens Journal, Vol. 9,
2000.
11
Applications in the Leather Industry

Johannes P. Dix and Werner Kirchner
11.1
Introduction
Leather making is an ancient art. Methods for converting the fresh animal hide into
leather (Fig. 11-1) have been known for approximately 100 000 years [1].
Fig. 11-1
Structure
of leather.
Stone Age man, for example, used smoke or fat for preserving the hides. Tanning
with vegetable tannins (vegetable tanning) and with alum, a naturally occurring aluminum sulfate (mineral tanning), then became established in the Middle Ages. It
was only about 100 years ago that the development of chrome tanning (tanning with
chromium salts) produced the decisive breakthrough which has made it possible to
produce leather in an efficient, economical manner.
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284
11 Applications in the Leather Industry
The excellent properties of chrome-tanned leather opened up new fields of use and
made possible the mass production of leather goods, for example in the shoe or apparel leather sector. This created the need for fashionable styling of these leather
goods and for making them resistant to soiling and damage. It is this function that is
performed by leather finishing [17].
11.2
Market Situation
To describe the economic importance of polymer dispersions, a brief look at the

structure of the leather industry is helpful.
The leather industry is one of the oldest and most complex industries world-wide.
It is closely coupled to raw hide production and hence to meat consumption. Livestock is bred world-wide. Accordingly, tanneries are located all around the globe. The
articles made from leather differ greatly, ranging from shoe upper leather to apparel
leather and to automotive leather.
The leather industry has undergone global changes in the last decades. This structural change is still not complete. It is driven by the high proportion of leather processing and leather production costs attributable to wages (Fig. 11-2). This has led
and is still leading to a relocation of leather manufacture from the traditional industrialized countries of Europe and from the U.S. to low wage countries, especially in
the Far East (Fig. 11-3). At the same time, the industry, which is predominantly
based on small and medium size companies, is undergoing a process of consolidation.
Costs of leather production in Europe: ca. 7.5 e/m2
Breakdown of leather production costs (without raw hide costs)

in Europe.
Fig. 11-2
Regional distribution of finished leather production.
Fig. 11-3
11.2 Market Situation
Since finished leather production is determined by raw hide production (Fig.11-4),

the annual growth rate of leather produced is only small (ca. 0.8 % year1). The predominant portion of leather produced is cattle hide (ca. 60 %), followed by small-animal skins (sheep, goat) at about 30 % and pork leather at ca. 10 %.
Fig. 11-4 World-wide raw hide

production in 1990 to 1995.
The market volume of chemicals used in leather manufacture is about Euro

2.5 billion world-wide. The largest segment by far in terms of value is the product
range for tanning (ca. 50 %), followed by finishing (ca. 30 %). The finishing segment
subdivides into the categories of binders/top coats, finishing dyes and finishing auxiliaries (Fig. 11-5).
Finishing market volume: ca. e 0.75 billion
Fig. 11-5 Distribution of market

volume in leather finishing between
individual product ranges.
Base coats and pigmented coats are today already commonly applied in low-solvent and solvent-free processes. Polyacrylate or polybutadiene dispersions are preferred here. Polyurethane dispersions and casein formulations are used as well,
depending on the end use. In the case of top coats, aqueous systems based on
polyurethane dispersions are used as well as, still, solvent-containing lacquers or
emulsions. However, here too increasingly tougher environmental regulations are
driving a changeover to solvent-reduced and waterborne systems.
About 180 000 tons annum1 of binders are estimated to be used in leather finishing world-wide. Of that, about 60 % are polyacrylate and polybutadiene dispersions
and about 12 % polyurethane dispersions (Fig. 11-6). At about 20 %, the solvent-containing lacquers still account for a relatively large share today. However, this share
will in future decrease further in favor of polyurethane dispersions.
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World-wide use of binders
in leather finishing.
Fig. 11-6
11.3
Leather Finishing
The tanned animal hide, i.e., the leather, usually becomes a sailable article with an
upgrading post-treatment. The further processing takes place in two stages:
In wet finishing, the character of the leather article (softness, strength, water repellency) is substantially determined by the retanning and the fat-liquoring operations. The leather is also dyed. This is done using soluble dyes.
This is followed by the further processing of the dried leather (crust). It is this operation which is commonly referred to as finishing. It makes a significant contribution to enhancing the performance characteristics. A surface coating provides better
protection against wetness, soiling and mechanical action. Surface properties such
as hue, luster or feel and also light- or rub-fastness are imparted or improved. At the
same time, leather damages or unlevelness (grain defects, scratches) are covered up.
The finishing of buffed leather or split leather permits the use and upgrading of otherwise less suitable leather qualities. Similarly, many fashion effects are not possible
without finishing.
Interestingly, leather finishing was one of the first industrial applications for polymer dispersions. In Corialgrund E, the then I.G. Farben commercialized a dispersion based on poly(methyl acrylate) in 1931. This was the first polymer dispersion on
the market and the starting point for the immense development of polymer dispersions for other applications too.
While Corialgrund E was primarily used as a barrier to avoid migration of the plasticizer out of the nitrocellulose lacquers then used and thus to counteract finish embrittlement, the immense potential of polymer dispersions as binders for finishing
was soon recognized. They make it possible to apply thicker finish coats on the
leather. The thermoplasticity of polymer dispersions makes it possible to emboss the
leather surface and so create any desired surface texture. The use of polymer dispersions provides not only better adhesion of the finish to the leather, but also highly
flexible finishes that are stable to light and aging. It is accordingly no surprise that
polymer dispersions have become widely established in leather finishing.
11.3 Leather Finishing
11.3.1
Modern Finishing
The various leather articles with their specific requirements each require a specific
optimized process in the tannery. Classifying leather finishes according to, say, the
binders used or the method of application, the appearance or the ready-produced
leather article is thus possible only to a limited extent. Frequently there are many different ways of producing the desired article. Leather finishing is therefore regarded
as being more an art than a science.
11.3.2
General Construction of Finishing Coats
The finish is generally made up of a number of coats. Each coat has a certain purpose. The coating technique can be the same for each coat, but need not be. It
depends primarily on the type of leather used and the effect desired.
11.3.3
Spray Dyeing
Metallized dyes, for example, are used to dye, or correct the hue of the surface of
leathers which have not been drum dyed and to match it to the hue of the finish. As
a result, damages to the finish in the course of the use of the leather article are less
pronounced.
11.3.4
Grain Impregnation
Grain impregnation is used to improve the firmness of the buffed grain layer. The
impregnating float or liquor has to absorb into the leather and must not become deposited at the surface. To this end, very dilute, finely divided acrylate dispersions
(solids content about 10 %) are applied in combination with capillary-active substances known as penetrators.
11.3.5
Base Coat
Depending on the crust leather used, the adhesion of the finish layer to the leather
has to be improved in some cases by means of a separate base coat. Adequate adhesion is the precondition for many application properties and important to achieve the
required physical fastnesses for the ready-produced leather articles. Soft, finely divided polyurethane dispersions have won out in this sector over polyacrylate dispersions.
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288
11.3.6
Pigment Coat
Its components are pigments, binders and auxiliaries such as waxes and fillers. The
pigment coat imparts the desired appearance to the leather and levels out the leather
surface. The choice of binders is made according to the finishing effect and fastness
profile desired. Generally, polyacrylate dispersions are used in the pigment coat.
A distinction is made between finishes which preserve the natural character of the
leather (e.g., semi-aniline finish) and high hiding finishes which receive the desired
grain structure through embossment. Finely divided acrylate dispersions (<100 nm)
are useful for less hiding finishes. The butadiene-based dispersions used in leather
finishing have high filling effect and can enhance the hiding power of the finish.
As well as the degree of hiding, the hardness/softness balance of the pigment coat
has a significant influence on application and processing properties. Especially on
thin, soft leather types (e.g., nappa), hard pigment coats lead to an unwanted doubleskin appearance. Soft binders, however, tend to be tacky and cause processing problems in leather production. Auxiliaries (waxes and fillers) can be used to reduce the
tackiness within certain limits. The glass transition temperatures of the polyacrylate
dispersions used are typically between 10 and +10 C.
Polyurethane dispersions are used in the pigment coat in particular when very
high fastness properties are required.
11.3.7
Top Coat
The top coat determines the ultimate appearance and the feel of the leather surface.
It further substantially influences the fastness properties of the finish. Instead of organic, solvent-containing lacquers and top coats (e.g., nitrocellulose emulsions), today there is an increasing trend towards waterborne top coat systems. These are usually polyurethane dispersions which, owing to their specific properties (no emulsifier, good film formation despite relatively high hardness), are superior to polyacrylate
dispersions in application terms.
The degree of luster of the finish is controlled using matting agents (e.g., silica derivatives).
11.4
Application Methods
The application method used depends not only on the processing step but also on
the type of leather and the desired finishing effect. Currently applied methods of
coating will now be briefly described.
11.4 Application Methods
11.4.1
Spraying
Spraying is the most widely used method of application in leather finishing. Rotating
spray guns inside spray machines (Fig. 11-7) apply the low-viscosity finish liquor to
the horizontal leather. Even soft leathers can be processed by this technique.
Fig. 11-7
Spray machine.
Modern spray units are equipped with computer-controlled spray guns which recognize the outlines of the leather and so minimize overspray. They further operate
under high volume, low pressure conditions to reduce spray drift.
As well as the HVLP process there is the airless process whereby the spray jet is
not mixed with compressed air, but is generated by very high pressure in the spray
nozzle. This method is suitable for high amounts applied.
11.4.2
Roll Coating
Roll coating (Fig. 11-8) is the second most important method for application after
spraying. The leather passes between two rolls (color print roll and transportation
roll) by means of a transportation belt. The top roll transfers the relatively viscous
color to the leather. The texture and the direction of rotation (synchronous or reverse) of the color print roll determine the amounts applied. Soft leathers can be
processed on this machine only if the rolls turn in the same direction. Consequently,
these types of leather can be roll coated only with finishes that do not require high
amounts.
11.4.3
Curtain Coater
The casting process comes from the surface coating of wood. In this process
(Fig. 11-9) a casting head creates a curtain of liquid. The horizontal leather passes
through this vertically descending curtain. Casting finds application in particular in
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290

Fig. 11-8
Roll coater.
grain impregnation and in pigment finish applications for patent leather and buffed
leather. This technique is not suitable for processing very soft leathers, since they
buckle as they pass through the curtain of liquid. This application technology places
particularly high demands with regard to shear stability and foam control on the dispersions used. The use of antifoams is limited by wetting and flow-out requirements.
Fig. 11-9
coater.
Curtain
11.5 Binders
11.5
Binders
Binders are among the most important components of a finish system, whether it is
a pigment finish or a top coat. They bind the color-conferring pigments, which have
no inherent affinity for leather, and protect the leather surface through their filmforming property. Aqueous finishes generally utilize aqueous polymer dispersions.
As well as from binders and pigment preparations, finishes are prepared from rheological additives (thickeners, flow control agents, solvents in appropriate cases), matting agent, crosslinker and handle modifier. The following product classes are available as polymer dispersions:
polyacrylate (copolymers)
polybutadiene (copolymers)
polyurethanes
The multiplicity of possible monomer combinations and their different blend ratios, the various molecular weight distributions and degrees of crosslinking of the
polymers, the effect of process conditions and the colloid-chemical properties of the
dispersions make for an immense range of binder properties that can be obtained.
These include, for example, hardness and softness, elasticity, water resistance, coldflex stability and hiding power. In addition, film formation in the course of drying
has a decisive effect on many fastnesses of the finish. Owing to their different
chemistries, the three types of polymer dispersion differ in their application properties:
11.5.1
Polyacrylate Dispersions
Typical leather-finishing polyacrylate dispersions are based on ethyl acrylate or

copolymers of butyl acrylate with acrylonitrile or methyl methacrylate. Glass transition temperatures range from 10 C to +10 C. The polyacrylate dispersions used
are lightfast and compatible in the color batch. Owing to the monomers on which
they are based, polyacrylate dispersions are relatively inexpensive. They provide finishes having good application properties. However, they do not (as yet) meet the
highest requirements, as required for automotive leather for example.
11.5.2
Polybutadiene Dispersions
The polybutadiene dispersions used are customarily copolymers based on butadiene,

styrene and acrylonitrile. Their advantage is the substantial flexibility in thick layers,
as required in the finishing of split leathers for example. These systems are typically
crosslinked using zinc oxide. As the hiding component, polybutadiene dispersions
are also used in combination with polyacrylate dispersions. The double bonds in the
polymer make polybutadiene dispersions susceptible to oxidative aging (light, heat)
and sensitive to heavy metals.
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292
11.5.3
Polyurethane Dispersions
Polyurethanes are polyaddition compounds of isocyanates with polyols and/or

NH-functional compounds. Owing to the incorporation of hydrophilic groups in the
polymer, polyurethanes form stable usually anionically stabilized dispersions in
water. Unlike the systems described above, polyurethane dispersions can be made
without an emulsifier. Finishes with polyurethane dispersions are notable for a very
high fastness level. Flexing endurance, even at low temperatures, and rub-fastness
(after crosslinking) meet the highest standards. Owing to the hydrophilic groups,
polyurethane dispersions possess very good adhesion to leather. Their chemistry
makes carboxylate-stabilized systems pH-sensitive. Since monomer costs are distinctly above those of the acrylates, the use of polyurethane dispersions is mainly restricted to applications where the special properties of polyurethane dispersions are
essential.
Depending on the polyol component used, there are polyetherurethanes and polyesterurethanes. With regard to the isocyanate component, a distinction is made between aromatic and aliphatic monomers. The somewhat less costly aromatic systems, however, do not meet the extreme aging resistance requirements of automotive leathers, for example.
11.6
Production of Selected Leather Articles
Guideline recipes for finishes for some selected leather articles will now be used by
way of example to discuss the particular requirements that have to be met by the
polymer dispersions used. The finisher has to adapt these guideline recipes to the
leather to be finished and to the final properties demanded (feel, appearance, fastness).
11.6.1
Shoe Upper Leather
In terms of area, about 60 % of all leather produced is further processed as shoe upper leather. Shoe upper leather is the largest sector by far. Finish requirements are
dictated not only by the performance characteristics but also greatly by the particular
processing methods in the footwear industry.
In shoe making, the previously moistened leather is wiped (pulled) over the last by
heated irons. The folds appearing at the round edges of the shoe are smoothed away
by heat treatment with a hot air blower or a smoothing iron (the leather shrinks at
these high temperatures). So the finish has to be heat resistant. In addition, the finish must not scratch under the rubbing by the irons. The shoe sole is injection molded on in a further operation. The finish coat therefore has to be solvent-fast and the
dyes may not migrate into the shoe sole.
11.6 Production of Selected Leather Articles
Shoe upper leather requires good flexing endurance and good adhesion of the finish. Rub-fastness is of minor importance.
An example of a finish recipe for shoe upper leather is:
Leather type:
Cattle leather box-type
Base coat:
(depending on crust)
Pigment finish: Pigments 100 parts
Polyacrylate dispersion (40 %) 200 parts
Waxes (40 %) 50 parts
Casein binder (20 %) 100 parts
Water 350 parts
Top coat:
Polyurethane dispersion (35 %) 400 parts
Crosslinker (50 %) 30 parts
Water 550 parts
Thickener to a 4 mm Ford cup viscosity of approximately 24 s
Processing:
Pigment coat:
2 spraying (each ca. 80 g m2); dry
Plating: 2 s at 80 C and 150 bar
1 spraying (ca. 50 g m2); dry
Top coat:
The non-thermoplastic casein binder ensures processability in the wiping process
by reducing sensitivity to heat and improving hot rub resistance. Useful top coats include a nitrocellulose lacquer or an aqueous system with a very hard and hence plating-fast polyurethane dispersion. If necessary, the latter can be crosslinked to improve the rubfastness.
11.6.2
Apparel Leather
Apparel leather is the second largest sector after shoe upper leather. It accounts for
about 20 % of leather production in terms of area.
Apparel leathers preferably utilize sheep and goat leathers, but in some cases also
calf leather. Inevitably, fashion aspects are of primary importance with apparel
leathers. Other decisive aspects are wear properties such as softness and feel. With
regard to processing, the finish does not have to meet special requirements. One important performance characteristic is the light-fastness of the finish. Flexing endurance and rub-fastness are of lesser importance.
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294
An example of a finish recipe for apparel leather is:

Leather type:
Sheepskin
Pigment coat:
Pigment 50 parts
Spray dye 50 parts
Wax (40 %) 100 parts
Water 600 parts
Top coat:
Nitrocellulose emulsion (15 %) 500 parts
Wax (40 %) 20 parts
Water 480 parts
Processing:
Pigment coat:
Plating: 2 seconds at 80 C and 30 bar
Top coat:
Hydraulic ironing: 0.5 s at 120 C and 30 bar
Apparel leathers generally are not provided with a base coat. The pigment content
in the pigment coat has been reduced in favor of the spray dyes in order that a more
transparent, less coated appearance may be obtained for the finish. This is intensified by means of low concentration of the pigment finish and the large number of
spray applications. At present, solvent-containing top coats are still customary for apparel leathers, but, as with shoe upper leather, there is an increasing trend toward
the use of aqueous top coats.
11.6.3
Automotive Leather
Although the amount of leather processed in the automotive sector, as leather seats
or steering wheel leather, amounts to only about 2 % in terms of area of total leather
production (and rising), finishing chemical demand greatly outweighs those for shoe
upper leather or apparel leather, for example, because of the high fastness requirements. These high fastness requirements in the automotive leather sector include
depending on the specific requirements of the automotive manufacturer adhesions
of greater than 4 N cm1, flexing endurances (dry, 23 C) of 100 000 cycles and
30 000 cycles at 10 C. Similarly, rub-fastness has to meet extreme requirements:
>1000 rubs wet and a swelling resistance of >2000 rubs. In addition, these leathers
have to be aging resistant, i.e., they have to have adequate flexing endurance and rubfastness even after simultaneous exposure to heat, UV light and moisture. Nor may
any color shifts occur. To achieve these very high fastnesses it is predominantly necessary to use polyurethane dispersions.
11.6 Production of Selected Leather Articles
A guideline recipe for automotive leather is:

Leather type:
Cattle hide
Base coat:
Water 600 parts
Pigment coat:
Pigment 100 parts
Matting agent 80 parts
Water 290 parts
Thickener to a 4 mm Ford cup viscosity of 1618 s
Top coat:
Water 420 parts
Thickener to a 4 mm Ford cup viscosity of approximately 24 s
Processing:
Base coat:
Hydraulic ironing: 2 s at 80 C and 80 bar
Pigment coat:
1 spraying (70100 g m2); dry
Press embossing: 5 s at 80 C and 250 bar
1 spraying (5070 g m2); dry
Top coat:
The polyurethane dispersions used in the base coat are soft and very finely divided.
In contrast, the polyurethane dispersions used in the pigment coat are of medium
hardness. A portion of the polyurethane dispersions may also be replaced by polyacrylate dispersions. These must not have an adverse effect on the cold flexing endurance and so the polyacrylate dispersions used must have a low glass transition
temperature. The high rub-fastnesses are primarily achieved by the crosslinking of
the top coat. Useful crosslinkers include, for example, modified aliphatic polyisocyanates. The leathers are strongly embossed to conform the surface structure of the
leathers to the interior styling of the car.
As an alternative to the application method described, the base and pigment coats
can also be applied by synchronous roll coating. However, for this the recipe needs to
be adjusted to a smaller water quantity and a higher color batch viscosity (about 50 s
in 6 mm Ford cup).
11.6.4
Furniture Leathers
Furniture leathers, unlike automotive leathers, need less high fastnesses. Light-fastness is an exception. Primary furniture leather criteria are the feel properties and the
visual appearance of the leather. The use of soft polyacrylate dispersions has proved
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296
advantageous here. The greater use of inferior leather grades increasingly forces the
use of binders that provide high covering.
An example of a recipe for furniture leather is:
Leather type:
Cattle hide, buffed
Base coat:
(depending on crust leather used)
Pigment coat:
Pigment 100 parts
Matting agent 80 parts
Wax (40 %) 80 parts
Polybutadiene dispersion (40 %) 100 parts
Water 290 parts
Top coat:
Water 520 parts
Processing:
Pigment coat:
Embossing: 3 s at 80 C and 150 bar
Top coat:
Hydraulic ironing: 0.5 s at 120 C and 30 bar
The requisite hiding performance is achieved through the partial use of the
polybutadiene dispersion. Furniture leathers are softer than automotive leathers.
Embossing is accordingly done under less pressure. Since the fastness requirements
are lower, the top coat is less crosslinked and the applied amount is lower. For aesthetic reasons, the leather is briefly plated after the application of the top coat.
11.7
Test Methods in Leather Finishing
The primary purpose of the test methods is to ensure that the finished leathers are as
a whole suitable for the stated purpose. Accordingly, many test methods simulate the
stresses to which the finished leathers are exposed in use. It must always be noted in
this context that the leather itself has a substantial influence on the tests as well as
the finish coat on the leather. The different leather types vary greatly in thickness,
softness, surface structure, hydrophilicity, etc. Even a single hide is not homogeneous in itself. For example, fiber density, leather thickness, pore structure and absorbency are different in the belly than in the butt. For this reason, the corresponding test descriptions (e.g., DIN or ISO standards) provide precise definitions of the
areas of the leather from which the test specimens are to be taken. The test results
11.7 Test Methods in Leather Finishing
depend not only on the sampling position but also on the moisture content of the
leather specimens. The drier the leather is, the harder and less elastic are the leather
fibers. For this reason, the test methods prescribe that the test specimens must be
conditioned under standard atmospheric conditions (e.g., 50 % relative humidity
and 23 C or 65 % and 20 C).
Since finished leathers are predominantly used in the shoe industry, test methods
are largely adapted to these requirements. From experience, these test methods are
also suitable for evaluating other leather articles such as upholstery leather, apparel
leather and leather for bags and suitcases. The fastness level to be achieved varies
from article to article.
The International Union of Leather Technologists and Chemists Societies has developed, mostly binding, Methods of chemical leather analysis (I.U.C. methods)
and Methods of physical leather testing (I.U.P. methods). The German DIN sheets
for testing leather have in most cases been conformed to the above methods. I.U.F.
(International Union Fastness) describes guidelines and test methods drawn up by
the International Fastness Commission for leather dyes and dyed leathers.
The following methods are only the most important tests in common use. In addition, there are a multiplicity of specific test methods, either designed for certain
leather articles or required by certain customers.
11.7.1
Flexing Endurance
This test describes the behavior of the finish coat on repeated flexing of the leather.
It is among the most important tests of the finish.
The test is carried out both on dry and on wet leathers. It is described in
DIN 53351 or I.U.P. 20. The rectangular leather specimens are clamped into a flexometer (Bally flexometer, Fig. 11-10) with a fold. The rotational movement of the up-
Fig. 11-10
Bally flexometer.
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298
per axis makes the fold move back and forth on the surface of the leather. The finish
is assessed after 1000, 5000, 10 000, 20 000, 35 000, 50 000 flexes. For particularly demanding requirements, the test is continued to 100 000 flexes. Wet specimens are
flexed only 20 000 times at most. Any more will dry the leather too much.
After visual examination, the test specimen is evaluated according to the degree of
damage of the finish coat.
High flexibility is demanded, for example, by the shoe industry for work and
sports footwear. But leathers for the automotive sector (e.g., leather seats) also have
to meet such high requirements.
A variation of this test is flexing endurance at temperatures below freezing. Typical requirements are 30 000 flexes at 10 C or 10 000 flexes at 20 C.
11.7.2
Rub-fastness
The rub-fastness test examines resistance of the pigment coat to abrasion and the
transfer of color to other surfaces (crocking). The test is carried out on the VESLIC
rub-fastness tester (Fig. 11-11). This test is governed by the standards DIN 53339 and
I.U.F. 450.
Fig. 11-11
VESLIC rubfastness tester.
On a stretched leather a felt is rubbed back and forth. The felt is 10 mm 10 mm

in size and weighted with 1 kg. The leather is stretched 10 %. The test is customarily
carried out in three variations:
Dry rub-fastness:
dry leather, dry felt
Wet rub-fastness:
dry leather, wet felt
Swelling resistance: wet leather, dry felt
The damage or change in the finish coat and the transfer of color to the rubbing
element are assessed after fixed rubbing intervals. This method provides data on the
sensitivity of the finished leather surface to rubbing through, abrasion or transfer of
color from the pigment coat under both dry and moist conditions.
Rub-fastnesses are also tested using the SATRA rub-fastness tester. In this test
a rotating pad of felt acts on the leather surface under a certain pressure and at a
defined speed of rotation. The leather is evaluated after fixed numbers of cycles. This
test is likewise carried out with both a dry and a wet felt pad.
11.7 Test Methods in Leather Finishing
As a further variation, the test can be carried out under exposure to various,
defined test liquids: perspiration rub-fastness, chemical rub-fastness, etc.
11.7.3
Dry and Wet Adhesion
This test determines the adhesion of the finish coat to the leather surface. It also provides evidence of possible inter-adhesion problems within the finish coat. These
arise in particular when excessive auxiliary quantities (especially waxes) are used or
the crosslinking of the preceding layer is excessive. Ideally, the adhesion of the finish
to the leather is such that, in this test, the finish can only be pulled off together with
the grain layer.
Strips of leather having a certain length and width are glued to a fixed basis
using a defined adhesive. The tensile tester is then used to pull this leather away
from the basis at an angle of 90. The force measured during the pulling is recorded
and its average reported. This test is repeated at least four times with half the test
specimens being punched out along the backbone and the other half at right angles
to it.
To test the wet adhesion, the adhered specimens are immersed in water and tested
after a predetermined time.
11.7.4
Fastness to Ironing
This test is important for finished shoe upper leathers (see above) in particular. An
iron is moved once back and forth across the leather surface over a slightly rounded
edge as a preliminary test. The damage to the finish and any shift in hue are then
evaluated. The test temperatures are increased in intervals of 20 C. A more sensitive
version of this test is carried out on the VESLIC rub-fastness tester using a heatable
test punch. Again the temperatures are increased in intervals of 20 C. The result is
assessed in each case after five rubs.
11.7.5
Hot Air Fastness
In this test, which is likewise important for shoe leathers, the leather samples are
subjected for 1 min to the flow of hot air from a hair dryer (150 C). The damage to
the finish and the change in hue are then assessed.
11.7.6
Aging resistance
The leather specimens are aged (a) at 50 C for 7 days or (b) at 80 C for 3 days. They
are then assessed to see whether heat aging has resulted in embrittlement, yellowing
or a change in the flexing endurance.
299
300
11.7.7
Fogging test
This test, which is important for automotive leathers in particular, determines the
condensation on cooled glass panes of volatiles from the leather or the finish coat. It
is described in DIN 75201. There are two different methods of measurement: (a) the
reflectometric method and (b) the gravimetric method. While the gravimetric
method indicates the condensed mass, for example after 16 h at 100 C, the reflectometric method describes the clouding of the cooled glass plate after 3 h at 100 C.
11.7.8
Light-fastness
The test is carried out using not only daylight (I.U.F. 401) but also artificial light
(xenon lamp) (I.U.F. 402). The leather strip to be tested is exposed to the light together with a light-fastness scale. The light-fastness scale is made up of eight colored
cotton strips having different, defined light-fastness. The color change of the leather
is compared with the color change of the light-fastness scale.
11.7.9
Hot light aging
This test is important for automotive leather in particular. It assesses the effect of
light, heat and moisture on the flexing endurance, the rub-fastness and the color
fastness of the leather finish. Finished leather strips are exposed to a defined dose of
radiation in a test chamber at 20 % relative humidity. The color fastness is examined
after the first cycle, the flexing endurance after the second cycle, the rub-fastness after the third cycle and the color fastness once more after the last cycle. Requirements
differ from one car producer to the other.
References
1 Stather, F., Gerbereichemie und Gerberei-
5 Science and Technology for Leather
technologie, Akademie Verlag, Berlin,

1967.
2 Schubert, R., in: Herfeld, H. (Ed.) Bibliothek des Leders, Vol. 6; Lederzurichtung,
Oberflchenbehandlung des Leders, Umschau Verlag, Frankfurt am Main, 1982.
3 Heidemann, E., Ullmanns Enzyklopdie
der technischen Chemie, Vol. A15
(Leather), Verlag Chemie, Weinheim.
4 Schubert, R., in: Kittel, H. (Ed.) Lehrbuch
der Lacke und Beschichtungen, Vol. 5,
W. A. Colomb. Heenemann Verlagsgesellschaft, Berlin, 1977.
into the next Millennium, Proc. XXV

IULTCS Congress, 1999, Tata
McGraw-Hill, New Delhi, 1999.
6 Wood, G., Osgood, M., Leather Finishing, in Leather Technologists Pocket Book,
The Society of Leather Technologists
and Chemists, 1999, Chapter 9.
7 Heidemann, E., Fundamentals of
Leather Manufacturing, Eduard
Roetherdruck, Darmstadt, 1993,
and references cited therein.
12
Applications for Asphalt Modification

Koichi Takamura
12.1
Introduction
The annual worldwide consumption of asphalt was over 90 000 000 metric tons in
1995 and the US used approximately one-third of that total [1]. The global asphalt
consumption in 1996 is represented in Fig. 12-1 [2]. Greater than 85 % of 30 000 000
metric tons consumed in USA was used to maintain and improve more than
3 000 000 km (2 000 000 miles) of asphalt roads (Fig. 12-2) with an annual road budget of $85 billion [2]. Federal Highway Trust Fund Authorizations reached nearly
$21 billion in 1996. There are more than 6 000 000 km (4 000 000 miles) of roads, and
asphalt roads account for 94 % (3 270 000 km) of the paved roads in the US. The other 6 % (200 000 km) are paved with Portland cement concrete, which is primarily
used for the heavy traffic area of the interstate highway [1].
Global Asphalt Consumption

Asia/
Australia
Fig. 12-1 The annual global asphalt

consumption. North America and
Europe consume two-thirds of total
90 000 000 tons.
Others
North
America
Europe
Asphalt production is not very uniform throughout the US. The Midwest has the
highest production (40 %), followed by the Gulf Coast (25 %), the East Coast (17 %),
the West Coast (11 %), and the Rocky Mountains.
Over 90 % (16 % of total asphalt consumption as in Fig. 12-2) asphalt used in the
US for non-paving purposes is sold to the roofing industry. Two thirds of that is con-
301
302
12 Applications for Asphalt Modification

Emulsions for
Paving
Fig. 12-2
Others
Use of asphalt in the US.
Roofings
Asphalt
Cement for
Paving
sumed in the manufacture of shingles for houses, and the other third is used in commercial built-up roof.
Almost 90 % of US paving asphalt consumption is for hot mix. The remaining
10 % of the paving asphalt usage (approximately 7 % of the total asphalt consumption) is comprised of asphalt emulsions, primarily used for preventive maintenance and
rehabilitation techniques such as chip seal, slurry seal and microsurfacing. Emulsified asphalts are also used for construction in recycling of old paving materials.
The use of polymer modified asphalts for hot mix and asphalt emulsions has
grown significantly in the US during the last 10 years. The National Center for Asphalt Technology (NCAT) has published a list of reasons for the use of asphalt modification [3, 4]. Asphalt has been modified to:
stiffen binders and mixtures at high temperatures to minimize rutting and reduce
the detrimental effects of load induced moisture damage
soften binders at low temperatures to improve relaxation properties and strain tolerance, thus minimizing non-load associated thermal cracking
improve fatigue resistance, particularly in environments where higher strains are
imposed on the asphalt concrete mixture
improve asphaltaggregate bonding to reduce stripping,
reduce raveling by improving abrasion resistance,
minimize tender mixes, drain-down, or segregation during construction,
rejuvenate aged asphalt binders,
replace asphalt cement as an extender,
permit thicker films of asphalt on open-graded aggregates for increased durability,
reduce flushing or bleeding,
improve resistance to aging or oxidation,
stiffen hot mix asphalt (HMA) layers to reduce required structural thickness,
improve pavement durability with an accompanying net reduction in life cycle
costs,
replace Portland cement concrete with asphalt construction methods that reduce
lane closure times and user delay costs, and
improve overall performance as viewed by the highway user.
12.2 Hot Mix Asphalt Paving
According to the article by King et al. [3], patents for modifying asphalt with natural and synthetic polymers were granted as early as 1843 [5]. The polymers are added
to alleviate pavement problems and to realize economic, environmental, energy, application and/or performance benefits. Test projects were placed in Europe beginning in the 1930s [6]. In North America, neoprene latex was introduced in the 1950s
and found a small but steady market, primarily in Canada and the Western United
States [7]. Natural rubber latex, one of the materials mentioned in the earliest
patents, is still being used today, primarily in water-based emulsion applications
such as microsurfacing. Neoprene modified asphalts have been used for many years,
but have more recently been replaced by other types of elastomeric polymers such as
styrene-butadiene-styrene, SBS block co-polymers. Water based styrene-butadiene
rubber (SBR) latex has found wide usage as an additive to asphalt emulsions to improve chip retention. The introduction of polymers into asphalt emulsions allows
them now to be successfully used for almost any paving application. Recent emphasis on sustainable development and the concern about global warming has encouraged further development of cold paving technology using asphalt emulsions. Asphalt emulsions for paving already account for more than 40 % of total asphalt consumption in France and nearly 30 % in Spain [2].
Polymer modified asphalt accounts for less than 10 % of total asphalt consumption for paving in the US, thus corresponding to approximately 3 000 000 metric tons
a year in the US. The polymer content in these modified asphalt is, on average, 3 %
by weight, resulting in less than 100 000 metric tons of polymers being used for this
application. Although the exact figure is not available, the synthetic and natural lattices account for approximately 30 % of the total polymer annually consumed in the
United States. Approximately 1 000 000 metric tons of polymer modified asphalt
were used in Europe in 1996 and 70 % of these are modified with elastomeric polymers.
12.2
Hot Mix Asphalt Paving
Hot mix paving and cold paving with asphalt emulsion are the two types of paving
technologies used for producing asphalt-based pavements [3]. In hot mix paving,
aggregates are heated to a temperature above 200 C to remove residual water and
mixed with molten asphalt, which is at a temperature as high as 160180 C [3, 8].
The aggregate-asphalt mixture is then transported to the job site, spread and compacted. The mix has to be sufficiently hot to be compacted adequately within the
specified density. In general, the job site has to be within a 1-h transportation distance from the mix plant. Because of the need for the aggregate and the asphalt to be
at high temperatures, there are considerable energy requirements and cost associated with the hot mix process. In fact heating aggregates accounts for nearly 90 % of
the total energy usage of hot mix paving.
The typical cold paving method includes mixing aggregates with asphalt emulsion
and thus it does not involve heating the components used to produce the asphaltbased formulation. Asphalt emulsions will be discussed in Sect. 12.3.
303
304
12.2.1
Asphalt Specification
Asphalt used for paving has been graded with regards to its viscosity at 60 C (140 F)
conforming to American Association of State Highways and Transportation Officials, AASHTO M226 specifications, or 25 C (77 F) penetration graded asphalt conforming to AASHTO M20. These specifications are based on properties at one specified temperature and do not necessarily predict asphalt performance over the wide
range of climatic conditions that the pavement is subjected to in its lifetime.
Changes in crude sources and refinery processes caused deterioration of pavements during the energy crisis in the late 1970s to early 1980s. The problem was recognized by the Federal government and led to the development of the Strategic
Highway Research Program (SHRP) to examine the entire paving technology for
both Portland cement and asphalt based pavements. For asphalt paving technology,
these studies included the entire road construction procedure, aggregate specification and compaction method. The study also defined the laboratory testing procedures and specifications for both the asphalt-aggregate mix, (such as a compaction
method for core sample preparation), rutting, fatigue and cold fracture testing of prepared samples. The SHRP study also developed Superpave Performance Graded
(PG) asphalt binder specifications based on the pavements temperature range [3, 4, 8].
The specification is based on the rutting, fatigue and cold fracture resistance of the
asphalt binder and defined by two numerical values representing the upper and lower temperature limits of particular asphalt in C (e.g. PG64-22). The asphalt binder
becomes too fluid during hot summer days under strong sun resulting in permanent
deformation, which is called rutting. In contrast, the binder becomes brittle during
cold winter nights. A perpendicular crack across the pavement lane develops when
the stress generated by thermal contraction exceeds a critical value. The freshly
applied pavement is most susceptible to rutting, but it becomes more susceptible to
fatigue fracture when the asphalt binder is oxidized and loses its flexibility during
usage. Therefore, rutting and fatigue resistances are based on the fresh asphalt and
after the rotating thin film oven test, RTFOT. This test simulates asphalt heat aging
during the hot mix process. Cold characterization is based on the asphalt binder after
the pressurized aging vessel, PAV, test which is intended to reproduce 710 years of
oxidative aging of the asphalt binder on the road.
All Superpave specifications are based on the SI unit, emphasizing importance of
international recognition. The World Road Association (PIARC) in France has been
active in developing similar international specifications [9, 10].
PG Grading
The Superpave asphalt mix design system includes the performance grade (PG) asphalt binder specification. The Superpave asphalt binder tests try to determine physical properties that can be directly related to field performance in terms of rutting,
fatigue cracking and low temperature cracking. Superpave characterizes asphalt at
the actual pavement temperatures it will experience, and at the periods of time when
distresses are most likely to occur. A part of the Superpave binder specification is
shown in Tab. 12-1. Detailed specifications as well as test apparatus, procedures and
the PG specification can be found elsewhere [8, 11].
Tab. 12-1
Example of Superpave binder specification.
Performance grade
PG64
10
PG70
16
22 28
34
40
10
16
22
28
34
40
Average 7-day
maximum
pavement design
temperature (C)
<64
<70
Minimum
pavement design
temperature (C)
>10 >16 >22 >28 >34 >40
>10 >16 >22 >28 >34 >40
Original binder
Flash-point temp.,
minimum (C)
230
Viscosity maximum
3 Pa s, test temp. (C) 135
Dynamic shear,
G*/sin( ), minimum
1.00 kPa, test temp.
at 10 rad s1 (C)
64
70
Rolling thin film oven residue

Mass loss,
maximum, %
1.00
Dynamic shear,
G*/sin( ), minimum
2.30 kPa, test temp.
at 10 rad s1 (C)
64
70
Pressure aging vessel residue

PAV aging
temperature (C)
100
100 (110)*
Dynamic shear,
G*sin( ), minimum
5.00 MPa, test temp.
at 10 rad s1 (C)
31
28
25
Creep stiffness,
S, maximum,
300 MPa, m-value
minimum, 0.300,
Test temp.,
at 60 s (C)
61
12 18
*110 C PAV for the desert climate
22
19
16
34
31
28
25
22
19
24
30
12
18
24
30
305
306
Pumping and handling: The maximum viscosity of the unaged binder should be below 3 Pa s at 135 C to ensure that the binder can be pumped and handled at the hot
mix facility. A rotational viscometer (ASTMD4402) is used.
Permanent deformation: The rutting resistance of the binder is represented by the
stiffness of the binder at high temperatures that one would expect in use. This is represented by G*/sin( ), where G* is the complex shear modulus and is the phase
angle determined by the dynamic shear rheometry, DSR, measured at 10 rad s1
(1.59 Hz). The complex modulus can be considered as the total resistance of the
binder to deformation under repeated shear, and consists of elastic modulus, G and
loss modulus, G (recoverable and non-recoverable components). The relative
amounts of recoverable and non-recoverable deformation are indicated by the phase
angle, . The asphalt binder will not recover or rebound from deformation if = 90.
In practice, to minimize rutting, G*/sin( ) must be a minimum of 1.00 kPa for
the original binder and 2.20 kPa after aging the binder using the RTFO procedure.
To address rutting resistance, the Superpave specification promotes the use of stiff,
elastic binders.
Fatigue cracking: The Superpave specifies G*sin( ) < 5.00 MPa, thus promotes the
use of compliant, elastic binders to address fatigue cracking. Since fatigue generally
occurs at low to moderate pavement temperatures after the pavement has been in
service for a period of time, the specification addresses these properties using binder
aged in both RTFO and PAV.
Low-temperature cracking: When the pavement temperature decreases, asphalt
pavement shrinks. Since friction against the lower pavement layer inhibits movement, tensile stresses buildup in the pavement. When these stresses exceed the tensile strength of the asphalt mix, a low temperature crack occurs. The bending beam
rheometer is used to apply a small creep load to a binder beam specimen and measure the creep stiffness. If the creep stiffness is too high, the asphalt will behave in a
brittle manner, and cracking is more likely to occur. To prevent this cracking, creep
stiffness has a maximum limit of 300 MPa.
The rate that the binder stiffness changes with time at low temperatures is regulated through the m-value. A high m-value is desirable since this leads to smaller tensile stresses in the binder and less chance for low temperature cracking. A minimum
m-value of 0.300 after 60 s of loading is required by the Superpave binder specification. Since low temperature cracking usually occurs after the pavement has been in
service for some time, this part of the specification addresses these properties using
binder aged in both the RTFO and PAV.
As a part of the Superpave activities, chemical and physical properties of more
than 70 asphalt samples commonly used in the United States were analyzed. These
asphalt samples were available through the Material Research Library (MRL) for researchers in the field [12]. An example of the Superpave analysis of one of the MRL
asphalt, AAA-1 (Lloydminster) modified with 3 % Butonal NS175 (SBR latex from
BASF Corporation) is shown in Tab. 12-2. The rotational viscosity measured by the
Brookfield viscometer is 1.11 Pa s at 135 C, which is within the specification of
<3 Pa s. G*/sin( ) of the original (unaged) asphalt were 1.91 and 0.59 kPa at 64 and
70 C, respectively, which allow us to estimate G*/sin( ) = 1.0 kPa at 67 C. The
same measurement for the RTFO residue gave G*/sin( ) = 3.47 and 1.89 kPa at the
same temperatures, thus G*/sin( ) = 2.2 kPa at 69 C. The upper limiting (rutting
resistance) temperature of this asphalt is 67 C and thus this modified asphalt meets
specification of PG64.
Tab. 12-2
Example of Superpave characterization of SBR modified asphalt.
Viscosity at 135 C (Pa s)

Rutting resistance by DSR
Original asphalt
After RTFO
Fatigue resistance by DSR
After RTFO and PAV
Low-temp. crack resistance by BBR
After RTFO and PAV
Temp. at G*/sin() = 1.0 kPa (C)

Temp. at G*/sin() = 2.2 kPa (C)
Limiting high temperature (C)
Temp. at S = 300 MPa (C)
Temp. at m = 0.30 (C)
Limiting low temperature (C)
PG grading (C)
1.11
G*/sin( ) at 64 C (Pa)
1.91
0.59
3.47
1.89
G*sin( ) at 7 C (MPa)
G*sin( ) at 10 C (MPa)
2.98
2.38
Creep stiffness, S, at 24 C (MPa)

Creep stiffness, S, at 18 C (MPa)
Rate of change of S, m value at 30 C
186
108
0.298
0.364
67
69
67
29
24
34
6434
The Superpave analysis specifies the PAV temperature of 100 C for 20 h for this
sample (Tab. 12-1). The DSR analysis of the PAV residue gave G*sin( ) = 2.98 and
2.38 MPa at 7 and 10 C, respectively. These values are significantly lower than the
requirement for the PG64 asphalt.
Polymer modification improves the rutting and fatigue resistance mostly through
enhancement in the recoverable, elastic component, G of the asphalt as seen in
Fig. 12-3. The elastic and loss moduli, G and G of the unmodified asphalt were
0.035 and 0.80 kPa, respectively with phase angle u = 88 at 64 C, resulting
G*/sin( ) = 0.80 kPa. G increased nearly 11 to 0.37 kPa upon modification with
3 % SBR latex but non-recoverable, viscous component, G showed only moderate
increase of 2.3 to 1.80 kPa, which gives the phase angle m = 78 at the same temperature. This resulted in G*/sin( ) = 1.91 kPa as shown in Tab. 12-2. The phase
angle alone makes only a limited contribution for determination of the rutting re-
307
sistance since sin( ) = 0.999 and 0.981 at u = 88 and m = 78, respectively, for the
unmodified and modified asphalt.
10
G*
G" (Viscous Behavior), kPa
308
Unmodified
1
SBR Modified
0.1
m
u
0.01
0.01
0.1
G' (Elastic Behavior), kPa
Fig. 12-3 Complex modulus G* of

unmodified and 3 % SBR latex modified asphalt measured at 64 C. The
polymer modification results in 11
increase in the elastic component, G
with moderate increase in viscous
component, G.
The bending beam rheometry (BBR) of the PAV residue was conducted to establish the low limiting temperature of the modified asphalt. The creep stiffness values
were 186 and 108 MPa, and the m-values were 0.298 and 0.364 determined at 24
and 18 C, respectively (Tab. 12-2). Thus, S would be 300 MPa about at 29 C and
m would be 0.300 at approximately 24 C. Taking the higher value, 24 C is the low
temperature limit of this asphalt determined at a condition of 60-s loading.
The desired value of creep stiffness was originally developed as a correlation between thermal cracking of in-service asphalt pavement and binder stiffness values
estimated at 2 h loading time. However, using the concept of timetemperature superposition, it was confirmed that by raising the test temperature 10 C, equal creep
stiffness could be obtained after a 60-s loading. Thus, 34 C would be the low temperature limit from the BBR measurement. We conclude that this asphalt meets the
PG64-34 specifications as shown in Tab. 12-1.
Improvement in both the rutting and cold fracture resistance of the asphalt with
the polymer modification are demonstrated in Tab. 12-3 where Superpave analysis of
unmodified and modified with 3 % Butonal NS175 for AAA-1 and AAK-1 (Boscan)
asphalt are compared. In addition to the Superpave analysis, values of conventional
measures of unmodified and modified asphalt, such as ductility (ASTM D113), penetration (ASTM D5), softening point (ASTM D36) and absolute viscosity measured at
60 C (ASTM D2171) are also included.

Tab. 12-3
Superpave analysis of unmodified and SBR modified asphalts.
Asphalt
Properties
Brookfield viscosity
at 135 C (mPa s)
Temp. at G*sin() = 1 kPa (C)
Temp. at G*sin() = 2.2 kPa
after RTFO (C)
Temp. at S = 300 MPa (C)
Temp at m = 0.30 (C)
Limiting high temperature (C)
Limiting low temperature (C)
PG Grading
Ductility at 4 C
Penetration (mm) at 25 C
Softening Point (C)
Absolute viscosity at 60 C (Pa s)
AAA-1
AAK-1
Unmodified
Modified
Unmodified
Modified
280
58
1100
67
560
63
2000
79
58
21
24
58
31
5828
>150
16
44
0.086
69
29
24
67
34
6434
>150
11
56
0.34
65
14
17
63
24
6422
28
6.7
49
0.33
78
19
14
78
24
7622
86
4.5
63
1.6
The results of modifying asphalt with additives are highly dependent upon the
concentration, the molecular mass, the chemical composition, and microscopic morphology of the additive as well as the crude source, the refining process and the grade
of the base asphalt used.
Superpave binder specifications are successful in predicting the rutting resistance
and cold fracture resistance of the unmodified asphalt. A new DSR procedure is under development for the better prediction of fatigue resistance. Integration of the
bending beam rheometry data and direct tension measurement in the near future
will provide a better description of the benefits of the polymer-modified asphalt.
One of the primary benefits of polymer modified asphalt binders is a reduced susceptibility to temperature variation [13]. Because many Performance Grade asphalt
specifications can only be met with polymer modification, it is expected that the use
of polymer modified binders will increase as these specifications are implemented
during the late 1990s and the early 2000s. A 1997 survey of state highway agencies
found that 35 agencies reported that they will be using greater quantities of modified
binders; 12 agencies reported they will be using the same amount of modified
binders; and no agency reported they will be using less modified binder [14].
Storage Stability
A polymer-modified asphalt is a two phase system, forming a continuous fine polymer network, that is highly swollen with aromatic components in the asphalt. The
polymer is mixed in the asphalt and stored at elevated temperature, which could
cause chemical reaction within polymer chains and with some components in the asphalt. The degree of swelling, and thus the microscopic morphology of the polymer
phase, varies widely dependent on the crude source, the refining process and the
grade of the base asphalt [1517].
309
310
When the chemical and physical properties of the polymer and asphalt are not
matched to each other, a polymer rich phase could develop near the surface of the
asphalt when stored at 160170 C for a few days without agitation as reported by
Brl et al. with SBS modified asphalts [16]. The asphalt composition in the polymer
rich phase is vastly different from the original asphalt.
One of their results with Asphalt E modified with 5 % SBS polymer is shown in
Fig. 12-4. The aromatic and saturate components preferentially partition to the polymer phase, thus concentrating the asphaltenes and polar resin fractions in the asphalt phase. The majority of asphaltenes are retained in the asphalt phase, resulting
in an increase in the asphaltenes/aromatic ratio. This potentially leads to reduced
swelling of asphaltenes, which would have negative effects on low temperature flexibility of asphalt.
Polymer phase
Original Asphalt E
Asphaltene
Saturate
Resin
Asphalt phase
Aromatic
Fig. 12-4 Difference in asphalt composition among original asphalt and

the polymer rich and asphalt phases developed during storage.
The phase separation during storage can be visualized with hot stage optical microscopy, which allows us to observe changes in the polymer morphology at the mixing and storage conditions. Here, the other MRL asphalt, AAB-1 (Wyoning Sour),
was modified with 3 % Butonal NS175. Photomicrographs shown in Fig. 12-5 illustrate the presence of a fine polymer network in the freshly mixed sample observed at
110 C at 200 magnification. The polymer phase transfers to macroscopic polymer
globules without agitation when the sample is slowly heated to 170 C. These polymer blobs migrate to the top due to the density difference.
Fig. 12-5 Photomicrographs of conventional SBR modified asphalt taken

at 110 and 170 C.
Wegan et al. [17] reported observing similar macroscopic polymer globules and/or
a polymer layer surrounding the aggregate surface in the paved asphalt mixtures,
even though only fine structures existed in the modified binder observed at room
temperature using fluorescence microscopy, which is the traditional method of
studying polymer morphology [1517].
The photomicrograph shown here (Fig. 12-5) demonstrates that polymer modified
asphalt behaves as a dispersion consisting of two immiscible fluids; a highly viscoelastic fluid dispersed in a less viscous one. The dispersed phase elongates to fine
fluid columns under agitation. When the agitation is removed, these elongated
columns transfer to a series of spherical droplets as minimizing the total surface
area and thus the total energy.
Numerous inventions are reported in the literature to overcome the polymer incompatibility in the modified asphalt, which often involve introduction of a controlled cross-link reaction in the polymer phase. Cross-linking reduces solvent
swelling and increases the visco-elasticity of the polymer phase. Butonal NX1129 is
an example of the new type of SBR latex. As shown in Fig. 12-6, a fine polymer network remains even when the modified asphalt is observed at 170 C for 10 min. Stable polymer structures of this latex also extend the low temperature limits of certain
modified asphalts, as determined by the direct tension measurement.
12.2.2
In-line Injection (Pump-in)
Pre-blending infers that the latex and asphalt have been mixed at a central location
using a batch process as discussed above. In-line injection (also known as pump-in)
implies that the latex and asphalt are blended immediately before being applied to
the aggregate at the hot-mix plant. This process eliminates potential separation of
311
312
Fig. 12-6
Butonal NX1129 maintains stable, fine polymer network even
at 170 C.
polymer and asphalt during transportation and storage of incompatible materials,

and the need for an asphalt storage tank for the polymer modified asphalt, thus reducing handling costs.
With the pre-blending process, polymer and asphalt are thoroughly mixed and the
binders can be tested and certified before application to the aggregates. Recent advancement in quality control at the mixing process guarantees adequate mixing and
performance of the asphalt produced by the in-line injection process. An optical photomicrograph demonstrating polymer networks in the asphalt prepared by the direct
injection process is shown in Fig. 12-7.
Photomicrograph demonstrating
the presence of polymer networks in the
asphalt prepared by
the in-line injection
(pump-in) process.
Fig. 12-7
12.3 Paving with Asphalt Emulsion
12.3
Paving with Asphalt Emulsion
Asphalt emulsions used in road construction and maintenance are either anionic or
cationic, based on the electrical charge of the asphalt particles, which is determined
by the type of the emulsifying agent used. The asphalt contents of these emulsions
are, in most cases, from 55 to 75 % and prepared using a high shear mechanical device such as a colloid mill. The colloid mill has a high-speed rotor that revolves at
10006000 rpm with mill-clearance settings in the range of 0.2 to 0.5 mm. A typical
asphalt emulsion has a mean particle size of 25 m in diameter with distribution
from 0.3 to 20 m. A photomicrograph and typical size distribution of an asphalt
emulsion are shown in Fig. 12-8. Asphalt emulsion properties depend greatly upon
the emulsifier used for their preparation.
Fig. 12-8 Particle size distribution and photomicrograph of a typical

asphalt emulsion.
A latex modified asphalt emulsion can be prepared using several methods: addition of the latex in the aqueous emulsifier solution, direct injection in the asphalt
line just ahead of the colloid mill or post-addition to the pre-manufactured emulsion,
as schematically shown in Fig. 12-9. Addition to the aqueous phase is the most commonly used method. The direct injection process often helps to produce an emulsion
with a desired high viscosity for chip seal application (Sect. 12.3.1). This is due to the
narrow particle size distribution of the asphalt emulsion produced with this process.
Asphalt emulsions are classified with their charge and on the basis of how quickly
the asphalt will coalesce, which is commonly referred to as breaking, or setting. The
terms RS, MS and SS have been adopted to simplify and standardize this classification. They are relative terms only and mean rapid-setting, medium-setting and slowsetting. An RS emulsion has little or no ability to mix with an aggregate, an MS
emulsion is expected to mix with coarse but not fine aggregate, and an SS emulsion
is designed to mix with fine aggregate. The emulsions are further subdivided by a series of numbers and letters related to the viscosity of the emulsions and the hardness
of the base asphalt cements. The letter C in front of the emulsion type denotes
313
314

Fig. 12-9 Schematic illustration for latex modified asphalt
emulsion production.
Latex
Asphalt
Water
Emulsifier
Acid or
Base
Latex
Storage
Colloidal
Mill
Latex
cationic. The absence of the C denotes anionic. For example, CRS-2 is a cationic
rapid setting emulsion typically used for chip seal application.
ASTM and the American Association of State Highway and Transportation Officials (AASHTO) have developed standard specifications for the grades of emulsions,
shown in Tabs 12-4 and 12-5 for anionic and cationic emulsions, respectively. The
h that follows certain grades means that harder base asphalt is used. The HF preceding some of the MS grades indicates high-float, as measured by the Float Test
(ASTM D139 or AASHTO T 50). High float emulsions have a specific quality that
permits a thicker asphalt film coating on the aggregate particles.
12.3.1
Applications of Asphalt Emulsions
The Cold-mix recycling operation, which utilizes milled old asphalt pavement mixed
with asphalt emulsion, is gaining popularity for rehabilitating deteriorating roadways. In this method, the old asphalt pavement is crushed, often in place. An inplace aggregate base can also be incorporated or new aggregates can be added to the
old materials and asphalt emulsion added. Then, materials are mixed together,
spread to a uniform thickness, and compacted. Slow setting SS and CSS asphalt
emulsions are used currently without polymer modification.
Surface treatments applied to an existing pavement for preventive maintenance
are the most significant application of polymer modified asphalt emulsion. They are
economical, easy to place, resist traffic abrasion and provide a long lasting waterproof cover over the underlying structure. There are several types of surface treatment, but in this chapter, we will limit our discussion to chip seal and slurry surfacing. Detailed descriptions as well as recommended performance guidelines of various paving technologies using asphalt emulsions can be found elsewhere [18, 19].
75400
63
75400
63
65
100+
100250
<40
Test on residue from distillation

Penetration at 25 C, 100 g, 5 s, (dmm)
Ductility, 25 C, 5 cm min1 (cm)
100250
<40
100400
65
100250
<40
50450
65
CMS-2
CRS-1
20100
60
Medium-setting
Rapid-setting
CRS-2
65
100+
100200
<40
1200
20100
20100
55
HFMS-1
4090
<40
50450
65
CMS-2h
MS-2h
100200 100200 4090

<40
<40
<40
44
20100
Selected requirements for cationic asphalt emulsion (ASTM D2397).
Test on emulsion
Viscosity, Saybolt Furol at 25 C (s)
Minimum residue by distillation (%)
Test
Tab. 12-5
Test on residue from distillation

Penetration at 25 C, 100 g, 5 s, (dmm) 100200 100200 100200
<40
<40
<40
Ductility, 25 C, 5 cm min1 (cm)
Float test, 60 C (s)
1200
55
20100
MS-2
MS-1
HFRS-2
RS-1
RS-2
Medium-setting
Rapid-setting
Selected requirements for anionic asphalt emulsion (ASTM D977).
Test on emulsion
Minimum residue by distillation (%)
Test
Tab. 12-4
100+
100+
65
100250
<40
57
20100
CSS-1
Slow-setting
100200 4090
<40
<40
1200
1200
100+
100+
65
20100
20100
57
SS-1h
4090
<40
57
20100
CSS-1h
100200 4090
<40
<40
20100
20100
57
HFMS-2 HFMS-2h SS-1
Slow-setting

315
316
Chip seal: This treatment involves spraying asphalt material (heated asphalt or asphalt emulsion) followed immediately by a thin (one stone thick) aggregate cover as
schematically shown in Fig. 12-10. The aggregate is immediately rolled with a pneumatic roller and a light brooming may be necessary to remove any excess aggregate.
Cutback asphalts have been used in the past for this purpose but asphalt emulsion is
now preferred due to environmental and safety (fire hazard) concerns associated
with cutback asphalt. A rapid setting RS, HFRS or CRS is usually used, though a
medium setting MS, HFMS or CMS asphalt emulsion could be used (ASTM D977
and D2397 for anionic and cationic emulsions, respectively). The cationic asphalt
emulsion often provides better asphalt adhesion to the aggregate. The polymer modified asphalt emulsion (24 % polymer by weight of asphalt) improves chip retention
and enhances pavement durability (Sect. 12.3.5).
Aggregate Particle
Emulsion Residue
Schematic diagram
illustrating chip seal paving.
Fig. 12-10
Slurry seal: A slurry seal is a homogeneous mixture of well-graded fine aggregate,

asphalt emulsion, water and mineral fillers applied to a pavement as a surface treatment. Slurry seal is usually applied in a thickness of 3 to 6 mm. A small amount of
mineral filler, hydrated lime, limestone dust, Portland cement or fly ash, aids in setting the slurry. The Slurry comes directly from a traveling mixing plant into an attached spreader box that spreads the slurry by a squeegee-type action as shown in
Fig. 12-11. The machine used for production of slurry seal is a self-contained, continuous-flow mixing unit. The asphalt emulsion used in the slurry mix may be SS-1,
SS-1h, CSS-1 or CSS-1h. Quick-setting (QS) asphalt emulsion is used when early
opening to traffic is necessary.
Microsurfacing: A new slurry technique, microsurfacing, takes advantages of polymer modified asphalt emulsions. It can be applied at greater thicknesses than conventional slurry seals, allowing its use for rut-filling and is maintains a friction resistant surface throughout the service life. The microsurfacing mix has to set quickly
enough to accept traffic within 1 h after placement [20]. Polymer modified CSS-1h
asphalt emulsion (ASTM D2397 and AASHTO M208) is used with a minimum polymer level of 3 %. The International Slurry Seal Association has established recommended performance guidelines A105 and A143 for the slurry seal and microsurfacing, respectively. A careful mix design (ISSA TB-139, TB-09, TB-114, TB-100, TB147A, TB-144 and TB-113) confirming compatibility of the aggregate, polymer modified asphalt emulsion, mineral filler, and other additives is essential for successful
slurry seal and microsurfacing operations.
Fig. 12-11 Schematic diagram of a typical microsurfacing paver.

Courtesy Akzo Nobel Asphalt Applications Inc.
12.3.2
Asphalt Emulsion Tests
Standard tests and procedures for testing asphalt emulsions are specified in ASTM
D244 and AASHTO T59. These include particle charge, viscosity, storage stability,
demulsibility and others. A distillation or evaporation test is used to recover the asphalt (emulsion residue) from the emulsion. In these tests, the asphalt emulsion is
subjected to a maximum of as high as 260 C for the distillation method or 167 C for
the evaporation. The most common tests run on the recovered residue include penetration, softening point, ductility, elastic recovery and torsion recovery. These tests
are meant to be used as a quality control tool, (e.g. to confirm a designed polymer level in the modified asphalt), but are not designed to correlate the binder performance
for each application [21]. During the residue recovery process, excess heat applied to
the polymer modified asphalt emulsion causes formation of macroscopic polymer
globules that are as large as a few mm in diameter. A minor difference in the temperature and length of the distillation would cause variation in the polymer morphology, which explains the poor reproducibility reported by the AEMA Materials
Committee Round Robin Studies on emulsion residue characterization [22].
12.3.3
Polymer Honeycomb Structure in Cured Asphalt Emulsion
Modified asphalt emulsion with latex is not just an emulsion of polymer-modified

asphalt, but rather an emulsion containing dispersed latex particles in the aqueous
317
318
phase, as schematically shown in Fig. 12-12. Menisci of water containing latex particles (and Portland cement particles for microsurfacing) form among asphalt particles when water starts to evaporate from the asphalt emulsion. The SBR latex for asphalt modification is designed to create a polymer film without coagulum formation;
promoting early strength development. The majorities of latex particles migrate together with water and accumulate in the menisci, and thus act as spot welding of
asphalt particles to ensure maximum binding power, as shown in the right side of
Figure 12-12. To form the finest honeycomb structure the asphalt emulsion should
not break (coalesce) during the process.
Asphalt
Asphalt
Latex Film
Latex
Latex Modified Emulsion

Left: Schematic illustration of latex
modified asphalt emulsion showing that latex
particles remain in the aqueous phase.
Fig. 12-12
Cured Asphalt Emulsion

Right: Latex particles transform to a continuous
polymer film surrounding asphalt particles,
which cures to form the honeycomb structure.
Scanning electron microscope observation of the microsurfacing pavement confirmed the presence of the polymer honeycomb structure [22]. Here, a sample of the
freshly applied pavement sample was treated with OsO4 and the asphalt was extracted with MEK (methyl ethyl ketone) solvent. The treatment with OsO4 makes the SBR
polymer insoluble to the organic solvent and also improves the contrast for the scanning electron microscope, SEM, observation.
A series of SEM photographs of the fractured surface were taken and shown in
Fig. 12-13. These photographs, especially (b) and (c) demonstrate the honeycomb
structures of the SBR polymer formed around asphalt particles. Some latex polymers
are also adhering on the aggregate surface as seen in (c). It is important to realize
that the latex polymers should remain in the aqueous phase, not in the asphalt, and
transform to a continuous polymer film during the curing process. Since Portland
cement particles also remain in the aqueous phase, the flexible polymer-cement
complex creates these honeycomb structures. In contrast, the honeycombs made
only with Portland cement would also be very brittle and this would be the case when
the polymer is present in the asphalt phase.

(b)
5
m
(a)
25
m
(a)
(b)
(c)
(c)
m
10
Fig. 12-13 A series of scanning electron microscope photographs of the cured microsurfacing
specimen demonstrating (a) and (b) SBR poly-
1m
mer honeycomb formed around asphalt particles. (c) Some polymers also adhere on the
aggregate surface.
Do these honeycombs strong enough to maintain their structure under repeated

poundings by heavy weight truck tires running at above 100 km h1 throughout the
lifetime of the pavement? Pavement samples were taken from Texas State Highway
84 near Waco. This highway was treated with the microsurfacing in 1998. Samples
were taken from the wheel path as well as the shoulder of the pavement. As seen in
Fig. 12-14, the honeycomb structure with the SBR latex polymer-cement complex is
flexible enough to withstand repeated stresses after three years service at the highway condition. Advantages of this flexible honeycomb structure with SBR latex will
be discussed later in the emulsion residue characterization.
An optical microscope observation simulating chip seal was also conducted using
SBR latex modified CRS-2 emulsion [23]. When the emulsion is placed on sand particles, which are placed on the microscope slide glass, spontaneous formation of the
polymer network was observed as shown in Fig. 12-15.
12.3.4
Asphalt Emulsion Residue Characterization
The need for an appropriate residue recovery procedure for asphalt emulsion has
been recognized in both Europe and the US. The forced airflow drying method,
which dries the emulsion at ambient temperature, provides a sufficient amount of
residue samples within 35 h for the Superpave binder characterization [22]. An
example of estimating the rutting resistance temperature, Tr (temperature at
G*/sin( ) = 1 kPa) of microsurfacing emulsion residue is shown in Fig. 12-16. A typ-
319
320
5m
SEM photographs of microsurfacing pavement taken under

the wheel path; Texas State Highway 84 near Waco, paved in 1998, and
samples taken in 2001.
Fig. 12-14
Photomicrograph demonstrating spontaneous

formation of polymer
network upon curing
of the CRS-2 asphalt
emulsion modified
with 3 % cationic SBR
latex.
Fig. 12-15
Latex Polymer
Network
50m
ical microsurfacing formulation consists of 100 g aggregates, 12 g of 65 % asphalt

emulsion containing 3 % latex polymer, 10 g water and 1 g Portland cement. The formulation used for this study is the same but without the aggregate and 10 g water.
As seen in Fig. 12-16, the unmodified asphalt emulsion was made with a PG64 asphalt and the rutting resistance temperature increased slightly from 66 C to 68 C
after one month. The sample with Portland cement shows a gradual increase in Tr to
71 C within three weeks. This increase in Tr is mostly due to stiffening of the asphalt as the phase angle of the residue increases from 82 to 88 at Tr. The value of Tr
showed a rapid increase to 76 C within the first 3 days of curing when 3 % of the
SBR latex is also present in the mix. Two PG grades improvement in the rutting resistance was achieved after two weeks of curing. The phase angle at Tr remained
nearly constant at 7778 throughout the curing, confirming that SBR modified asphalt binder maintains the elasticity. Differences in the phase angle of these three
samples are also summarized in Fig. 12-16.
Fig. 12-16 The rutting resistance temperature,

Tr, of microsurfacing emulsion, emulsion plus
cement and emulsion, cement and 3 % SBR
latex. Two PG grade improvement can be
observed with the polymer-cement system,

which maintains elasticity of the residue as
seen with the low measured phase angle.
To evaluate potential benefits on performance during its lifetime, an accelerated

curing test was also designed. Here, the emulsion was dried one day under the
forced airflow, and transferred into an oven at 60 C, and so simulating pavement
temperature during the daytime.
Two different latex polymer levels of 3 and 5 % were studied. Three PG grades improvement (from PG64 of the unmodified asphalt) with 3 % latex polymer takes only
10 days of curing, as seen in Fig. 12-17, demonstrating the rut filling capability of the
microsurfacing system.
The European Standard for emulsions of pure and polymer modified bitumen including a residue recovery procedure and characterization of the recovered residue is
currently under preparation.
12.3.5
Application Tests for Chip Seal and Microsurfacing
Microsurfacing: Jones et al. [24, 25] analyzed the performance of seven polymer-modified asphalt emulsions for microsurfacing application. The objective of their studies
was to examine effects of different polymers on microsurfacing performance. The
same asphalt, surfactant and aggregates were used to eliminate all other variables
321

Accelerated curing
of the microsurfacing residues
at 60 C after drying under
forced airflow for one day.
Fig. 12-17
60
15
40
10
20
N
eo
pr
en
e
EV
A
SB
S
N
at
ur
al
0
SB
R
Wheel Track Deformation, %
from the mix design. Results of the Wet Track Abrasion Test, WTAT, and Loaded
Wheel Test, LWT, are reproduced in Fig. 12-18.
Wet Abrasion Loss, g/ft2
322
The wet track

abrasion test and loaded wheel
test of cured microsurfacing
specimen prepared with five
different polymers reported by
Jones [23, 24].
Fig. 12-18
The authors concluded that SBR latex continues to perform well in virtually all the
laboratory tests to which it has been subjected. They also recognized that the materials which were received as latices, tended on average to outperform the solid polymers. These conclusions, especially LWT results, can now be understood in the light
of the formation of the polymer honeycomb structure providing excellent rutting resistance of the asphalt emulsion residue. This is demonstrated in Figs 12-13 to
12-16].
12.4 Eco-efficiency Analysis
Chip seal: Loose chips from a freshly paved road are the major safety concern for
chip seal operation, and several attempts were reported in the literature to develop a
laboratory procedure to simulate the field experience. A modified fretting test (also
know as the abrasion cohesion test Esso, ACTE) appears to be the most successful [26, 27]. In this test, a known amount of CRS-2 asphalt emulsion and aggregates
are spread on a roofing felt, and then rolled with a 30 kg rubber roller. The sample is
subjected to the shearing action of a horizontal steam-hose, which is attached to a
Hobart sun and planet mixer, and the percentage of retained chips is recorded as a
function of curing time.
An example of the test results is shown in Fig. 12-19, which demonstrates early cohesion development with the latex modified asphalt emulsion [28]. Marchal et al. [27]
report that the maximum chip retention does not exceed 80 % even with a fully cured
asphalt emulsion, and approximately 50 % chip retention is considered to be strong
enough to be open to traffic. Use of a specially designed brush appears to reduce a
problem of chip build-up around the steam-hose [29].
Chip retention, %
80
Fig. 12-19 Results of modified

fretting test demonstrating
advantages of the early chip
retention with cationic SBR
latex modified emulsion.
60
Latex Modified
40
Unmodified
20
0
0
30
60
90
120
Curing time, min.
12.4
Eco-efficiency Analysis
Recent study by Queiroz et al. [30] demonstrated a statistically significant relationship between a countrys economical development and its road infrastructure
(Fig. 12-20). A well-developed and well-maintained highway system is credited for
improvements in access to goods and services, education and employment opportunities. A person living in Australia has, on average, access to 27-lane meters of paved
road. In comparison, it is only 16-lane centimeters for people in China! Improvement in cold mix technology to provide durable pavements would result in significant impact on the well being of people living in these developing countries. A cold
mix plant, using asphalt emulsion, requires less initial capital investment and lower
energy consumption than a hot mix plant.
For developed countries, environmental focus has shifted from pollution prevention to sustainable development. BASF developed a so-called eco-efficiency analysis,
as an internal decision making tool, to help in evaluating products and processes for
323
324
A linear correlation with R2 = 0.76

exists between a countrys economical wellbeing and road infrastructure. Here,
Fig. 12-20
PGNP = GNP/Capita in $ and paved roads

in km/million inhabitants are plotted for 98
countries [30].
sustainable development. The eco-efficiency analysis takes equal account of both the
ecological and economic aspects and compares pros and cons of each choice. The
main goal of the eco-efficiency analysis is To offer customers the best possible alternatives with the least environmental impact at the best cost.
It has been realized that preventive maintenance of existing roadways is the most
financially effective use of available resources [3, 31, 32]. The eco-efficiency analysis
was applied to compare three different paving methods of hot mix, polymer modified hot mix and asphalt emulsion based microsurfacing [33]. The study integrates
environmental impact analysis and economical consideration. The base study assumes a 7-year life for the microsurfacing treatment (812 mm thick), a 10-year life
for the thin (4 cm) hot mix overlay and a 13-year life for the polymer modified hot
mix overlay.
The environmental impact analysis is based on the life-cycle analysis [34], which
evaluates environmental aspects and potential impacts throughout a products life
cycle (e.g., cradle-to-grave evaluation) from raw material acquisition through production, use and disposal. For asphalt emulsion based paving, this analysis includes not
just for production of the asphalt emulsion and paving operations, it starts from the
crude oil production, refinery process, chemical additives and aggregate production.
12.5 Concluding Remarks
It also includes waste production, recycling operation, and transportation and distribution of all these activities.
These environmental impacts are classified into five parameters: raw materials
consumption, energy consumption, emission, potential health effects, and risk of
accident and misuse. When all factors were considered, microsurfacing had a lower
environmental footprint as shown in Fig. 12-21. The thicker hot mix layer let to a
greater use of natural resources, as well as higher energy consumption and emission
involved in its manufacture and transportation.
Energy
1,00
0,50
Raw material
Emissions
0,00
Potential health
effects
Risk potential
Fig. 12-21 Environmental profiles for microsurfacing and thin hot mix overlays. Microsurfacing
has a lower environmental footprint than two
other alternative treatments.
Cold-mix microsurfacing
Hot-mix asphalt
Modified hot-mix asphalt
These environmental impacts were weighed according to how surveys said the
public viewed their relative importance. When this result is combined with the annual costs of the treatments, the overall conclusion is that microsurfacing provides a
better balance between cost-effectiveness and environmental impact than does a thin
hot mix overlay as shown with the eco-efficiency portfolio of the preventive maintenance in Fig. 12-22. Here, all costs and environmental impacts were averaged over
0,2
High eco-efficiency
Environmental impact
Cold-mix
microsurfacing
1,0
Fig. 12-22 Eco-efficiency portfolio combines environmental

impact with costs of treatments. Results demonstrate
that microsurfacing is more
Eco-Efficient than hot mix
overlays.
Modified
hot-mix
asphalt
Hot-mix
asphalt
Low eco-efficiency
1,8
1,8
1,0
Costs (relative)
0,2
325
326
each year of the life of the treatment. The study also suggests that future improvement in microsurfacing techniques could lead to additional cost and environmental
advantages [33].
12.5
Concluding Remarks
Asphalt roads account nearly 95 % (3 300 000 km) of the paved roads in the US Addition of as little as 23 % of polymers in the asphalt improves rutting resistance, and
prevents premature fatigue and cold fracture crack formation. The latex can be used
for both hot mix and emulsion based paving. Recent studies [33] on eco-efficiency
analysis clearly demonstrate economical and ecological advantages of the asphalt
emulsion based microsurfacing for preventive maintenance.
Latex, because it is an aqueous dispersion, is the ideal polymer for modification of
an asphalt emulsion. Commercial availability of the cationic form makes SBR latex
ideal for chip seal, slurry seal and microsurfacing applications, which are predominantly used for preventive maintenance.
Acknowledgement
The author is grateful to Glynn Holleran of Valley Slurry Seal Co., Drs Alan James
and Julia Wates of Akzo Nobel Surface Chemistry LLC, Dr. Per Redelius of AB
NYNS Petroleum, Jeremy Kissock of BASF New Zealand and Mike Taylor of BASF
Corporation for their valuable comments and advice.
References
1 The Asphalt Institute, The Asphalt
2
Handbook, Manual Series No. 4 (MS-4).

Symposium of World Road Bitumen
Emulsion Producers, Bordeaux, September 1997.
F. L. Roberts, P. S. Kandhal, E. R.
Brown, D. Y. Lee, T. W. Kennedy, Hot
Mix Asphalt Materials, Mixture Design
and Construction, NAPA Research and
Education Foundation Textbook, 2nd
Edition, 1996.
G. King, H. King, R. D. Pavlovich, A. L.
Epps, P. Kandhal, Additives in Asphalt,
J. Assoc. Asphalt Paving Technol. 75th
Historical Review and Index of Journals,
19751999, 1999, 68A, 3269,.
T. Hancock, UK Patent No. 9952,
November 21, 1843.
6 S. Shuler, J. A. Epps, Presented to the
7
8
10
Rubber Division, American Chemical

Society, Philadelphia, PA, 1982.
D. C. Thompson, J. F. Hagman, Assoc.
Asphalt Paving Technol. 1958, 55.
Construction of Hot Mix Asphalt Pavements, Manual Series No. 22, 2nd edn,
Asphalt Institute, Lexington, KY.
Use of Modified Bituminous Binders,
Special Bitumens and Bitumens with Additives in Pavement Applications, World
Road Association (PIARC) Technical
Committee Flexible Roads (C8), Laboratoire central des Ponts et Chausses,
September 1999.
World Road Association,
www.piarc.icpc.fr
References
11 Superpave Binder Manual, Superpave
12
13
14
15
16
17
18
19
20
21
22
Series No. 1 (SP-1), Asphalt Institute,

Lexington, KY.
D. A. Anderson, D.W. Christensen,
H. U. Bahia, M.G. Sharma, C.E. Antle,
J. Button, Binder Characterization and
Evaluation Volume 3: Physical Characterization, Strategic Highway Research Program (SHRP-A-369), National Research
Council, Washington, DC 1994.
W. Arand, O. Harder, B. Herr, Asphalt
Containing Conventional and PolymerModified Bitumens in High and Low
Temperature Conditions, PIARC XIXth
World Road Congress, Marrakesh,
Sept. 1991.
H. Bahia, W. Hislop, H. Zhai,
A. Grangel, Classification of Asphalt
Binders into Single and Complex Binders,
Association of Asphalt Paving Technologist, 67, 1998.
L. H. Lewandowski, Polymer Modification of Paving Asphalt Binders, Rubber
Chemistry Technol. 1994, 67, 447480.
B. Brl, Y. Brion, A. Tanguy, Paving Asphalt Polymer Blends: Relationships Between Composition, Structure and Properties, J. Asphalt Paving Technol. 1988,
57, 4164.
V. Wegan, B. Brl, The Structure
of Polymer Modified Binders and
Corresponding Asphalt Mixtures,
J. Assoc. Asphalt Paving Technol. 1999, 68,
6488.
AEMA Recommended Performance Guidelines, 2nd edn, Asphalt Emulsion Manufactures Association, Annapolis, Maryland.
A Basic Asphalt Emulsion Manual,
Asphalt Institute Manual Series
No. 19, 2nd edn, Lexington, KY.
R. Hassan, State-of-the-practice Design,
Construction and Performance of Microsurfacing, FHWA-SA-94-051, Federal
Highway Administration, Washington,
DC, 1994.
L. D. Coyne, Evaluation of Polymer Modified Chip Seal Coats, J. Asphalt Paving
Technol. 1988, 57, 545575.
K. Takamura, Comparison of Emulsion
Residues Recovered by the Forced Air-
23
24
25
26
27
28
29
30
31
32
33
34
flow and RTFO Drying, AEMA/ISSA

Proc. 2000, 117.
K. Takamura, W. Heckmann, Polymer
Network Formation in the Emulsion
Residue Recovered by Forced Air Drying, Proc. Int. Symp. Asphalt Emulsion
Technology, 1999, pp. 185194.
D. R. Jones, AEMA Annual Meeting,
Nov. 1988.
D. R. Jones, A. C. Ng, ISSA Annual
Meeting, Feb. 1989.
E. Cornet, Esso Abrasion Cohesion
Test, A Description of the Cohesive
Breaking of Emulsions for Chip Seals,
Proc. Int. Symp. Asphalt Emulsion Technology, 1999, pp. 346355.
J. L. Marchal, P. Julien, N. Boussad,
Bitumen Emulsion Testing: Towards
a Better Understanding of Emulsion
Behavior, ASTM Symp. Asphalt Emulsion, 1990.
J. Wates, A. James, Akzo Nobel internal results.
L. Barnat, Predictive Capabilities for
Maintenance Products, AEMA/ISSA
Proc. 2000, 1949.
C. Queiroz, R. Haas, Y. Cai, National
Economic Development and Prosperity
Related to Paved Road Infrastructure,
Transportation Res. Record 1455, 1994.
M. S. Mamlouk, J. P. Zaniewski, Pavement Preventive Maintenance: Description, Effectiveness, and Treatments, Symp. Flexible Pavement Rehabilitation and Maintenance, ASTM STP
1349, 1999, pp. 121135.
I. M. Syed, T. J. Freeman, R. E. Smitn,
Effectiveness of Highway Maintenance
Treatments Used in Texas, Symp.
Flexible Pavement Rehabilitation and
Maintenance, ASTM STP 1349, 1999,
pp. 136150.
K. Takamura, K.P. Lok, R. Wittlinger,
AEMA/ARRA Annual Meeting, February, 2001.
A. Horvath, C. Hendrickson, Comparison of Environmental Implications of
Asphalt and Steel-Reinforced Concrete
Pavements, Transportation Res. Record
1626, 1998, 105113.
327
13
Applications of Redispersible Powders

Hermann Lutz and Christoph Hahner
13.1
Introduction
The building/construction industry is the main industry for redispersible powders.

Over the years the usage of dry mortar technology has been developed dramatically
and modernized the way mortars are being used on a job-site. The invention of redispersible powders enabled the industry for the first time to produce pre-packed,
polymer modified building materials that needed only the addition of water before
application. These materials, known as dry mortar mixes guarantee defined and consistent performance of construction materials.
In the past up until to the 1950s mortars were exclusively used and applied as jobsite mixed mortars, where the mineral binder (mostly cement) and the aggregates
(mostly silica sand) were transported separately to the job-site. The aggregates and
the mineral binders were then mixed together by hand in the appropriate ratio and
were gauged with water in order to obtain the fresh mortar ready to apply.
During the 1950s and 1960s both in Western Europe and the US, but especially in
Germany, there was a fast growing demand in the construction industry for new
building materials and technologies. Several reasons, like shortage of skilled workmen, the need of shorter construction time together with cost reduction, increasing
labor costs, the diversification of building materials suitable for specific applications,
the request for new materials and an increased demand for better quality of constructions were supporting a movement towards dry mix mortar technology.
The job-site mix mortar technology is not able to meet adequately all these requirements. As a practical consequence, the development of the modern construction and building chemical industry in the countries of the West from the 1960s onwards was influenced mainly by two important trends, which can be seen nowadays
in the whole world. First there was a replacement of the job-site mixed mortars by
premixed and pre-packed dry mix mortars, which are more and more applied with
machines. Secondly mortars started to be modified with polymer binders in order to
improve the product quality and to meet the requirements of the modern building
industry. As a consequence the two-pack systems (mortar + dispersion) as well as
329
330
13 Applications of Redispersible Powders
ready to use products (liquid or paste) were substituted by one-pack systems, which
are modified with redispersible powders, pre-mixed and pre-packed dry mix mortars.
13.2
Manufacturing of Redispersible Powders
A redispersible powder is by definition a polymer in a powdered form that can be

redispersed by adding water to it. The resulting emulsion will fulfill the functionality of a polymeric dispersion binder, normally within a cementitious or gypsum based
system. Redispersible powders are manufactured by spray drying an emulsion
(Fig. 13-1).
Spray-dried
polymer particle.
Fig. 13-1
Over 90 % of all industrial manufactured polymer dispersions are produced by

emulsion polymerization. The most important monomers, which are being used for
applications in the building/construction industry, are vinyl acetate, ethylene, versatic acid esters, vinyl chloride, styrene and acrylics. Especially the use of ethylene as a
co-monomer offers some extraordinary advantages:
environmentally safe,
no saponification,
UV-resistant (no yellowing),
very hydrophobic,
ideal for co-polymerization with vinyl acetate,
very low glass transition temperature, Tg, of 93 C,
very flexible, and
good adhesion to most of the substrates.
To guarantee the performance of a redispersible powder in its final application a
protective colloid is added to the emulsion before the spraying process. The colloid
protects the polymer particles from film forming during the spray drying process
13.2 Manufacturing of Redispersible Powders
and is also responsible for that the powder will redisperse in water again (Figs 13-2
and 13-3).
dispersion
particle concentration
100 69
% ppm
80
weight distribution curve
69
ppm
60
40
20
0
0
10
particle size (diameter)
redispersion
100 92
% ppm
80
weight distribution curve
92
ppm
60
40
20
0
0
10
particle size (diameter)

Fig. 13-2
Dispersion/redispersion comparison of particle size distribution.
spray
drying
adding
water
drying
dispersion
Fig. 13-3
protective
colloid
The spray-dry process.
redispersible
powder
redispersion
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332
Over the years poly vinyl alcohol (abbreviated PVOH or PVAl) proofed to be the
most preferred protective colloid for that purpose. In a cementitious environment
PVOH will be partly saponified and also absorbed of fine particles within a mortar,
i.e. cement and fillers. This results in a film forming of the dispersed polymer and finally the polymer film is not redispersible any more. Since the polymer film (acting
as a binder) is distributed throughout the cement matrix it improves dramatically the
adhesion, abrasion resistance, flexural strength, flexibility, water impermeability/water repellency (hydrophobicity) and workability of a cementitious system.
13.3
Dry Mortar Technology
The invention of redispersible powders by Wacker-Chemie in 1953 made for the first
time the production of polymer modified dry mix mortars possible, which are nowadays referred to as one pack or one component system (bagged materials). New
construction methods and building materials, which had the need for more safety,
reliability, durability, efficiency and economy, have been achieved by using modern
methods like the dry mix mortar technology. As a consequence worldwide the jobsite mix technology and the modification of mortars with liquid polymers on jobsites were and are substituted by polymer modified dry mix mortars. The product
characteristics are very well adapted to the requirements of modern construction
technologies, materials and climates.
Pre-mixed and pre-packed dry mix mortars not only increase significantly the production performance and the productivity on construction sites, but guarantee also
that high and constant quality binder, aggregates, and additives are being mixed exactly in the same ratio, thus ensuring a consistent high quality level within dry mix
mortars. Furthermore, dry mix mortars offer solutions to specific problems that are
precisely tailored to certain types of construction/material specifications. Especially
in the USA, the legal aspect of a reliable, properly conducted construction job is very
important to each manufacturer of construction materials.
The use of redispersible powders and therefore also the use of polymer modified
powdered mortars is already for many decades standard in the construction industry
in Europe and North America (predominantly in the USA). Other marketplaces all
over the world like South America, Asia, Africa and Australia are in the process following that example. More and more environmental reasons ask also for the usage of
dry mortars, since the recycling of buckets becomes more and more an issue. Dry
mortars are also easy to store, transport and do not require biocides.
Typically dry mortar mixes contain the components listed in Tab. 13-1 and are
defined according to German standard DIN 18557.
The application areas of dry mix mortars are:
ceramic tile adhesive,
tile grouts,
E.I.F.S. (exterior insulation and finish systems)/E.T.I.C.S. (exterior thermal insulation compounds),
13.4 Markets and Application Areas of Redispersible Powders

Tab. 13-1
Dry mortar mixes.
Mineral binders
Portland cement
(OPC)
High Alumina
Cement (HAC)
Special cement
Hydrated lime
Gypsum,
anhydrite
Aggregates fillers
Polymer binder
Additives
Silica sand
Redispersible powder
Cellulose ether
Hydrated lime
Dolomite sand
Marble sand
Lightweight fillers
Special and functional fillers
Pigment
Defoamer
Air-entraining agent
Retarder
Accelerator
Thickener
Hydrophobing agents
Plasticizers
self-leveling over- and underlayments, screeds,

stucco, skim coat,
topcoat/finish coat,
patch and repair mortar,
adhesive mortars (for all kind of substrates),
crack isolation membrane,
powder paints,
gypsum based compounds (joint fillers),
waterproof membranes/sealant slurry,
pool decking, and
stamped concrete.
The following paragraphs will describe the most important and most developed
application areas for redispersible powders as they are ceramic tile adhesives/ tile
grouts, thermal insulation systems (E.I.F.S.), self-leveling underlayments, patch and
repair mortars, as well as water proof membranes (sealant slurries).
13.4
Markets and Application Areas of Redispersible Powders
To meet todays technical requirements, almost all dry mix mortars require polymer
modification. Many cementitious mortars contain cellulose ethers as an additive to
improve water retention and workability. However, after setting and drying they will
adhere poorly or not at all to most of the substrates used in modern construction
technology such as polystyrene panels, fiber panels, wood panels, closed and non-absorbent substrates or old tiles. In addition, cementitious mortars are very hard, brittle and inflexible materials, whereas for many applications flexible and deformable
cementitious materials are essential. As a consequence for almost all applications in
modern construction, the modification of cementitious mortars with polymers is a
must. In dry mix mortars the mineral binder, cement, and the polymer binder, redispersible powder, are ideal partners. The combination of both in a dry mix mortar
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334
provides outstanding synergistic properties and characteristics, which cannot be

achieved by either of the binders alone.
13.4.1
Adhesives for Ceramic Tiles
Ceramic tiles as well as natural stone were previously installed exclusively by using
the thick bed mortar technique. Silica sand and cement were mixed together on the
job-site, in order to produce a simple cement mortar with a cement/sand ratio of approximately 1:4 to 1:5. In some countries only cement is still used in order to set
tiles. After having applied (buttered) the mortar at a thickness of 15 to 30 mm (0.6
to 1.2 inch) on the reverse side of the water-soaked or pre-wet tile, the tile is pressed
into the pre-wet surface. The tiles have to be tapped to ensure uniformity and flatness of the tile surface, thus obtaining a final mortar bed of 10 to 25 mm (0.4 to 0.8
inch). This procedure causes not only compaction of the mortar, but leads in addition to the migration of the fine cement particles into the porous back side of the tiles
and the porous substrate as well. This process assures the mechanical fixing of the
tile in the mortar bed. This type of mortar has no slip resistance. Therefore tiling of
a vertical substrate has to be started at the bottom and distance splinters become
necessary. The described procedure shows very clearly that the thick bed method is a
very time, cost and material consuming process. More significantly, there are technical restrictions using this technique. One of the examples is that only small,
porous tiles can be applied over porous, solid and strong mineral surfaces. The application of tiles over wood would be almost impossible, since a mortar without any
polymer modification would not only be not flexible enough to withstand the movement of a wood substrate over an extended period of time, it would also have no sufficient adhesion to the substrate. Consequently severe damage could occur and
therefore the thin bed mortar technique has replaced the thick bed mortar technique
in most industrial countries.
It started in the USA in the early 1950s by adding a polymeric binder in form of a
liquid latex dispersion to a job-site mixed mortar (see Chapter 8). Nowadays dry mix
mortars modified with redispersible powders dominate this market segment more
and more. After gauging the polymer modified dry mix mortar with water, it can be
applied with a notched trowel, producing a ribbed mortar bed of uniform thickness.
Due to the good water retention capacity of the thin bed mortar, neither the tiles nor
the substrate have to be pre-wet. The tiles are pressed into the thin layered mortar
with a slightly twisting movement of the tile. An anti-sag ceramic tile adhesive allows
installing tiles on vertical substrates without using distance splinters between the
tiles. The tile installer can also start from the top of the wall instead of the bottom.
The mortar bed, which fixes the tiles, has a thickness of approximately 2 to 4 mm (up
to 0.25 inch). Since this method clearly uses less material, it is more cost effective,
can be used more universally; its execution is clearly simpler, faster and safer. The
clear advantages of dry mix mortars modified with redispersible powders, which apply also for tile grouts, are:
good workability, fast and easy to use, creamy consistency,

good water retention, which results in a long open time and good adjustability
even at high temperatures, and
substantial anti-sag properties, if required.
As far as the formulations for ceramic tile adhesives go there is a high variety of
mortars offered in the market place in order to meet all the specific requirements. A
major difference, for example, between Europe and the United States is the usage of
wood as a substrate in the USA. Differences in the formulation are also determined
by requirements of specifications or application circumstances like interior or exterior, wall tile or floor tile, vitrified tile or more porous tile, fast setting or regular
setting, flexible or even highly flexible. The availability of certain raw materials i.e.
silica sand determines very often how a formulation will perform.
The two most important specifications worldwide are the European Norms EN
and the American Standards ANSI 118.1-1999. The biggest difference between the
two standards is the principal test setup. The European Standards require mostly
tensile bond adhesion testing where else the American Standard uses shear bond
testing. The other difference is clearly the storage conditions for the specimen before
testing. A listing of both standards is shown in Tab. 13-2.
Tab. 13-2
EN and ANSI standards for CTAs.
European standards
EN 12004
Definitions and specifications
EN 1308
Anti-sag
EN 1347
Wetting capability (coverage)
EN 1346
Open time
EN 1348
Tensile adhesion testing, including heat and freeze-thaw storage
EN 1324
Shear-strength for mastics
EN 12002
Deformability of cementitious CTA
US standards
ANSI A 118.4
ANSI A 118.11
Specifications for Latex Portland cement mortar

Specifications for EGP (exterior glue plywood) LatexPortland cement mortar
Cement-based standard tile adhesives can be classified in very simple (low quality)
tile adhesives, which do not contain any polymeric binder. They do not meet European or American Standards. Such tile adhesives, providing a pure mechanical fixation can only be used for fixing small, very porous tiles. The substrate is supposed to
be dimensionally stable, sound and solid as well as not showing any shrinkage or
movement. If exposed to higher temperature or frost, there is a higher risk of failure.
Non-modified mortars show for the most part no long-term performance.
Simple tile adhesives have already a polymer modification of 1 to 1.5 % of a redispersible powder (calculated on total formulation). Such tile adhesives meet some
parts of the mentioned national standards, but usually fulfill not all requirements.
Only the usage of tiles with a medium porosity and small size could result in acceptable results with these types of adhesives.
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336
Standard ceramic tile adhesives of good quality need approximately 1.5 to 3 % of

redispersible powder on total dry mix. They meet the new European Norm for tile adhesives (mostly only C1 level) and pass also the ANSI specification 118.4 and 118.11.
Larger formatted tiles can be applied with these materials over porous or less porous,
dimensionally stable substrates. They are suitable for interior as well as exterior application. For standard applications these modified mortars provide higher quality
security and a certain long-term stability, very much depending on the factors like
climate conditions, weight traffic etc.
Finally flexible (5 to 8 % of redispersible powder) and very flexible ceramic tile
mortars with a polymer modification beyond 8 % up to even 25 %, guarantee the best
performance over all, very good adhesion on all types of substrates with all types and
sizes of tiles. These adhesives are used more universally and offer a much greater application variety, safety, as well as long-term durability and reliability. Nowadays
these mortars are more and more used to fix the very popular highly vitrified tiles
(water absorption <0.1 %) and natural stone tiles (like marble) in any format. The
substrate can be non-porous and inorganic as well as wood. Even if the substrate still
shows to a certain degree of shrinkage or expansion, including other types of movements or vibrations, these quality adhesives could be used to set tiles in a safe and
durable way. Typical application examples for flexible ceramic tile mortars are:
floor heat system within the substrate,
to heat exposed surfaces, like i.e. tiles on a porch exposed to sunlight,
tiles over tiles,
over gypsum boards,
over backer boards,
over wood,
on water proof membranes,
on thermal and sound insulation panels, and
on light-weight concrete blocks.
Tests conducted by international research and test institutes have proved that it is
of high importance that cementitious adhesives provide a sufficient deformability
and a certain degree of plasticity [14]. Only in that way, long-term durability and
functionality can be guaranteed. Adhesive mortars have to be able to absorb stresses
that occur between two materials as tiles and substrate in order to prevent damages.
Typical damages are cracking or even delaminating of the tiles. Irreversible differential movement, such as shrinkage causes always stress between tile and substrate
(fresh concrete is always likely to shrink). Reversible movements of the substrate like
vibrations and thermal movements due to heat or cold are also sources of stress between substrate, adhesive and tile. The different modulus of elasticity of tiles and
substrate is also enhancing the stress within a ceramic tile mortar (Fig. 13-4).
European Norm EN 1348 addresses this issue in a heat test as well as in a freeze/
thaw test. Shear stress between substrate and tile normally concentrates in the peripheral zones of a tile. That means, the bigger the tile the higher the flexibility of the
adhesive has to be in order to avoid cracking or delaminating of the tile. The flexibility (deformation capability) of a ceramic tile adhesive depends on the polymer/cement ratio. It is one of the two most important ratios to be determined in a ceramic
tiles
tiles
deformable
adhesive mortar
substrate
eg. concrete
substrate
eg. concrete
initial
dimension
initial
dimension
shrinkage of substrate
eg. shrinkage of concrete
expansion of tiles
eg. thermal expansion
tiles
tiles
rigid, non-deformable
adhesive mortar
substratre
eg. concrete
initial
dimension
Fig. 13-4
substrate
eg. concrete
initial
dimension
The stress between substrate and tile.
tile mortar (the other one is the water/cement ratio). The German test DIN 18156/3,
as well as EN 12002, measures the flexibility of ceramic tile adhesives. As a result of
these tests it can clearly be shown, that the higher the polymer/cement ratio the
higher the flexibility of a mortar system (Fig. 13-5).
Fig. 13-5
The flexibility of ceramic tile adhesives.
It is very important to mention that the deformation capability of a given cementitious system also depends to a large extent on the degree of hydration of the cement.
Consequently, the flexibility of different adhesives can only be compared at identical
337
degrees of hydration of the cement. Unfortunately this is very often not considered
within the storage conditions of different standards, that deal with the testing of flexibility (Fig. 13-6).
16.0
14.0
12.0
Flexion/deformation [mm]
338
10.0
8.0
6.0
4.0
2.0
0.0
50% Portland Cement
40% Portland Cement
35% Portland Cement
30% Portland Cement
Traverse deformation test according to EN 12002 - 5% polymer modification at

different cement levels
standard conditions
Fig. 13-6
water storage (full hydration) 7d sc/ 14d in water/ 21d sc
EN 12002 results on flexibility.
The relative humidity of approximately 95 % at the beginning is not kept constant

during storage and is not sufficient for a full hydration of the cement. Over the time
cementitious adhesives will reach their full hydration thus resulting in sometimes
very low flexibility of the mortar. For example, the use of additives and/or polymers
with a strong retardation effect on the cement will cause an incomplete hydration of
the cement and will lead temporarily to a higher polymer-to-cement ratio. The flexibility measured at this point will not reflect the real flexibility of the system after full
hydration of the cement phase. After complete hydration of the cement, soft polymers (lower glass transition temperature, Tg) will perform at an appropriate dosage
level better compared to polymers with a higher Tg, especially if used and tested at
lower temperatures (Fig. 13-7). (The glass transition temperature describes the flexibility of a polymer. The rule of thumb is the lower the Tg the higher the flexibility.
Tg is determined from the ratio of different monomers and their individual Tg in a
polymer, by use of the Fox equation [5]).
The adhesion of tiles to the substrate is certainly as important for a ceramic tile adhesive as the flexibility. The European Norm uses a pull off test to determine the
adhesion, where as the US standard ANSI 118.1 1999 prefers the shear bond test.
A simple ceramic tile mortar with no polymer modification will fail in the adhesion
test especially after heat aging or over wood (ANSI 118.11 1999). The same mortar
modified with only 2 % of redispersible powder will pass both tests. With the pull-off
Fig. 13-7
Flexibility at lower temperatures.
test, it can be demonstrated that a ceramic tile adhesive without polymer or with a
low polymer level will only be able to pass, if wall tiles (very porous, high absorptive
tiles) are used. In addition, it can be demonstrated that only a sufficient amount of
redispersible powder provides a significant adhesion on critical substrates like PVC,
wood or tiles (Fig. 13-8).
A sufficient high polymer modification of the ceramic tile adhesive is necessary especially when non-porous, highly vitrified tiles (low to no water absorption) are used.
In this case, there will be no mechanical anchoring like described earlier for porous
tiles. The redispersible powder (chemical bonding), in this case, only provides the adhesion. This is, besides the outlined reasons for sufficient flexibility, another important factor for a higher polymer modification.
A ceramic tile adhesive that performs very well over almost all substrates, with all
types of tiles (size, water absorption) should contain at least 6 % of redispersible
powder and the cement content should be limited to 30 to 35 %. An adhesive formulation that considers these two important components at the right amount is very
likely to pass all international standards. However, in an adhesive formulation has
more to be considered than only the polymer and cement level.
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340
Fig. 13-8
Adhesion of ceramic tile adhesives to different substrates.
13.4.2
Tile Grouts
Tile grouts, which are used to fill the joints in between the tiles, are very similar to ceramic tile adhesives in their formulations. They are expected to be water repellent
(hydrophobic), to have good adhesion to the substrate and the edges of the tile, sufficient hardness, a low tendency for staining, cohesion strength, abrasion resistance
and flexibility. In the USA the field of tile grouts is much more diversified than, for
example, in Germany, because US manufacturers offer a much greater variety of colors. Therefore, color consistency is of high importance as well. Redispersible powders with a hydrophobic effect are normally used to achieve all requirements of a tile
grout. They reduce the risk of efflorescence as well as staining of the grout. The standards in the US and Europe are summarized in Tab. 13-3.
The fields of ceramic tile mortars and tile grouts are certainly the most developed
for redispersible powders in cementitious applications. The use of redispersible
powder improves adhesion bond strength to all types of substrates, the deformability (flexibility), the cohesive and flexural strength, the open time the wetting capability as well as the workability within dry mix mortars.

Tab. 13-3
EN and ANSI standards for tile grouts.
European standards*
EN 12808-1
Determination of chemical resistance
EN 12808-2
Determination of abrasion resistance
EN 12808-3
Determination of flexural and compressive strength
EN 12808-4
Determination of shrinkage
EN 12808-5
Determination of water absorption
EN 12002
Determination of deformability
US standards
ANSI A 118.6
ANSI A 118.7
* There
Specification for standard cement grouts for tile installation

Specifications for polymer modified cement grouts for tile installation
is also a draft of Tile grout mortars for tiles, definitions and requirements
13.4.3
Exterior Insulation and Finish Systems and Top Coats
With the beginning of the 1970s exterior insulation and finish systems (E.I.F.S) were
used in Germany. (E.I.F.S. is predominantly used in North America. The abbreviation used in Europe is ETICS exterior thermal insulation compounds.) The first oil
crisis in Germany 1973 together with financial support of the government for homeowners had helped tremendously to promote the system. Some of the advantages of
E.I.F.S. are saving energy, healthier climate condition inside the house, less damages of facades and possible savings at the over all building costs. Between 1973 and
1993 approximately 300 million square meters of E.I.F.S. were applied on facades in
Germany. As a consequence more than 18 billion liters of oil were saved (approximately 113 million barrels). This also means considerably less CO2 was released into
the atmosphere, that also emphasizing a positive environmental aspect of E.I.F.S.
After Germany, the country with the most usage of E.I.F.S. is the United States.
However, the use of E.I.F.S. in the past within the United States has been more for
optical reason. Recently more and more the energy saving aspect of the system has
become a more considered aspect for homeowners. In both countries, organizations
exist representing the E.I.F.S. industry and its interest: representative of Germany is
the Fachverband Waermedaemm-Verbundsysteme and of the USA the Exterior
Insulation Manufacturer Association, EIMA.
The technology used in both countries is predominantly based on the usage of
polystyrene as an insulating material. In the early 1970s, the materials for E.I.F.S. offered in Germany were shipped to a construction site as ready to use systems (pasty
consistency). They had to be mixed with cement before usage. Mistakes occurred by
not meeting the polymer cement ratio according to the manufacturers requirement,
resulting in damages and complaints. The industry shifted almost completely to dry
mix systems in order to avoid the mentioned problems. The use of machines also
promoted dry mix mortars modified with redispersible powders. The time and cost
savings remain tremendous. In the US, reliability and control over the formulation
out of production as well as time and cost savings of machine applicable systems,
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342
has clearly set the trend over the last 510 years towards more and more usage of the
dry mortar technology and, therefore, towards redispersible powders/polymers.
Because of the use of redispersible powders, the application of E.I.F.S. has reached
such a high level of reliability and quality consistency that manufacturers in Germany normally allow a 30-year warranty for their systems. So far this level of warranty is not yet achieved in the US.
In Europe, as well as in the US several technical tests are conducted in order to
prove the performance of E.I.F.S. under different test conditions. The testing of such
systems is very severe. Some of the most important types of tests conducted on an
E.I.F. system are:
stability and flammability,
insulation properties,
adhesion of cementitious materials on polystyrene,
water absorption,
impact resistance, and
flexural and compressive strength.
Most of the tests are still very much depending on the country (Europe). In the US
there are different authorities (regional and city codes) like the American Society for
Testing and Materials ASTM, the Building Officials and Code Administrators
BOCA, the International Conference of Building Officials ICBO and the Southern Building Code Congress SBCC. Information on test procedures is also available through EIMA. More specific information can be gathered through the different
organizations. In Europe the entire E.I.F. system needs even a technical approval
granted by testing institutes according to the European Organization for Technical
Approval, EOTA. The principle layers of an E.I.F. system are shown in Fig. 13-9.
1. Substrate
2. EPS-Adhesive
3. EPS-Board
4. Base Coat
5. Top Coat/Finish
Fig. 13-9 The principle structure

of an E.I.F. system.
Substrates might vary. In the US it is normally plywood. Normally one will find
concrete/brick as a substrate. Right on top of the substrate the insulation board is
glued with an adhesive. In addition sometimes mechanical fasteners are use as well.
85 % of the insulation material used in Germany is Extruded Polystyrene EPS. The

EPS adhesive is normally the same material as the base coat. The functionality of the
base coat is protection and reinforcement of the EPS panel. Without polymer modification there would be no adhesion of the EPS to the substrate and no adhesion of
the base coat to the EPS panel. Besides adhesion, the right polymer modification becomes also very important when impact resistance, water absorption or deformation
capability (flexibility) is tested. The base coat has an important functionality within
the entire system. The right modification of the base coat with at least 3 to 6 % redispersible powder will finally guarantee good performance values and as a consequence contribute to an excellent weather stability of the entire system. The integrity
of the base coat, meaning a crack free base coat, is a precondition for good technical
performance. For that purpose the polymer-to-cement ratio should be as high as
possible. This is one of the main differences between Europe and US . Normally the
cement content in US systems is higher than in Europe. Assuming the polymer
content is very similar, this results in a higher polymer-to-cement ratio in European
systems compared to US systems. This has to do with the fact that the preference in
Europe is towards more flexible system where else in the US a hard surface appearance of the base coat is preferred by contractors.
Certainly as important as the base coat is the topcoat for the entire system. Here
we find probably the biggest difference between, for example, Germany and the
United States. In the US cementitious topcoats are almost not used at all. They are
synthetic, cement free systems that are very often ready to use and based on emulsion technology. In Europe, as with Germany, topcoats are cement based as well.
Top/finish coats must meet certain critical physical and technical requirements.
These include:
good adhesion to the substrate (tensile adhesion strength),
low water absorption or water repellency (hydrophobicity),
good drying characteristic (high water vapor permeability),
low susceptibility to cracking (good relaxation properties, flexibility),
the modulus of elasticity of the top coat should be lower than the modulus of elasticity of the substrate (layer below),
resistance to weathering,
mechanical stability (high impact resistance),
low dirt pick up,
very low flammability.
(Finish or topcoats can also be named render, plaster or stucco. Normally slight
differences apply, for example in thickness of the coating depending on the technology used. As far as the use of redispersible powder is concerned, they can be considered equivalent.)
The addition of organic polymeric binders in form of redispersible powders to
mineral plasters and stuccos can significantly enhance certain properties, such as
adhesion to the substrate, mechanical resistance, low water absorption (hydrophobic
effect by using special redispersible powders) and long-term durability. In order to
meet these requirements the preferred redispersible powders used in topcoats are
vinyl acetate/ethylene copolymers. Especially when it comes to flammability vinyl
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344
chloride containing systems perform the best closely followed by vinyl acetate ethylene containing polymers. Topcoats/E.I.F.S based on acrylics and acrylates, like
styrene acrylics, perform the worst in this respect.
The addition of approximately 0.5 to 2 % special hydrophobic redispersible powders to dry mortars additionally imparts uniform water repellency throughout without effecting the water vapor permeability.
Mineral topcoats are composed of lime and cement as mineral binders, aggregates
(fillers like silica sand), pigments and additives, such as cellulose ethers, starch
ethers, lightweight fillers, fibers, thickener, hydrophobic agents, wetting agents and
sometimes even surfactants. With the exception of any mineral binder this list
applies also to synthetic topcoat which are almost exclusively used in the US. Table
13-4 shows some of the specifications for topcoats in Europe (Germany) and the US.
Tab. 13-4
Specifications for topcoats.
German-US standards
DIN 18555/ASTM C 109
DIN 18555-6/*
DIN 52615/ASTM E 96
DIN/EN 196/ASTM C 580
* ASTM
Compressive strength
Tensile bond adhesion
Water absorption
Water-vapor permeability
Air content
Flexural strength
E 2134-01 for E.I.F.S.
One aspect that is very important to the E.I.F.S. industry as well as to topcoat manufacturers is certainly the hydrophobicity of their base coats and/or topcoats.
What is the mechanism behind a hydrophobic effect achieved by using a hydrophobic redispersible powder?
When water is added to the dry mix topcoat, the polymeric binder in the form of a
redispersible powder is very quickly redispersed. Then the polymer particles accumulate mainly in the pores, forming a film that coats the pores without actually
blocking them [68]. Because the pores (capillaries) are coated with a water repellent
polymer film with good adhesion to the cement, the capillary water absorption is reduced. Thus a permanent effect is achieved throughout the mortar. If the amount of
redispersible powder stays within 3 to 6 % there is no loss of water vapor permeability. This, of course, depends also very much on the hydrophobicity of the used redispersible powder. Because of the mentioned adhesion of the polymer to the cement
pores the adhesion as well as the flexural strength and toughness of the material is
improved also. Scanning electron micrographs are shown in Fig. 13-10 and demonstrate the formation of the polymer film within the cement matrix.
The SEM technology was also used to demonstrate that the redispersible powders
continue to fulfil their functionality over an extended period of time. This is also
shown by experiments to determine physical factors such as water absorption and
water vapor permeability on defined test specimen after long-term exposure to outdoor weathering conditions. Figure 13-11 shows the capillary water absorption of test
specimen after up to 6 years outdoor exposure at different polymer levels.

Fig. 13-10 SEM of polymer
film in cement matrix.
Capillary water absorption of mineral topcoat - long term exposure

4
water absorption coefficient

according to DIN 52617
3.5
3
2.5
2
1.5
1
0.5
0
0.5%
1.0%
2.0%
3.0%
3.5%
percentage redispersible powder on total formulation
21 days standard conditions
Fig. 13-11
1 year outdoor exposure
6 years outdoor exposure
Long-term performance of cementitious topcoats.
13.4.4
Self-leveling Underlayments
The area of self-leveling underlayments (SLU) is out of a technical perspective probably the most complex one if it comes to applications of redispersible powders. On a
given uneven substrate (i.e. screed or surface to be refurbished), self-leveling mortars have to provide a suitable, smooth and solid substrate in order to apply all kind
of flooring materials like carpets, wood parquet, PVC, tiles etc. Self-leveling underlayments should be applicable in an easy and efficient manner, even for large areas.
345
346
Therefore, the SLU material has to have very good flow characteristics, self-leveling
and self-smoothing properties. In addition, it should perform fast setting/drying,
saving time and thus the floor surface can be applied after only a few hours. The SLU
material should adhere to all kind of substrates, provide low shrinkage, high compressive strength and abrasion resistance.
The technical requirement of a SLU reaches from very simple to highly sophisticated products. They vary in thickness from a very thin layer of 110 mm (1/252/5
inch) (feather finish, self-leveling/troweling mortars and underlayments), up to 60
mm (approx. 2.5 inch) for self-leveling screeds, which are always applied by machines (mixing and pumping in one set up). The set time (walk over time) of these
materials changes from normal/regular setting to very fast setting products. Normally this is a question of the requirement of a specific job, allowing putting down
the floor above the SLU in a certain time frame. The shorter the setting/drying time,
the thicker the mortar is applied, the more complicated and expensive the formulation becomes. Self-leveling compounds (underlayments and screeds) are based on
special hydraulic binders like Portland cement (OPC), high alumina cement (HAC)
and gypsum (anhydrite), in order to achieve fast curing and drying by avoiding excessive shrinkage or expansion.
So far there are no standards on self-leveling underlayments (SLU) in Europe or
the U.S. However, the techniques and the application is very well known for many
years. Polymer modification is absolutely necessary within this technology, since the
requirements are very sophisticated. According to their use and the specific requirements, SLUs are polymer modified by 110 % of redispersible powder calculated on
total formulation. Standard products are normally modified between 2 and 4 %,
highly modified mortars are mainly used for refurbishment of wooden floorings
with self-leveling compounds. The redispersible powder increases the adhesion to all
kind of substrates, decreases the internal stresses (reduced crack formation and high
abrasion resistance), improves the flexural strength, elasticity and the abrasion resistance. Special powder grades will also support the self-leveling and self-flowing
characteristics of the mortar. Figure 13-12 shows the results of an abrasion test for a
self-leveling compound with and without modification with a redispersible powder.
Depending on the dosage of the redispersible powder, the abrasion resistance can be
reduced significantly. This becomes especially than very interesting, when the SLU
is also used as a wearing surface in an overlayment application.
13.4.5
Patch and Repair Mortars
Concrete is a very versatile, long-lasting and durable building and construction material if it is applied according to the state of the art. In the past, and even today,
unfortunately, repeated disregard of the fundamental principles of concrete and
structural concrete application has lead, and, in many cases, still leads to severe and
serious damage in the building industry. The cost of the repair of concrete structures
has dramatically increased over the last 30 years in all industrial countries. In Ger-
Fig. 13-12
Abrasion resistance with and without redispersible powder.
many approximately 20 % of the cost of the volume of structural concrete work is attributed to the repair and maintenance of existing buildings and structures.
The degradation of structural concrete is caused by corrosion of the steel reinforcement due to chemical processes, which often occur over a long period of time.
One of the main reasons is the carbonation of concrete. Acidic carbon dioxide (CO2)
from the atmosphere and other aggressive media (such as SO2, acid rain) neutralizes
the alkalinity of the concrete. Once the alkaline environment of the steel reinforcing
no longer exists, the steel starts to corrode and, due to its volume increase, causes
splitting of the concrete on top of the steel reinforcement. A secondary cause of corrosion is the penetration of free chloride ions into the concrete, leading to chloride
ion attack on the steel.
347
348
In the construction industry concrete repair work can be classified in two types:
concrete repair, which does not contain steel reinforcement and which does not
have load-bearing functions. The repair is normally done for aesthetic reasons
(cosmetic repair work) only, with namely patching mortars/compounds
repair and reconstruction of damaged reinforced and load-bearing concrete structures, in order to maintain and reconstitute their structural stability. This is done
in stages with different kind of mortars, which are part of a concrete rehabilitation system (typical applications: repair work and rehabilitation of bridges, parking decks, tunnels, etc).
Patching mortars for re-profiling and cosmetic repair are mainly based on dry mix
mortars and are not part of an entire repair or rehabilitation system. Usually, cement-based mortars are used for indoor and outdoor applications, whereas gypsumbased products are only used for some specific indoor applications (cosmetic repair).
Patching mortars are used to repair defective or damaged areas of mineral surfaces
without taking on a load bearing function, i.e. for filling small holes, voids, cracks
and cavities in order to restore the original dimension. Typical applications are
patching mortars for walls, ceilings, floors, steps of staircases, etc. These mortars
must have the following characteristics:
good workability,
easy to apply,
good adhesion to all construction substrates,
high durability and abrasion/wear resistance, if exposed to direct wear/load,
sufficient flexibility to reduce the risk of crack formation,
low shrinkage, and
water repellence for outdoor applications.
To meet the required technical criteria, these patching mortars are applied as a
polymer modified pre-packed dry mix mortar. Polymer modification with redispersible powder will depending on the dosage improve the:
workability of the mortar,
wetting capability of the substrate,
adhesion to all kind of substrates,
flexural strength,
abrasion resistance,
flexibility (lower modulus of elasticity than substrate),
durability, and
water repellent effect by using special grades of hydrophobic redispersible powders.
To be able to guarantee the durable and reliable repair of structural concrete, three
main fundamental requirements of a concrete rehabilitation system must be fulfilled simultaneously:
restoration of the corrosion protection of the steel reinforcement (alkaline environment),
restoration and re-profiling of the concrete structure including its load-bearing
functions, and
restoration of the durability of the whole construction (protection against weathering and environmental damage caused by CO2, SO2, Cl2, salts, etc.).
Today, polymer modified cement concrete (PCC) mortars, which can be applied by
hand, in a wet or even a dry spraying process, are usually used for the rehabilitation
of concrete structures. Different kind of mortars with different characteristics and
functions are used as the components for concrete rehabilitation systems:
primer and adhesion promoter for the reinforced steel (polymer modified cementitious slurry or epoxy based coating materials),
adhesion promoter slurry (primer or key-coat) for the concrete to be repaired (polymer modified cement based slurry),
restoration and re-profiling mortar (polymer modified cement based mortar),
fine stopper or smoothing mortar (polymer modified cement based mortar containing fine aggregate), and
protection and finish coat (dispersion paints, crack over bridging paints, cementitious waterproofing sealing slurries, etc.).
The improvement of adhesion to concrete and steel, using a polymer modified reprofiling mortar, with and without applying a cementitious primer, is demonstrated
in Fig. 13-13; Fig. 13-14 shows the improvement in flexural strength of a typical reprofiling mortar applied by hand with and without different grades of redispersible
powder.
Tensile bond adhesion after 28 d standard conditions
polymer/cement ratio = 0.07
3
Tensile adhesion [N/mm2 ]
2.5
1.5
0.5
0
over concrete
over steel
without primer
Fig. 13-13
with primer
Adhesion to concrete and steel with and without primer.
The flexural strength of the mortar is already significantly improved by adding

only 2 % of redispersible powder without affecting the compressive strength too
much.
349
Flexural strength of repair systems modified with different

redispersible powders and applied by different techniques
14
12
Flexural Strength [N/mm2 ]
350
10
8
6
4
2
0
shotcrete spray applied
no polymer
Fig. 13-14
redispersible powder 1
hand applied
Flexural strength improvement by use of redispersible powders.
Almost the same improvements are obtained by applying the repair mortar
through a dry shotcrete process. Within this process the water is mixed with the dry
mortar only in the jet. After that the mixed mortar is immediately sprayed onto the
surface. Despite this extremely short mixing and almost no slake time, the redispersible powder redisperses quickly and completely enough in order to improve the
tensile adhesion strength and the flexural strength in almost the same magnitude
compared to a conventional application by hand.
13.4.6
Waterproof Membranes
Water in liquid or in vapor form is the most destructive weathering element for
building constructions, like concrete, masonry, and natural stone structures. Waterproofing and damp-proofing techniques are used to preserve a structures integrity,
functionality and usage throughout its lifetime. For preventing all possible water intrusions, the exterior of a building has to be protected form top to bottom with waterproofing materials. Exterior parts of a building could be classified in roof coating,
below-grade waterproofing materials, which are materials to prevent surface- and
ground water or water under hydrostatic pressure from entering into a structure.
Typically metal and plastic films, cementitious waterproofing sealing slurries and bituminous waterproofing systems are used for that type of application. Above-grade
waterproofing materials, which prevent water intrusion into exposed structure elements, could be categorized into:
decorative and finishing barrier systems, i.e. all kinds of paints;

mineral topcoats (renders, plasters);
damp-proofing materials, which reduce or prevent water vapor transmission
through building materials and are not subjected to weathering or water pressure
(water vapor barrier foils); and
flashings, materials or systems installed to direct water entering through the wall
cladding back to the exterior like metal foils in walls to prevent capillary water uptake.
All waterproofing has to be part of a whole system and must interact integrally to
reach complete effectiveness and to prevent water infiltration. In case one of these
system parts fails or does not perform with all other protection systems, leakage will
occur. Adequately controlling groundwater, rainwater and surface water, as well as
the transport of humidity in the form of water vapor will avoid unnecessary repairs to
buildings exterior or its damage or even destruction (deterioration). Apart from protecting the exterior of building constructions, there is a multiplicity of waterproofing
materials for interior use. Some of the waterproofing materials are used to protect
against the detrimental action of aggressive substances like salts and acids transported by the water.
Traditional sealing and waterproofing systems, i.e. according to the German standard DIN 18195, include bituminous materials, plastic waterproofing foils and metal tapes for interior and exterior applications. Different types of materials can be
used in order to seal and protect the surface of buildings or its structural components against the intrusion of dampness and water. Nowadays products for that purpose are based on reactive resins like epoxy and/or polyurethane, dispersions
(paintable waterproofing membranes) and mineral binders like cement, which are
known as waterproofing membranes or sealant slurries.
Cementitious waterproofing membranes have been successfully used for more
than 40 years in Europe for protection of a wide range of building structures and
structural components. The structures were either exposed to periodically or longterm wettings (surface water, seepage water), low hydrostatic pressure (soil dampness) or in combination with appropriate engineering even high hydrostatic pressure. Cementitious membranes (slurries) are used to waterproof wet rooms and
water tanks, and due to their excellent weathering resistance they are also used for
exterior surface protection. Further typical applications are the sealing and waterproofing of basement walls, swimming pools, walls and floors, in bathrooms, on balconies and porches (as a waterproofing layer to be tiled over). Especially in the case of
a tile application these slurries can also act as crack isolation membranes. In addition, flexible, cementitious waterproofing membranes are often used as a protective
surface-coating system for structural concrete (i.e. protection of reinforced structural
concrete within new structures as well as for concrete structures after restoration). It
is applied for the protection against penetration of water, chlorides and free carbon
dioxide in order to avoid corrosion of the reinforcing metal and can provide a protective layer to a building against aggressive chemicals (sulfates, acids, i.e. in waste-water drains). Some of the advantages of cement-based waterproofing membranes are:
351
352
excellent resistance against water, even if exposed permanently;

excellent resistance against long term weathering;
good scratch resistance;
good load-carrying capacity; and
much higher water vapor permeability compared to most of the other systems.
Consequently there are no problems with blistering since water vapor passes
through the membrane.
Cement-based waterproofing slurries are easy to use, non toxic, provide a fully
bound and monolithic surface without joints and can be easily applied on substrates
with complex surface shapes. In contrast to other systems, cementitious waterproofing slurries can even be used on damp and wet mineral surfaces. Their physical
properties are also less temperature dependent compared to bitumen based materials.
Simple, non-polymer modified cement based slurries are still used for the protection against surface water, but they are not suitable to seal against water under hydrostatic pressure. In order to improve the poor adhesion, the poor water tightness,
and the extremely low deformability or flexibility of these non modified systems,
polymers are added in form of liquid dispersions on the job-site or in form of a redispersible powder already mixed in the dry mix mortar. The use of special additives
in the dry mix mortars like water retention agents, thickening agents and rheological
additives in combination with the polymeric binder, the redispersible powder, provide an excellent workability and make sure that there is no need for a post watertreatment of the applied slurry.
Today, in principle, two different systems of cementitious waterproofing membranes or slurries are available:
1. Standard or rigid mineral waterproofing slurries, which are polymer-modified,
pre-packed dry mix mortars containing approx. 3 to 6 % of redispersible powder.
They are used for mineral substrates, which are stable, sound and solid. There
should be no risk for crack formation, movements or dimensional changes like
shrinkage.
2. Flexible and highly flexible cementitious waterproofing slurries (as two-component or one-component systems).
In addition to the traditional, rigid waterproof membranes, developments in the
late 1970s led in Europe to flexible waterproofing slurries, which are to a certain extend capable to over-bridge small cracks (up to approx. 1 mm) in the substrate. The
flexibility of such products strongly depends on the polymer/cement ratio and certainly also on the flexibility of the polymer itself. Flexible and highly flexible waterproofing cementitious slurries are used on substrates still undergoing shrinkage, vibrations, movements, stresses, crack formation and on substrates difficult to be coated like wood, steel, aerated light weight blocks and gypsum. Due to their high polymer content (up to 2540 % on total formulation), they are diffusion and chemically
resistant against chloride, sulfate ions and carbon dioxide or other aggressive materials.
Thus far these flexible cement based waterproofing, sealing slurries have been
mainly used as two-component systems (liquid dispersion/emulsion added to the
13.5 Summary
pre-packed dry mix). But due to the many disadvantages of modifying mortars with
liquid dispersions on a job-site, in modern construction technique more and more
the one-component, flexible cementitious slurries, modified with high dosages of
special redispersible powders are used. These one-component, premixed polymermodified dry mix mortars are offering advantages as they were already discussed
within this chapter.
13.5
Summary
The need for new construction methods and building materials, that are safely, reliably, efficiently and economically to apply, promotes modern technologies like the
dry mix mortar technology. Redispersible powders make the production of complete pre-manufactured high quality mortars (bagged mortars) possible. As a consequence, job-site mix technology and job-site modification of mortars with liquid
polymers is being replaced all over the world. Especially since product characteristics
can be specifically designed for modern construction requirements and climate conditions by using dry mix mortars.
Dry mix mortars modified with redispersible powders provide a significantly improved productivity on the construction site. They allow a high degree of rationalization coupled with an easy, rapid, more efficient and safer handling and processing of
the product. This eliminates onsite mixing errors and ensures, consistently, excellent results. The quality of the workmanship is consistent on a high level thus improving the warranty status of a construction job dramatically.
Dry mix mortars, mainly based on cement but also on gypsum, that are modified
with redispersible powders have been successfully used for many decades all over
the world. The most typical applications are:
ceramic tile adhesives,
tile grout mortars,
mortars for the thermal insulation systems,
stuccos, skim-coats and finishing renders,
patch and repair mortars,
self-leveling under- and overlayments,
waterproofing sealing slurries (membranes),
joint compounds, and
powder paints.
The modification of dry mix mortars with dry polymers in the form of redispersible powders also significantly improves the technical performance of the mortars. The combination of the mineral binder with a polymeric binder in the form of
an redispersible powder in dry mix mortars guarantees outstanding synergistic properties and characteristics, which cannot be achieved by either of the binders alone.
The sufficient modification of mineral dry mix mortars by redispersible powders will
improve workability, adhesion to various substrates, flexibility and deformability of
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354
the mortars, abrasion resistance, density (impermeability), flexural and cohesive

strength and the long-term durability.
Manufacturers, contractors, applicators and end-users (Do it yourself market) all
benefit significantly from dry mix mortars modified with redispersible powders.
That technology almost exclusively makes machine applications, which become
more and more popular with all kinds of construction materials, possible.
References
1 Research report No. 13 of Vereinigung
von Systembouwers van de Werkgroep

SA 5, Tegels, Het vermijden van Schade
aan gelijmd Wandtegelwerk; March
1975, Vereinigung von Systembouwers,
Gravenhage, Netherlands.
2 Publications of G. Wesseling (TNO Institute, Netherlands); in Tonindustrie
Zeitung No. 8 1971, 95, 211.
3 Research report B II 5 800177-118;
Ermittlung des Verformungsverhaltens
von Duennbettmoerteln bzw. Klebstoffen fuer keramische Fliesen; August
1979 von Prof. Dr. Kirtschig; Technische
Universitaet Hannover.
4 Rapport Lim for keramiske fliser;
5
6
7
8
methode for proving av even tile

aoverfore relative bewegelser mellom
underlag og fliser (flexksibilitet) von
BYGGFORSK, Norwegisches Bauforschungsinstitut, Forskningsveien 3 b;
Postboks 123 Blindern, 0314 Oslo 3,
Projekte E 3593, Trondheim
04/08/1992.
Fox T.J.; Bull. Am. Phys. Soc. 1956, 1, 23.
Schulze, J.; Tonindustrie-Zeitung 1985,
109, 698.
Schulze, J.; Beton 1991, 5, 232.
Adler, K.; Schweizer Baublatt 1988, 31,
44.
14
Applications for Modification of Plastic Materials

Chuen-Shyong Chou and Jane E. Weier
14.1
Introduction
The global plastics industry is growing rapidly with an annual average rate of 46 %.
This is primarily due to the fact that plastics continue to replace traditional materials
such as metals, wood, and minerals. In a very dynamic market such as building and
construction, the compounded annual growth rate (CAGR) of plastics was about
78 % between 1992 and 1997. In the same period of time, PVC poly(vinyl chloride),
accounted for more than half of the plastics consumption in the segment, achieving
CAGR of 9 % [1]. The successful application of plastic materials has substantially enabled the incorporation of additives to the resins. Amongst the numerous additives
used, polymeric impact modifiers and process aids provide some of the most unique
and valued performance and processing enhancements [2, 3]. Toughening, rheology
control, aesthetics, processing, and economics are the major performance attributes.
These additives have been around for many years, and they have evolved over that
time into a broad array of product offerings. A key reason is the versatility of emulsion polymerization, which enables scientists to design proper polymer composition, polymer structure, polymer morphology, and polymer molecular weight/
molecular weight distribution. Emulsion polymerization is commercially attractive
because of the low manufacturing cost and ease of isolation for the resulting latex
products.
The first polymeric additives produced using emulsion polymerization technology
were core-shell impact modifiers made of methacrylatebutadienestyrene (MBS),
which were introduced in 1956. These were followed by all-acrylic process aids and
acrylic impact modifiers [4, 5]. The additives were originally aimed at improvements
in PVC processing capability and toughness. Nevertheless, the application has been
extended to polyolefin and many engineering resins such as nylon, polycarbonate,
and polyesters. In addition to toughening of thermoplastic matrices, core-shell impact modifiers were also applied to fracture toughening of thermoset resins such as
epoxy and unsaturated polyesters [611]. Processing aids are mainly applied to a PVC
compound for fusion promotion, melt strength, dispersion and surface quality. Ultra
355
356
14 Applications for Modification of Plastic Materials
high molecular weight processing aids are critical components in foamed PVC. With
the help of the processing aid, more uniform cell structures with less rupture and
lower foam density can be achieved. Lubricating type processing aids prevent the
melt plastic from sticking to metal surface, improve surface quality, and increase
productivity. In addition to PVC, polymeric processing aids are becoming popular in
other thermoplastics for certain limited applications.
In addition to impact modifiers and processing aids, a number of polymeric modifiers have been promoted for controlling gloss, improving heat distortion temperature (HDT), enhancing compatibility in polymer alloys, broadening the thermoforming window, controlling light diffusion and optical properties, and improving the
plastic and cellulose composites processing. These polymeric modifiers offer some
unique properties and many of the developments are also tied closely to emulsion
polymerization technology.
14.2
Emulsion Polymerization and Isolation Technology
A comprehensive description of emulsion polymerization chemistry can be found

in books written by Gilbert [12] and Lovell and El-Aasser [13] and Blackley [14].
Although the process appears straightforward, the technology is extremely complicated. Several possible polymerization loci can be present simultaneously including
the aqueous phase, micelles, monomer droplets, particle-water interface, and latex
particles. Emulsion polymerization techniques are in wide commercial use because
of their many advantages; however, the process is not without its drawbacks. The
major advantages include:
The rate of polymerization is usually considerably greater than in a bulk process.
An emulsion polymerization can easily achieve a relatively high conversion of
monomer to polymer; hence any problems with residual monomer are minimized
and monomer consumption is maximized.
The polymer usually has a considerably higher average molecular weight than that
from a solution polymerization or bulk process, and has a different molecular
weight distribution. The polymer molecular weight can be controlled with appropriate initiator and reaction conditions.
Because the molecular weight is very high in the absence of chain-transfer agents,
molecular weight is easily controlled by the addition of chain-transfer agents, and
allows for additional control of the properties.
Various polymer morphologies with different molecular structures and molecular
weights can be achieved with a multiple-stage process. It is possible to control the
morphology of the system with layers, lobes or isolated domains of specific composition.
A core-shell impact modifier is probably the best model to illustrate the utility of
emulsion polymerization technology. The core polymer is based on a low glass transition temperature (Tg) rubber and is surrounded by a hard polymeric shell (high Tg
material). The core rubber is made in the first stage of the emulsion polymerization,
14.2 Emulsion Polymerization and Isolation Technology
and serves as the part of the modifier that promotes impact. It is typically made with
monomers such as butyl acrylate (BA) and/or butadiene (Bd). The monomers used,
the polymer molecular weight, and the internal structure of the rubber core affect the
impact performance. The shell of the particles, occasionally referred to as the outer
or hard stage, consists of a polymer that is chemically grafted onto the core. Typical
commercial examples of polymers used in the outer stage are poly(methyl methacrylate), polystyrene, and styrene-acrylonitrile (SAN) copolymers. The shell polymer
provides ease of isolation and/or handling and facilitates dispersion and interaction
with the matrix.
Polymeric processing aids are generally high Tg copolymers and contain a large
fraction of methyl methacrylate (MMA) or styrene-acrylonitrile. Products with a
wide range of weight average molecular weights, from about 100 000 g mol1 to over
6 000 000 g mol1, are commercially available. Ultra high molecular weight polymers
can only be achieved by an emulsion polymerization process. The polymeric processing aids can be grouped by their specific function and/or application. The references shown in Tab. 14.1 provide additional details on the emulsion polymerization
process for specific type of polymeric modifiers.
14.2.1
Isolation Technology
Free-flow powders, granules or pellets are the common product forms used in the
plastic industry. Isolation of the emulsion is therefore an important part of commercial processes. The product form can have a significant effect on its ease of handling,
compounding and incorporation into the matrix. It also affects the powder storage
stability such as compacting tendencies. The three most common approaches to isolation are contrasted below:
Feed
Residence time in dryer
Powder particle size (m)
Spray dryer
Fluid-bed dryer
Flash dryer
Emulsion
5100 s
10500
Wet cake
1300 min
103000
Wet cake
15s
10300
Spray drying is an attractive approach as long as the polymer solids content is

high, thus requiring less water removal. Spray drying involves injecting the emulsion with hot air and forcing it rapidly through a rotating nozzle, to evaporate the water quickly [74]. Although highly efficient, this method results in the retention of
non-volatile elements added during the polymerization, such as emulsifier and inorganic salts, which might affect the resin. To this end, a full range of technology has
been developed around controlled coagulation of the emulsion, followed by filtration
of the aqueous phase and final drying of the resulting wet-cake. A much cleaner
product can be produced in this manner. Details of these methodologies have been
published extensively [7578].
357
358

Tab. 14-1
Polymeric modifiers classified by function.
Type
General Composition
Function/Application
Refs
General purpose
MMA/BA, EA, BMA
PVC processing aids MMA/Sty, SAN,
SAN/MMA
Promote PVC fusion, improve

melt elasticity and strength,
reduce melt fracture, and
improve surface quality
1553
Lubricating
processing aids
BA/Sty/MMA,
BA/MMA, EVA
Promote PVC fusion, prevent

polymer melt from sticking to hot
surface, assist mold release,
improve surface quality and
throughput
5459
Foamed PVC
processing aids
MMA/BMA, EA, BA
SAN/MMA, SAN
Promote PVC fusion, reduce

foam density, improve surface
quality, provide good cell
uniformity, increase process
flexibility
51, 6062,
157183
Melt rheology
modifiers
Methacrylate-based
polymer
Lower melt viscosity in PVC and

ABS, improve melt strength
in polyolefin and engineering
resins, improve mixing and
homogeneity in ABS/SAN blend
6370,
146
PVOH processing
AIDS
MMA/NVP/
methacrylic acid
Enable melt processing, maintain

rigidity and barrier properties
of the polymer
7173
Acrylic impact
Modifiers
BA//MMA,
2-EHA/MMA
Toughen PVC, engineering resins,

epoxy and other thermoset resins.,
weatherable
115118,
122, 123
MBS impact
modifiers
Bd//MMA/Sty,
Bd/Sty//MMA/Sty
Toughen PVC, engineering resins,

epoxy and other thermoset resins,
clear or opaque application
130134,
141, 144
HDT modifiers
-Methylstyrene/
AN, MMA
INCREASE service temperature,

improve melt strength and grain
retention
147153
Flatting agent/
light diffuser
MMA, BA, Sty
Reduce surface gloss, diffuse light

in polycarbonate
154155
14.3
Processing Aids
Many plastic materials have limited applications due to either undesirable physical
properties or poor processing capability. Processing aids were developed to enhance
melt processing, increase throughput, reduce downtime, and provide better product
quality [79]. The first commercial processing aid product was introduced by the
Rohm and Haas Company for processing rigid PVC in the 1950s [4]. This unique
14.3 Processing Aids
technology was well acknowledged and led to the surge of the PVC industry. Similar
development efforts have been applied to other thermoplastic materials and polymer
blends since the 1980s. Although processing aids are generally added to PVC and
other thermoplastics in small quantity (0.55 %), they dramatically alter the processing characteristics without a substantial effect on other application properties. Processing aids can be classified by functions such as fusion promotion, melt rheology
modification, lubrication, and dispersion promotion. Each processing aid may
provide more than one function. The function and performance of a specific type of
processing aid is affected by the chemical composition, polymer architecture, polymer molecular weight, and the matrix type.
14.3.1
Processing Aids for PVC
In a thermoplastic resin, to the mechanical properties of the final product are related
to the homogeneity of the polymer melt during the conversion process. Unlike the
majority of other thermoplastic resins, rigid PVC is not processable due to its inherent particulate structure. It requires a long processing time at high temperatures
which leads to thermal degradation. The history and development of processing aids
for PVC, as well as the proposed mechanism are well documented [3, 5]. Processing
aids offer several benefits to a PVC formulation, mainly related to the fusion and
melt rheology during processing [3]. Processing aids help to increase cohesion and
homogeneity of the melt, melt strength, melt extensibility, and elasticity. The composition and the polymer structure of the processing aid affects the compatibility
with PVC and alters properties such as fusion promotion and lubrication. On the
other hand, the molecular weight and molecular weight distribution play the major
role in controlling the melt rheology. The most common processing aids are methyl
methacrylate based polymers. PMMA based polymers have a high glass transition
temperature (Tg) and are also extremely compatible with PVC [80, 81], which help to
create and transfer localized shear heat to melt the PVC during fusion process.
Improving melt rheology, increasing dispersibility, improving efficiency, and
enhancing the overall balance of properties, (especially melt strength versus viscosity) have been the major goals of new processing aid development [82]. This has led to
the ability to get equal performance from lower levels of process aid, and, in the case
of clear applications, materials that disperse more rapidly with greater clarity.
Fusion promotion and melt homogeneity
The most common approach to characterize the PVC fusion process employs the
Brabender Plasticorder or Haake Rheometer, which consists of a mixing head with
two rolls. Figure 14-1 shows the PVC fusion process as reflected in the curve of
fusion torque vs. time. The melt temperature in each stage can also be recorded.
Point A is referred as the compaction peak and corresponds to compression and
densification of the powder. Point B refers to the beginning of melting, followed
by the appearance of the fusion peak. Point C occurs as PVC fuses into melt. The
difference in time between A and C is called fusion time. The torque observed at
359
point C is called the fusion torque. PVC is not completely melted at this stage
and the majority of melt is in the form of sub-microscopic particles. The fusion continues to occur as the torque drops down to an approximately constant value at point
D, which is referred as the equilibrium torque. The equilibrium torque can be interpreted as a rough estimate of melt viscosity. As the heating and shearing continue, dehydrochlorination and cross-linking of PVC chains can occur, producing the
torque increase at point E. The difference in time between A and E is called the
degradation time. The fusion curve is strongly influenced by the formulation type,
processing temperature, shear rate, and loading level.
A
C
Torque
360
Time
Fig. 14-1 Torque

rheometry of
a PVC compound,
torque versus time.
Faster fusion time does not indicate complete breakdown of the PVC particulate
structure, and does not correlate well with good melt homogeneity. However, the
smoothness of rolling bank in the roll mill can provide a rough estimate. With only
2 % acrylic processing aid in a tin-stabilized PVC (K-value = 61) at 180 C. 180 C processing temperature, the stock on the roll is clear, smooth, and homogeneous, and
the rolling bank is also smooth. In contrast, a non-homogeneous melt on the roll and
a badly fractured rolling bank can be observed when no processing aid is added. The
resulting sheets of both processes are shown in Fig. 14-2. With processing aid, the
sheet is strong, free of pinholes, and has no air streak and melt fracture. The
unmodified PVC film tears, crumbles, and loses its integrity. The PVC melt homogeneity can be examined under a transmission electron microscope. A Differential
Scanning Calorimetry (DSC) method can help to assess the degree of PVC fusion.
This technique provides the level of gelation and is related to the fusion of the PVC
specimen [83].

A tin-stabilized PVC (K = 61)
formulation was processed at 180 C for 4 min.
(A) Without the addition of processing aid,
(B) With 2 phr of Paraloid K-125. The sheet (A)
is hazy and has no film integrity. The sheet (B)
is clear, strong and has a smooth surface.
Fig. 14-2
Melt strength, extensibility, and elasticity

Melt strength is a phenomenon reflecting both elasticity and elongational viscosity.
Extensibility describes the PVC melts ability to undergo large elongation or stretching deformation without rupture. Elasticity is related to the tendency to return to its
original state when stresses are removed. It is difficult to separate these rheological
properties. A combination of tensile strength, elongation, and elasticity defines the
toughness of a melt. Without polymeric processing aid, PVC would not withstand
high stress or extension. The acrylic copolymers that are typically used as processing
aids are generally compatible with PVC, and with their long chains, interact to produce a stiffer and more elastic melt. Increased rupture stress and extensibility helps
the PVC become far more resistant to rupture-induced defects.
Although the practical effects of melt strength are abundantly clear to the processor, measuring the melt strength quantitatively is usually difficult. The Gottfert
Rheotens is a device that uses a gear-like strain gauge instrumental puller to
draw a fully fused melt from a right-angled (vertical drop) extruder. While the extruder output rate is stabilized, the geared take-off accelerates until the melt (extrudate) breaks. Therefore, the rheological properties of the PVC melt can be recorded
quantitatively. Die swell is another method for measuring melt elasticity. When a
polymer is deformed, it tends to return to its original form after external force is removed. This behavior is commonly observed as the swelling of an extrudate as it exits the die. The degree of swelling is related to the polymer recoverable strain or elasticity and is normally expressed as swell ratio (extrudate diameter/die exit diameter)
or by the comparison of the weight of a fixed length of extrudate. As shown in
Fig. 14-3, the extrudate weight is dependent upon the concentration of processing
aid. As predicted, the die swell is related to the polymer molecular weight. Melt elasticity is an important factor in establishing melt stability as the melt enters and pro-
361
50
Extrudate W eight (g)
362
A
B
C
D
45
:
:
:
:
Mw
Mw
Mw
Mw
=
=
=
=
1.5 million
2.5 million
3.5 million
6 million
40
35
30
25
0
2
3
4
Processing Aid Level (phr)
Fig. 14-3 Effect of Processing Aid Molecular Weight and Concentration

on Extrudate Weight. PVC formulation was based on 100 phr PVC (K = 57),
1.5 phr Advastab TM-181, 0.5 phr ALDO MS and 0.2 phr OP Wax.
ceeds through the die in extrusion. The higher die entry pressure observed when
processing aid is present is also a good indicator of higher melt elasticity [79].
One of the more recent advances in processing aids has been the development of
ultra high molecular weight materials specifically designed for use in PVC foam applications [84, 85]. With the help of a proper processing aid, the cell structure of an
extruded foam is more uniform with lower rupture tendencies [86, 87]. The PVC
melt can withstand great extension before it breaks [88]. Therefore, a low density
foam with fine cell structure and good surface quality can be achieved. As shown in
Fig. 14-4, an ultra high molecular weight processing aid with Mw = 8 106 is about
30 % more effective in terms of foam density, cell uniformity, and surface quality
compared with a similar processing aid with the Mw = 6 106. Without a proper processing aid, the foam can have large cells, poor surface structure, and gas containment can be low (blow out). The effect of processing aid level on the surface quality
of a PVC foam rod is shown in Fig. 14-5.
Melt viscosity
Many thermoplastic resins have excellent physical properties and high service temperature, which are often accompanied by high melt viscosity. High melt viscosity
makes processing more difficult and often decreases productivity as well as product
quality. Especially in injection molding, it is a major challenge for any material to fill
thin walls, long flow paths, and/or complex shapes. Most high molecular weight processing aids increase the melt viscosity. However, it has been demonstrated that a
low level of standard acrylic processing aid does not have a noticeable effect on melt
viscosity [44, 89]. On the other hand, a combination of multi-function processing
aids can balance the melt rheology and melt homogeneity. Rigid PVC compounds
Processing Aid Level (phr)

Processing Aid Molecular Weight (x106)
Foam Density (g/cc)
Surface Quality
6
6.5
0.38
Excellent
Fig. 14-4 Effect of processing aid molecular

weight on PVC foam extrusion, based on a
free foam formulation with PVC (K = 62),
Fig. 14-5 Effect of

processing aid level on
the surface quality of
free foam rods. The
formulation is based
on PVC (K = 62), tin
stabilizer (TM-950F),
and azodicarbonamide
as blowing agent and
different level of
Paraloid K-400 as
processing aid.
(A) 2 phr, (B) 3 phr,
(C) 4 phr, (D) 5 phr,
(E) 6 phr.
(A)
4.5
6.5
0.5
Good
4.5
8.0
0.37
Excellent
tin stabilizer (TM-950F), and azodicarbonamide as blowing agent.
(B)
(C)
(D)
(E)
have successfully met the challenge. Many appliance parts, business equipment,
electronic enclosures are made from PVC compounds formulated with processing
aids and impact modifiers. As mentioned earlier, equilibrium torque as measured in
a Haake Rheometer can serve as a rough estimate of melt viscosity provided a proper control is used. The melt viscosity can also be measured by many modern analytical rheometric instruments including capillary rheometers.
Effect of melt rheology on conversion process
The processing of polymeric materials such as plastics is characterized by a wide
variety of distinct methods or techniques. Each technique has a different set of melt
rheology requirements that are dictated by the processing mechanism and the equipment design. A qualitative assessment of the effect of major melt rheology properties
on selected conversion processes is shown in Tab. 14-2.
363
364

Qualitative assessment of major melt rheological properties versus selected conversion processes.
Tab. 14-2
Melt homogeneity
Calendaring Smooth
rolling bank
Uniform
thickness
Melt
strength
Melt
extensibility
Melt
elasticity
Melt
viscosity
Higher takeoff speeds

Better thermoformability

Bi-orientation
Deep draw
thermoforming
Reduced melt
fracture, but
can give flow
lines
Can generate
air bubbles
if too high
Can reduce
output if
too high
Blowmolding
Uniform melt Reduced

flow, enhanced parison sag
physical
properties
Uniform wall
thickness
Bi-orientation
Reduced melt
fracture at
high output
rates
Extrusion
Uniform melt Higher takeflow, enhanced off speeds

physical
Foam density
properties
Reduced melt
fracture
Surface finish
Foam cell
structure
Injection
molding
Uniform melt Reduce gate

flow, enhanced blush
physical
properties
Reduced
jetting
Can reduce
flow lengths
if too high
Lubrication
Lubricants are used to prevent plastic melt from sticking to metal surfaces during
processing. A number of disadvantages are associated with non-polymeric lubricants
including plate-out, clarity, migration, and delay fusion. Lubricating processing
aids [90, 91] were developed to help metal release, reduce plate-out, improve melt homogeneity, and minimize delays in fusion. Lubricating processing aids combine
both lubricants and processing aid functions. Compared with conventional processing aids, this family of processing aids is less compatible with the matrix polymers.
Therefore, significant haze is developed due to the immiscibility with the resin.
However, the haze can be corrected with proper adjustment of refractive index [92].
The commercial lubricant processing aids for PVC, such as Paraloid K-175, help to
reduce melt fracture and shear stress and improve surface quality and do not affect
the clarity of the matrix polymer.
Processing aid type
Commercially available processing aids can be divided into four types general purpose, high efficient, high melt strength, and lubricating. The performance attributes
of different types of processing aids are shown in Tab. 14-3.
General purpose processing aids provide a balance of melt strength and melt viscosity. They help to promote PVC fusion and have excellent dispersibility under low
shear conditions. An optimum balance of efficiency and clarity can be achieved using selected polymers such as Paraloid K-120ND and K-130D (Rohm and Haas),

Tab. 14-3
Processing aid type versus performance attributes.
Processing Aid Type
General
purpose
High
efficiency
High melt
strength
Lubricating
Molecular weight (Mw 106)

Melt homogeneity
Melt strength (increase)
Melt elasticity (increase)
Melt extensibility
Melt viscosity (increase)
Fusion time
Dispersion (under low shear)
Clarity in PVC
Stress whitening resist.
Hot metal release/lub.
13
++++
++
++
++
+
+
++++
+++
++++
+
35
++++
+++
+++
+++
+++
++
++
+++
++++
+
6+
++++
++++
++++
++
+++
+++
+
++
NA
+
<1
++
+
+
+
+
+
++++
++++
++++
++++
+ = least, ++++ = greatest
Kane Ace PA-20/30 (Kanegafuchi), Metablen P501(Atofina/Mitsubishi Rayon) and

Barorapid 3F(Barlocher). High efficiency processing aids produce even higher melt
strength than the general purpose type. This is attributed to their higher polymer
molecular weight. In addition to higher melt strength. This type of processing aid
improves melt homogeneity and processing rate, and provides better surface quality
dimensional control in the finished product, even in a highly filled system such as
pipe formulation. The most common high-efficient processing aids are Paraloid K125 (Rohm and Haas), Metablen P550/P551 (Atofina/Mitsubishi Rayon), Vestiform
R315 (Huls), and Vinuran 3833 (BASF). As mentioned in the previous section, melt
strength processing aids are mainly used in PVC foam applications, including profile, foam core pile, and foam sheet. These processing aids provide low foam density,
high surface quality, and a consistent processing. The recommended processing aids
are Paraloid K-400/K415/K-435 (Rohm and Haas), Metablen P530 (Atofina/Mitsubishi Rayon), Kane Ace PA-40 (Kanegafuchi), Baroropid 10F/20F/30F (Barlocher).
Polymeric lubricants that improve melt processing, hot metal release, melt fracture,
and process efficiency are defined as lubricating processing aids. The common lubricating processing aids include Paraloid K-175 (Rohm and Haas), Kane Ace PA101 (Kanegafuchi), Metablen P710 (Atofina/Mitsubishi Rayon), Vestiform R450
(Huls), and Vinuran 3833 (BASF).
It is very common that a PVC compound is formulated with more than one type of
processing aid. Historically, the combination of different types of processing aids
could provide the converters with optimum processing. The combination of a lubricating processing aid such as Paraloid K-175 with other types of processing aids,
such as Paraloid K-120ND, K-125, or K-130D, is commonly applied to applications
such as blow-molded containers, calendered or extruded sheet, siding, profile extrusion, high-flow injection-molded parts, pipe fittings, conduit, etc. The balance of
melt rheology, melt homogeneity, and hot metal release affects the aesthetics, as
well as the productivity. A proper level of each ingredient is critical and can affect
the product quality. As shown in Fig. 14-6, an optimal level of Paraloid K-130D with
365
366
K-175 helps to improve optical clarity as well as to eliminate flow-line and air marks
in a rigid clear PVC calendered sheet.
(A)
(B)
(C)
Fig. 14-6 Effect of processing aid on flow lines and air marks of calendered sheet. Clear and rigid PVC formulation (A) 1.5 phr Paraloid K-130D
and 0.75 phr Paraloid K-175, (B) 1.5 phr Paraloid K-130D and 0.25 phr
Paraloid K-175, (C) 1.5 phr Paraloid K-125 and 0.25 phr Paraloid K-175.
The film thickness is approximately 0.5 mm.
14.3.2
Processing Aids for Other Resins
The use of processing aids to improve melt processing behaviors in resins other than
PVC has increased in the recent years. Some of the polymeric processing aids are
manufactured by emulsion polymerization but some of them are not. Acrylic processing aids were found to improve melt strength and melt homogeneity in thermoplastics such as polyolefins, polyesters, polycarbonate, and ABS/SAN blends [6370].
Methacrylate based polymers are reported to enhance the mill-processing of polyethylene. The higher alkyl methacrylates based processing aids improve the melt
strength of polypropylene and are useful in thermoforming operations to produce
containers and appliance housings. Lower molecular weight methacrylate based processing aids were applied as rheology modifiers in ABS to lower melt viscosity and to
facilitate melt processing [93]. Addition of an extremely low level of fluorocarbon
processing aid reduces melt viscosity and eliminates melt fracture in a film extrusion
of linear low density polyethylene [94]. Poly(vinylidene chloride), also known as
PVDC, is used in packaging applications, especially multilayer film and sheet, due to
its high strength and barrier properties. However, PVDC is significantly less stable
than PVC and would normally degrade rapidly at the temperature required for processing. Acrylic based additives reduce the thermal degradation and preserve the majority of important properties [95]. Poly(vinyl alcohol), PVOH, is another thermoplastic with excellent barrier properties but poor processability upon heat and shear
stress. The use of high molecular weight polymers as processing aids for PVOH enables a smooth melt processing without compromising the rigidity and barrier properties [7173]. The melt strength and melt viscosity of aromatic polyesters such as
poly(ethylene terephthalate), PET, can be increased substantially by the addition of a
low level of processing aid [69].
14.4 Impact Modifiers
14.4
Impact Modifiers
Impact resistance, or toughness, refers to the ability of a material to withstand high

rates of applied loads, and thus high energy absorption, without undergoing catastrophic failure due to fracture. Many plastics suffer from inherent brittleness, and
even those commonly thought to have relatively high ductility, such as polycarbonate, may become embrittled at very cold temperatures, by physical aging or through
high stresses or flaws introduced into the material.
The key to improving the impact resistance of a plastic is to enable the polymer to
absorb larger amounts of mechanical energy, while at the same time avoid plasticizing or softening the polymer, which can lead to large tradeoffs in other mechanical
properties, such as tensile or flexural modulus. The most common solution to this
dilemma is the introduction of a second, softer polymer phase into the plastic. In the
final processed material, this soft, rubbery phase ideally exists as discrete domains
dispersed within the plastic to enable the impact energy absorption, while the continuous glassy phase dominates the surface hardness and other mechanical properties.
In some cases, a blend containing the discrete rubber domains may be created
in-reactor through chemical process modifications during the manufacture of the
base polymer matrix material. Often it is difficult to properly control the desired
blend morphology, and the extra process steps introduce additional complexity and
cost into the process. Another limitation to the in-situ approach is that a typical manufactured polymer resin may be used in a wide variety of downstream applications,
each with its own unique performance requirements, and therefore the desired material modifications may also vary. Improved flexibility in formulating and processing is provided by using an additive approach, in which the characteristics of the
final blend are produced by formulating and adding the desired type and amount of
modifying additives just prior to or during the final melt processing step. In the case
of impact modifiers, emulsion technology provides an ideal method for meeting the
requirements for such an additive system. Emulsion polymerization methods can
produce very high molecular weight, low Tg polymers having ideal elastomeric properties for impact modification. Particles of highly uniform particle size, in the range
of tens to hundreds of nanometers, may be synthesized. Through the use of standard
crosslinking techniques, particle size is permanently set so that the original emulsion particle is preserved during the plastic melt processing step. This ability to produce and control the optimal blend morphology and final domain size of the rubbery
phase is extremely important in achieving good impact resistance in the resulting
plastic material.
The development of multiple-stage, or core-shell emulsion graft copolymers was
an important milestone in impact modifier technology [96, 97]. Using core-shell
technology, the rubber core can be designed to optimize impact performance, while
a higher Tg outer stage eliminates the tackiness normally associated with rubbery
polymers and so allows for easier isolation, storage and handling. The outer stage, or
stages, can also be designed to enhance the processing and dispersion attributes of
367
368
the additive, most typically in the case where the shell polymer composition is chosen based on its compatibility with the matrix polymer, which promotes improved
mixing to form the optimal dispersed-phase blend morphology.
In addition to composition, the particle size and distribution of the rubbery modifier must be carefully controlled. It is well known that impact performance is highly
dependent on particle size [98]. Small particles are thought to be effective due to the
larger total number of particles distributed in the matrix, and the resulting shorter
interparticle distances [99101]. The thin sections or ligaments of matrix between
the particles are more susceptible to induced shear deformation and drawing than a
thicker part or section. In some matrix systems, the energy absorption mechanism
may occur via multiple crazing or cracking, in which case large particles may be favored due to their ability to initiate and arrest the growth of these localized fractures [102]. Recent work in understanding impact mechanisms has focused on the
possible role of cavitation, or voiding, within the rubber domains during the impact
event, which allows for stress release and increased deformation of the adjacent matrix [103105]. Larger particles are thought to be more conducive to this cavitation
mechanism. The optimal rubber domain particle size for impact resistance is therefore based on a balance of these competitive effects, and varies depending on the nature of the matrix resin system being modified [106, 107].
Impact specifications and test methods vary according to application. Most commonly, testing is done using a notched Izod or Charpy pendulum impact test, for example, as specified by ASTM D256 or ISO 179 protocols. Specimens are prepared by
cutting a small initial notch into a bar of the plastic material to be tested, and mounted onto a pendulum-type impact tester. The pendulum hammer falls and strikes the
sample to initiate fracture at the notch. The total energy absorbed in the fracture is
measured from the loss in potential energy of the pendulum. Impact energy is normalized and reported in units of energy per area or length of crack.
Another common impact test method involves the use of a dropped weight or dart
to impact a flat surface or sheet of processed plastic material. The dart may be instrumented, in which case the actual energy, load and elongation properties of the
material may be measured as the dart punctures the material. A more basic drop test
is the Gardner test, in which the drop height (and therefore potential energy) of the
weight is increased until material failure is observed [108].
14.4.1
Impact Modifiers for PVC
Poly(vinyl chloride) (PVC) is the largest and most important resin for the application
of emulsion-based impact modifiers. In 1999, over 25 million tons (50 billion lb) of
PVC were produced worldwide [109, 110]. Virtually all of the emulsion-made impact
modifiers for PVC applications are of the core-shell variety, with the largest commercial producers being Rohm and Haas, AtoFina, Kaneka and Mitsubishi Rayon.
PVC is a unique polymer in that, while the neat resin is virtually useless, it can be
modified by various additives to provide a tremendous range of properties, ranging
from soft and flexible to rigid and tough. PVC is an inherently tough polymer, but is
characterized as notch sensitive [111]. Notch or crack sensitivity refers to the inability of a material to resist fracture in the presence of a notch, crack, flaw or other site of
potential high stress concentration. This feature, along with the potential for embrittlement at sub-ambient use temperatures, lead to most PVC applications requiring
some form impact modification. In a typical impact experiment, as shown in
Figs 14-7 and 14-8, the inclusion of a moderate amount of impact modifier produces
an almost tenfold increase in impact energy absorption vs. the neat resin, and largely negates the negative effects of lower temperatures or sharper notches in the test
specimen.
1200
Notched Izod Impact Energy (J/m)
0.25 mm notch radius

1000
800
23 C.
20 C.
600
400
200
0
0
Impact Modifier Level in PVC (phr)
Fig. 14-7 Influence of temperature and core-shell modifier addition on the

impact performance of PVC.
Various mechanisms have been proposed to explain the effectiveness of rubber domains in improving the toughness of plastic resins [106]. It is now generally accepted that the primary source of energy dissipation occurs in the matrix resin itself,
rather than in the rubber domains [98112]. The primary role of the rubbery
domains is to provide multiple sites of highly localized stress concentrations, which
tend to occur when a load is applied at the interface of materials having different
moduli [101]. In the case of PVC, which is intrinsically ductile, the localized stresses
can exceed the yield stress of the material, and plastic flow or deformation occurs in
preference to crack initiation and/or propagation [101, 113, 114]. In this way, large
amounts of energy are absorbed through an increase in elongation of the material at
moderate load levels (Fig. 14-9).
369

2500
20 C.
370
0.25 mm Notch Radius

2000
1500
1000
500
0
0
2
3
4
Impact Modifier Level (phr)
Fig. 14-8 Notch sensitivity of PVC. At smaller notch radii (sharper notch),
the PVC specimen is embrittled. Core-shell impact modifiers reduce the
notch sensitivity.
Unmodified
Yield point
Load
Elongation
Impact
Modified
PVC
Fig. 14-9 Effect of impact
modification on the macroscopic tensile properties of a
polymer such as PVC. The impact modifier lowers the yield
stress of the polymer, allowing
the polymer to yield and undergo extensive elongation. The
energy absorbed is calculated
from the area under the stressstrain curve.
PVC building products

Rigid, unplasticized PVC is used extensively in the building and construction markets. Pipe, vinyl siding, and window profiles, all manufactured via profile or sheet extrusion, represent the largest building product markets. Examples of some formulations are shown in Tab. 14-4.
Building products often require a high degree of rigidity, heat distortion resistance, and intrinsic toughness, attributes which are aided by the use of high molecular weight PVC resins, with K values typically greater than 65. These applications are
generally formulated to be opaque, and white or light pastel in color, so that for the

Tab. 14-4
Examples of PVC formulations for building products (parts per hundred resin).
PVC, K-67
Tin stabilizer
Calcium stearate
Paraffin wax 165 F
Polyethylene wax
Bisamide wax
Oxidized polyethylene wax
Titanium dioxide
Calcium carbonate
Process aid (K-120 type)
Lubricating proc. aid
Acrylic impact modifier
Siding capstock
Window profile
Pipe
100.0
1.2
1.2
1.0
0.1
8.0
5.0
1.0
0.5
5.0
100.0
1.2
1.5
1.7
0.1
9.0
3.0
1.0
4.0
100.0
0.4
0.8
1.2
0.15
8.0
5.0
0.5
3.0
purpose of optical properties, additives can generally be designed without consideration to refractive index and particle size.
The key distinguishing feature of impact modifiers used in building products is
weatherability, allowing the final modified PVC parts to retain color and mechanical
properties after extensive exposure to UV radiation. This requirement is well met
through the use of all-acrylic polymer compositions, which contain no residual unsaturated sites susceptible to UV degradation [115, 116]. Acrylic impact modifiers
have a rubbery core based on low Tg acrylates with moderately long side chains.
Poly(butyl acrylate), with a Tg of approximately 45 C, is most commonly used commercially, providing good elastomeric properties at reasonable cost. The rubbery
core, which typically makes up 70 to 90 % of the total modifier, is crosslinked
through the addition of small amounts of multifunctional monomers during the free
radical acrylate polymerization, so that the resulting crosslinked core contains less
than 5 % extractable polymer. There are also examples of acrylic modifiers containing small amounts of non-weatherable, but very low Tg monomers, such as butadiene, which may enhance the rubbery features of the core at the expense of small
tradeoffs in weatherability [117, 118]. Optimal impact performance for all-acrylic
modifiers in PVC building products is attained through the use of particles with diameters in the 80300 nm range.
A hard stage or shell is polymerized around the rubber core to allow for isolation of
the emulsions into non-compacting, free flowing powders, as well as to provide various performance properties. The shell plays a critical role in impact modification by
enabling easier mixing and dispersion of the modifier into the polymer matrix. In
weatherable PVC applications, this is usually achieved through the use of a
poly(methyl methacrylate) based shell composition, which combines a suitably high
Tg with excellent miscibility in PVC [119121]. The shell polymer, unlike the rubbery
core, is generally not highly crosslinked, so that the shell polymer chains are free to
mix and interact with the surrounding matrix on the molecular level. A modifier
with insufficient amounts of PVC-compatible materials in the shell will result in
poorer dispersion of the modifier (Fig. 14-10), leading to poorer impact (Fig. 14-11).
371
1.0 m
1.0 mm
x 50.000
x 50, 000
Modifier shell effects on dispersion

in PVC. The all-acrylic modifier particles are the
small white particles in the micrographs, while
the larger white and black particles are voids
and inorganic fillers. Modifier A, containing a
Fig. 14-10
shell with poor PVC miscibility, produces large

agglomerates and there are significant areas of
unmodified matrix. Modifier B has a more miscible shell, resulting in more uniform dispersion in the PVC resin.
1200
10 % Modifier
372
Modifier A (poor dispersion)

Modifier B (good dispersion)
960
720
480
240
14
16
18
20
22
24
Impact Test Temperature (C.)
Impact performance of the two modifiers compared in

Fig. 14-10. Better compatibility and dispersion of the modifier in the PVC
results in superior impact efficiency.
Fig. 14-11
The shell can further be designed around desired rheological and secondary properties. Shell molecular weight, degree of grafting, and composition can alter processing and rheology properties such as viscosity, melt strength, die swell and PVC fu-
sion promotion [115, 122, 123]. Final performance properties such as surface gloss,
part shrinkage and thermal stability can also be controlled through the use of appropriate design of the outer shell. A well defined core-shell morphology, which can be
obtained through the use of many standard emulsion synthesis techniques, is also
key to achieving optimal performance of the impact modifier. Examples of current
commercially available modifiers are shown in Tab. 14-5.
Tab. 14-5
Commonly used commercial weatherable impact modifiers.
Manufacturer
Trade name
Product
Description
Rohm and Haas
Paraloid
Atofina
Durastrength
Kaneka
Kane Ace
KM-334
KM-355
KM-377
KM-350
D-200
D-200L
D-300
FM-10
FM-20
FM-22
FM-25
General purpose all-acrylic

High efficiency
Impact and low gloss
Low temperature PVC fusion
Weatherable with Bd content
Impact and low gloss
High efficiency
General purpose all-acrylic
High efficiency
Highest efficiency
Impact and rheology
Weatherable core-shell impact modifiers are highly efficient, requiring only 48

parts in most formulations, and are therefore the most commonly used impact modifiers for PVC building products. Alternatives to emulsion-based additives include
linear (non-graft) polymers such as ethylene vinyl acetate and chlorinated polyethylene. The latter polymer is a popular choice for low cost, lower performance applications, as in some types of PVC pipes. The disadvantage of these non-core shell additives is the absence of a well-defined, pre-set particle morphology. Optimal morphology and impact performance must be achieved through very careful control of the
processing and formulation conditions [124126].
In Europe, several manufacturers provide pre-toughened PVC resins or concentrates. These are an example of in-situ impact modification, where the rubber
polymer is introduced and grafted into the matrix during the PVC polymerization [127129]. These systems provide excellent impact properties without the need
for a separate hard shell or additive step. The corresponding disadvantage to the formulator and processor is the lack of flexibility in adjusting the additive types, levels
and morphology.
PVC Durables and packaging
Core-shell impact modifiers are commonly used in PVC packaging applications,
such as films, sheets and clear bottles, as well as some PVC durable items, including
interior ducts and appliance housings. Unlike PVC building products, which are
commonly manufactured by extrusion, packaging and durable applications are often
made by calendering, injection molding and blow molding. Processing requirements, along with final property needs such as flexibility, dictate that somewhat low-
373
374
er molecular weight PVC resins are used, typically in the K-50 to K-65 range. Since
lower molecular weight resins have intrinsically lower toughness, it is often necessary to add higher levels of impact modifier. Examples of some formulations are
shown in Tab. 14-6. Note that, in addition to the impact modifier, the combinations
of lubricants in these formulations differ from those associated with building products.
Tab. 14-6
Examples of non-weatherable PVC formulations (parts per hundred resin).
PVC, K-57-58
Tin stabilizer
Calcium stearate
Paraffin wax 165 F
Glycerol monostearate
Montan ester wax
Saturated ester wax
Titanium dioxide
Calcium carbonate
Process aid
Lubricating proc. aid
Bd-based impact modifier
MBS clear impact modifier
Heat distortion additive
Blue toner
PVC electrical box
Bottle
Clear film
100.0
2.0
1.0
1.5
5.0
0.4
1.2
30.0
100.0
1.5
0.5
0.2
1.0
12.0
100.0
1.2
0.6
0.6
0.2
0.1
1.0
1.0
20.0
10.0
0.06
Because weatherability is often not an important requirement, core-shell modifiers in this area are usually based on butadiene rubbers. Polybutadiene is economical, has an extremely low Tg of approximately 80 C, and superior elastomeric properties, leading to higher potential impact performance than all-acrylic compositions.
Core-shell modifiers based on a butadiene homopolymer core result in the highest
impact efficiency, but are useful only in opaque applications. Many packaging applications require high transparency, which can be achieved through refractive index
matching of the modifier composition with the PVC matrix [130]. Appropriate
amounts of styrene can be incorporated into the core and shell of the modifier to
adjust the modifier refractive index, at the expense of some embrittlement of the
p-Bd rubber and resulting lower impact efficiency. Crosslinking of the Bd or Bd/Sty
core is controlled through process-induced self-crosslinking of Bd, and also through
the use of added multifunctional cross-linkers, such as divinylbenzene.
The role of the shell is analogous to the case of all-acrylic modifiers, although the
molecular structure and composition must be tailored for different processing requirements and secondary properties. Methyl methacrylate and styrene-acrylonitrile
are common compositions that provide good processing and miscibility with the
PVC. In transparent applications, complete breakdown of the modifier powder particles and complete dispersion back to the emulsion particle size scale are necessary to
avoid haze and optical inhomogeneities cause by gels. Stress whitening is also a
common occurrence in transparent films, and can be minimized by proper design of

the modifier for adhesion and void resistance [131]. Antioxidants and heat stabilizers
are often added to Bd-based modifiers to prevent undue degradation of the modifiers
during the high temperature drying and melt processing operations. In food packaging applications, impact modifiers must also meet specific FDA toxicity and
organoleptic requirements.
Some examples of commercially available Bd-based impact modifiers, and associated applications, are shown in Tab. 14-7.
Tab. 14-7
Commonly used commercial non-weatherable impact modifiers.
Manufacturer
Trade name
Product
Description
Rohm and Haas
Paraloid
Atofina/Mitsubishi,
Rayon
Metablen
Kaneka
Kane Ace
BTA-730
BTA-833
BTA-715
BTA-753
BTA-751
C-201
C-132
C-223
B-52
B-51
B-22
Clear film and sheet

Clear bottles
Low crease whitening
High efficiency, opaque
High efficiency, opaque, injection molding
Clear film and sheet, bottles
Low Crease whitening
High efficiency opaque
High efficiency opaque
Low crease whitening
Clear film and sheet, bottles
14.4.2
Engineering Resins
Engineering resins offer superior performance in various mechanical, thermal and

aesthetic properties, and encompass a wide variety of compositions and applications.
These polymers range from those that are considered inherently tough, such as polycarbonate, nylon, and polyethylene terephthalate, to the more brittle polystyrene and
SAN [106]. Although the toughening mechanisms, morphologies and optimal particle size for impact modification are specific to each type of matrix, the general
approach of adding a second phase of rubbery material is common to most cases. In
contrast to PVC, a much broader range of rubber technologies, both emulsion and
non-emulsion based, is used commercially. The higher processing temperatures of
engineering resins require the addition of significant levels of heat stabilizers and
antioxidants to acrylic or butadiene based emulsion rubbers [132, 133]. Resins other
than PVC are usually compounded as pellets, rather than powders, which lessens
the advantages in powder properties provided by emulsion polymer isolation techniques.
The most widely used emulsion based additives are the all-acrylic or MBS coreshell polymers. Methacrylate-based shell compositions are generally not highly miscible with the various engineering resin compositions, creating a challenge for proper impact modifier dispersion and adhesion. Common approaches to this problem
375
include the incorporation of functional polymers in the shell, or a third compatibilizing polymer, to promote compatibility or chemical reactions between the modifier
shell and resin.
Common examples of toughened engineering resins include polycarbonate and
polyesters. Unlike most other engineering resins, polycarbonate has some miscibility with PMMA, and traditional core-shell modifiers can significantly enhance the impact performance (Fig. 14-12).
800
Notched Izod Impact Energy (J/m )
376
640
23 C
480
0C
320
160
0
0
10
12
% Acrylic Core-Shell Modifier in Polycarbonate
Impact behavior of polycarbonate modified with a core-shell

impact modifier.
Fig. 14-12
PET (polyethylene terephthalate) has poor affinity for traditional shell compositions, but the use of hydroxy-containing compositions can aid in allowing the use of
core-shell type additives for effective toughening [134] (Fig. 14-13).
Transparent PET applications require index refraction matching, imposing another constraint on the design of these emulsion additives [134, 135]. In the case of PET,
the additive systems also compete with PETG, available from Eastman Chemical,
which is an inherently tougher resin created by copolymerizing PET and cyclohexanedimethanol [2].
PBT (polybutylene terephthalate) is traditionally toughened using ABS resins,
which may be emulsion-based. Core-shell emulsion polymers, which can be compatibilized with PBT through the use of GMA (glycidyl methacrylate), can be used at levels from 10 to 30 % to efficiently increase impact resistance [2, 136, 137].
PC-PBT blends, offered by General Electric under the trade name Xenoy, are commonly used in many automotive applications and can be effectively toughened by
core-shell modifiers. An example of impact modified PC-PBT blend morphology

10
Dynatup Drop Dart Energy (J)
-10 C
10
12
% Acrylic Core-Shell Modifier in PET (0.94 IV C-PET)
Fig. 14-13 Impact behavior of a PET resin modified with a core-shell

impact modifier.
(Fig. 14-14), clearly shows that the core-shell impact modifier prefers to exclusively
reside in the more compatible PC phase.
ABS (Acrylonitrile-butadiene-styrene) is one of the oldest engineering resins.
Emulsion polymerization can be used to synthesize Bd or Bd-S rubber seeds, fol-
Fig. 14-14 Morphology of impact modified

two-phase PCPBT
blend. The blend contains 40 % PBT, 50 %
PC and 10 % core-shell
modifier. The coreshell modifier tends to
reside in the polymer
phase it is most com20,000 X
patible with, in this
case, PC.
1 m
377
378
lowed by additional polymerization of styrene and acrylonitrile to form an in-situ

impact modified resin. Alternatively, the composition can be blended with additional SAN polymer to produce the desired blend ratios and properties [138]. Core-shell
polymers can be created by minimizing and carefully controlling the SAN polymerization to create the desired morphology. These ABS polymers can be used as additives to modify SAN and other resin matrices.
Impact modification of nylons is generally achieved through the incorporation of
reactive groups in the rubber [139, 140]. Since these compositions react with the nylon during the melt processing, the conditions and compositions must be carefully
controlled to prevent undesired increases in melt viscosity. While core-shell modifiers have been applied successfully to these systems [141, 142], the most common
commercial approach is the use of olefin-based elastomers grafted with functional
monomers as maleic anhydride.
PMMA, commonly known as Plexiglas, provides an interesting example of the
application of emulsion synthesis to design multi-layer core-shell impact modifiers [143, 144]. A common three-stage polymer used to impact modify commercial
PMMA resins contains a hard, methacrylate based inner core, surrounded by an
inner, soft acrylate shell, and further encapsulated by a PMMA based outer stage.
The role of the inner hard core is to provide refractive index matching and improved
stiffness retention to the overall matrix. Additional studies have demonstrated the
effectiveness of a large number of alternative multilayer designs in improving the
toughness and balance of properties in impact modified PMMA [145].
Acknowledgment
The authors wish to thank the Rohm and Haas Company for their support.
379
References
1 S. K. Porwal, Modern Plastics Encyclope2
10
11
12
13
14
15
dia 99, 1999, A23A27.

C. A. Cruz-Ramos, Core-Shell Impact
Modifiers, in: Polymer Blends, Volume 2:
Performance, D. R. Paul, C. B. Bucknall
(eds), Wiley, 2000.
J. M Brady, C. A. Cruz-Ramos, Processing Aids, in: Polymer Blends, Volume 2:
Performance, D. R. Paul, C. B. Bucknall
(eds), Wiley, 2000.
J. T. Lutz, Jr, D. L. Dunkelberger, Impact
Modifiers for PVC, The History and Practice, J. Wiley and Sons, NY, 1992.
D. L. Dunkelberger, Processing Aids for
PVC, in: Plastics Additives and Modifiers
Handbook, J. Edenbaum (ed.), Van Nostrand Reinhold, NY, 1992, Chapter 60.
Y. Nakamura, H. Tabata, H. Suzuki,
K. Ito, M. Okubo, T. Matsumoto, J. Appl.
Poly. Sci. 1986, 32, 4865.
D. E. Henton, D. M. Pickelman, C. B.
Arends, V. E. Meyer, US Pat. 4,778,851
(1988).
J. Wiersma, J. Meyer, D. Leblanc,
R. Berardino, Toughening of Epoxy
resins Using Core-Shell Modifiers,
in: Fourth International Conference Additives 96, S. M. Andrews, C. A. Cruz,
A. Golovoy, C. A. Wilkie (eds), Executive
Conference Management, Houston,
1996.
J. Y. Qian, R. A. Pearson, V. L. Dimonie,
M. S. El-Aasser, J. Appl. Polym. Sci. 1995,
58, 439.
G. L. Shaffer, R. Bagheri, J. Y. Qian, V.
Dimonie, R. A. Pearson, M. S. El-Aasser,
J. Appl. Polym. Sci. 1995, 58, 465.
R. H. Backderf, C. D. Guiley, Jr, US Pat.
4.082,895, 1978.
R. G. Gilbert, Emulsion Polymerization:
A Mechanistic Approach, Academic Press,
1995.
P. A. Lovell, M. S. El-Asser (eds) Emulsion Polymerization and Emulsion Polymers, Wiley and Sons, Chichester, UK,
1997.
D. C. Blackley, Polymer Lattices, Science
and Technology, 2nd edn, Chapman and
Hall, London, 1997.
US Pat. 4,179,481 (December 18, 1977),
M. Tuzuki, K. Matuba (to Kanegafuchi).
16 US Pat. 4,699,948 (November 25,
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
1985), K. Kishida, K. Ueda, M. Kaneda

(to Mitsubishi Rayon KK).
US Pat. 4,668,740 (May 26, 1987),
K. Okano (to Mitsubishi).
US Pat. 3,883.686 (September 3, 1984)
R. J. Grochowski, R.K. Graham,
J. Whang (to Rohm and Haas).
Eur. Pat. 208585A1 (Jan. 14, 1987)
J. M. Paul, C. L. Cretenot, A.
Vigouroux (to Norsolor S.A.).
US Pat. 4,206,292-A (June 3, 1980)
Y. Iizuka, S. Midorikawa, M. Oya
(to Kureha).
Japanese Pat. 62086042-A (Apr. 20,
1987) Nagasawa, T. Okamoto,
K. Shudo (to Chisso Corp.).
US Pat. 3,027,347 (March 27, 1962)
H. Fikenstscer, K. Heerle (to BASF).
Eur. Pat. 484,723 (May, 13, 1992),
H. Goertz, G. Hatzman, W. Oschmann
(to BASF).
Eur. Pat. 484,723 (May, 13, 1992),
H. Goertz, G. Hatzman, W. Oschmann
(to BASF).
US Pat. 4,584,349 (April 22, 1987),
M. H. Lehr (to BF Goodrich).
US Pat. 4,699,948 (Oct. 13, 1987),
K. Kishida, K. Ueda, M. Kaneda
(to Mitsubishi).
US Pat. 4,730,024 (March 8, 1988),
K. Kishida, K. Ueda, M. Kaneda
(to Mitsubishi).
J. Zelinger, E. Volfova, V. Altmann,
M. Tomka, Sb. Vys. Sk. Chem. Technol.
Praze 1981, 5, 139.
A. P. Wilson, V. V. Raimondi, Polym.
Eng. Sci. 1987, 18, 887.
V.V. Raimondi, Plast. Compd. 1980, 3,
77.
US Pat. 4,547,428 (October 15, 1985),
V. Bekker, W. J. Buchleim, W. Vanderlinde, D. S. T. Wang (to Monsanto).
Ger. Pat. 3,131,609 (February 17,
1983), K. Flatau (to Chemische Werke
Huels AG).
Japanese Pat. 74 72341 (July 15, 1974)
F. Ide, M. Asao, K. Kishida, A. Hasagawa (to Mitsubishi).
R. D. Deanin, J. D. Mast, J. Vinyl Tech
1987, 9, 15.
380
References
35 Japanese Pat. 51026953 (August 29,
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
1984) F. Ide (to Mitsubishi).

Japanese Pat. 06,087,997A (Mar 29 1994)
(to Mitsubishi).
Eur. Pat. 189,872 (August 6, 1986),
M. H. Lehr (to BF Goodrich).
US Pat. 3,975,315 (August 17, 1976),
C. Parks (to BF Goodrich).
US Pat. 2,646,417 (July 21, 1953),
G. Jennings (to BF Goodrich).
US Pat. 4,668,741 (May 26, 1987),
L. J. Memering (to National Distillers
and Chemical Corp.).
H. G. Elias, F. Vohwinkel, New Commercial Polymers, Gordon and Breach, New
York, 1986, pp. 5865.
Japanese Pat. 62015249 (January 23,
1987), M. Kinoshita, H. Eguchi,
S. Maeda (to Dainippon Ink Chem KK).
US Pat. 3,928,500 (December 13, 1975),
P. Kraft, A.F. Kopacki, R. Brunner (to
Stauffer).
Eur. Pat. 195,942 (January 1, 1986),
T. Thunig, R. W. Terwonne (to Huls).
US Pat. 3,686,363 (August 22, 1972),
A. J. Yu, P. Kraft (to Stauffer).
Japanese Pat. 5411949 (June 30,1977),
K. Tsuda, H. Eguchi, H. Tanaka
(to Dainipon Ink).
US Pat. 4,105,624 (August 8, 1978),
K. Boehlke, P. Foerster, H. G. Matthies,
H. J. Sterzel (to BASF).
US Pat. 4,398,019 (May 19, 1982),
M. K. Cox, B. P. Griffin (to ICI).
US Pat. 4,137,280 (January 30,1979),
D. D. Dixon, M. E. Ford (to Air
Products).
Eur. Pat. 52460A1 (May 26, 1982), P. A.
Holmes, A. B. Newton, F. M. Willmouth
(to ICI).
US Pat. 5,206,296 (Apr. 27, 1993),
J. Dominique, M. Loidl (to GE).
Eur. Pat 99,938,955 (Aug. 24, 1999),
N. Sakashita, Y. Miki, A. Takaki (to
Kanegafuchi).
Eur. Pat. 921,138 (1999), Y, Nakanishi,
M. Kadokura, K. Janssen, A. Takaki,
M. Miki (to Kanegafuchi).
US Pat. 3,859,389 (January 7, 1975), D.
T. Carty, J. A. Oline (to Rohm and Haas).
Japanese Pat. 55160045 (December 12,
1980), H. Hosoi, K. Matsuba (to Kanegafuchi).
56 US Pat. 4,746,705 (May 24, 1988),
A. Courtis, M. B. Elser (to ICI).

57 Eur. Pat. 204,974 (December 17, 1986),
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
K. Kishida, K. Ueda, M. Kaneda (to

Mitsubishi).
US Pat. 5,371,149 (December 6, 1994),
K. Kishida, K. Ueda, M. Kaneda (to
Mitsubishi).
Japanese Pat. 07,278,237 (1995),
Y. Matsumoto, A. Nakada, S. Wakabayashi, M. Kaneda, H. Ito, K. Okano
(to Mitsubishi).
US Pat. 4,120,833 (Oct. 17, 1978),
M. Purvis, P. Grant (to Rohm and
Haas).
US Pat. 5,789,453 (August 4, 1998),
R. E. Detterman (to BF Goodrich).
WO. Pat. 9,943,741 (1999) N. Migita,
A. Nakata, S. Wakabayashi, S. Takei (to
Mitsubishi).
Eur. Pat. 216207A (April 1, 1987),
S. Matsumoto, K. Nishimoto, I. Mishima, F. Nagoshi (to Kanegafuchi).
Eur. Pat. 230,030 (July 29, 1987),
T. Maeda (to Denki Kagaku).
US Pat. 4,156,703 (May 29,1979),
W. H. Harp (to Rohm and Haas).
US Pat. 4,094,927 (June,13,1978),
W. H. Harp, D. Witiak, R. LaBar
(to Rohm and Haas).
US Pat. 5,102,952 (Apr. 7,1992),
N. A. Memon (to Rohm and Haas).
US Pat. 5,302,429 (Apr. 12,1994),
US Pat. 5,310,799 (May 10,1994),
W. Carson, C. H. Lai, N. A. Memon
(to Rohm and Haas).
US Pat. 5,506,307 (Apr. 9, 1996),
US Pat. 5,362,803 (1994), E. E. LaFleur,
R. M. Amici, W. J. Work, (to Rohm and
Haas).
US Pat. 5,378,759 (1995), R. M. Amici,
E. E. LaFleur, W. J. Work, (to Rohm
and Haas).
US Pat. 5,605,960 (1997), J. M. Brady,
T. C. C. Diaz, (to Rohm and Haas).
K. Masters, Spray Drying Handbook,
5th edn, Longman Scientific and Technical, New York, 1991.
US Pat. 4,463,131 (1984), R. J. Grandzol, A. J. McFaull, H. Wanger, I. S. Rabinovic, (to Rohm and Haas).
References
76 H. Morikawa, S. Kato, H. Yasui,
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
M. Hasegawa, T. Shimizu, Innovation of

MBS Powder, in: SPE Annual Technical
Conference, 1987, p.669.
H. Yasui, K. Higashitani, J. Colloid Interface Sci. 1988, 125, 472.
US Pat. 4,892,910 (January 9, 1990),
W. Kleese, H. Rauch, P. J. Aradt,
N. Suetterlia (to GmbH Rohm).
H-Y. Parker, J. L. Allison, Processing
Aids, in: Encyclopedia of Polymer Science
and Technology, Index, H. F. Mark, N. M.
Bikales, C. G. Overberger, G. Menges
(eds), John Wiley and Sons, New York,
1990, p. 307.
D. R. Paul, S. Newman, Polymer Blends,
Vol. 1, Academic, New York, 1978.
U. K. Saroop, K. K. Sharama, K. K. Jain,
J. Appl. Polym. Sci. 1989, 38, 14101437.
Y. Miki, Y. Nakanishi, A. Takaki,
Y. Yamazaki, SPE ANTEC Proc., 1999.
P. Choi, M. Lynch, A. Rudin, J. The,
J. Batiste, J. Vinyl Tech. 1992, 14(3), 156.
Y. Nakanishi, J. Silberman, R. Nishimura, SPE Vinyltec, Toronto, 1999.
J. R. Patterson, SPE ANTEC Proc., 1997,
Toronto.
M. Hou, J. Shen, C. Chen, Chengdu Keji
Daxue Xuebao, 1985, 3, 1.
F. Ide, K. Okano, Pure, Appl. Chem. 1981,
53, 489.
J. Zellinger, E. Vilfva, H. Zahradnikova,
Int. J. Polym. Mater. 1976, 5, 99.
J. Stevenson, R. Einhorn, J. Vinyl Tech.
1993, 15(4), 244.
R. K. Graham, Preprints of ACS Organic
Coatings and Plastics, 1974, 34, 172.
F. Ide, Kobunshi, 1972, 49, 74.
C. F. Ryan, Resin Review, 1969, 19, 15.
Eur. Pat. 216207A (April 1, 1987),
S. Matsumoto, K. Nishimoto, I. Mishima, F. Nagoshi (to Kanegafuchi).
Rudin, A. Worm, J. E. Blaklock, J. Plast.
Film Sheeting 1985, 1, 189.
M. C. Patterson, D.L. Dunkelberger,
J. Vinyl Technol. 1994, 16, 46.
US Pat. 3,448,173 (1969) to Rohm and
Haas.
US Pat. 3,251,904 (1966) to Rohm and
Haas.
A. J. Kinlock , R.J. Young, Fracture
Behavior of Polymers, Elsevier, Essex, UK,
1983.
99 S. Y. Hobbs, Polym. Eng. Sci. 1986, 26,
74.
100 S. Wu, A. Margolina, Polymer 1990, 31,
972.
101 C. B. Bucknall, Toughened Plastics,
Applied Science, London, 1977.

102 A. M. Donald, E.J. Kramer, J. Appl.
Polym. Sci. 1982, 27, 3729.

103 A. F. Yee, R. A. Pearson, J. Mater. Sci.
1986, 21, 2462.

104 R. A. Pearson , A. F. Yee, J. Mater. Sci.
1986, 21, 2475.

105 C. B. Bucknall, P. S. Heather, A. J.
Lazzeri, J. Mater. Sci. 1989, 16, 2255.

106 I. Walker, A. A. Collyer, Rubber
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
Toughening Mechanisms in Polymeric

Materials, in: Rubber Toughened Engineering Plastics, A.A. Collyer (ed.),
Chapman and Hall, London, 1994.
S. Wu, Polym. Eng. Sci. 1990, 30, 753.
ASTM Test Methods D-3029 and ASTM
Test Method D-4226, American Society
for the Testing of Materials, Philadelphia, USA.
Modern Plastics International, Feb.
2000, Chemical Week Associates, NY,
p 74.
R. Roman, Modern Plastics Encyclopedia
99, McGrawHill, NY, p. B-11.
P. I. Vincent, Impact Test and Service
Performance of Thermoplastics, Plastics
and Rubber Institute, London, 1971.
C. B. Bucknall, Adv. Polym. Sci. 1978,
27,121.
S. Newman, S. Strella, J. Appl. Polym.
Sci. 1965, 9, 2297.
H. Breuer, F. Haaf, J. Stabenow,
J. Macromol. Sci. 1977, B14(3), 387.
US Pat. 3,678,133 (1972) to Rohm and
Haas.
US Pat. 3,843,753 (1974) to Rohm and
Haas.
US Pat. 4,542,185 (1985) to M&T
Chemicals.
US Pat. 4,567,234 (1986) to M&T
Chemicals.
D. J. Walsh, G. L. Cheng, Polymer 1984,
25(4), 499.
L. M. Robeson, J. Vinyl Technol. 1990,
12(2) 89.
S. Fitzwater, ACS Conference, Polymer
Chemistry Division, San Francisco, CA,
USA, 510 Apr. 1992 , Polymer
Preprints 1992, 33(1), 712.
381
382
References
122 US Pat. 6,031,047 (2000) to Rohm and
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
Haas.
US Pat. 4,670,509 (1987) to Kaneka.
A. Siegmann, A. Hiltner, Polym. Eng.
Sci. 1984, 24(11), 869.
M. T. Berard, S. M. Williams, J. Vinyl
Add. Tech. 1996, 2(2), 117.
A. J. Whittle, R. P. Burford, Plast. Rubber
Composites, Proc. and Appl. 1998, 27(9),
395.
US Pat. 4,536,548 (1985) to Huls.
US Pat. 4,798,869 (1989) to Huls.
US Pat. 5,232,991 (1993) to Huls.
US Pat. 3,971,835 (1976) to Rohm and
Haas.
S. Ohtsuka, H. Watanabe, Y. Amagi, Soc.
Plast. Eng. Ann. Tech. Conf., May 1967.
US Pat. 5,164,434 (1992) to Rohm and
Haas.
P. R. Paolino, in: Antioxidants in Thermoplastic Polymer Additives, Theory and Practice, J. T. Lutz (ed.) Marcel Dekker, NY,
1989.
US Pat. 5,409,967 (1995) to Rohm and
Haas.
J. P. Meyer, D. LeBlanc, K. Nees-Brand,
Kunststoffe 1995, 85, 452.
S. Y. Hobbs, M. E. J. Dekkers, V. H.
Watkins, J. Mater. Sci. 1988, 23,1219.
S. Y. Hobbs, M. E. J. Dekkers, V. H.
Watkins, J. Mater. Sci. 1988, 23,1225.
H. Keskkula, D. Paul, in: Toughening
Agents for Engineering Polymers in
Rubber Toughened Engineering Plastics,
A. A. Collyer (ed.),Chapman and Hall,
London, 1994.
US Pat. 4,174,358 (1979) to DuPont.
R. J. M. Borggreve, R. J. Gaymans,
J. Schuijer, Polymer (1989), 30, 71.
US Pat. 4,086,300 (1977) to Rohm and
Haas.
142 R. J. Gaymans in: Toughened
143
144
145
146
147
148
149
150
151
152
153
154
155
Polyamides, in Rubber Toughened Engineering Plastics, A. A. Collyer (ed.),

Chapman and Hall, London, 1994.
N. Shah, J. Mater. Sci. 1988, 23, 3623.
US Pat. 3,793,402 (1974) to Rohm and
Haas.
P. A. Lovell, J. McDonald, D. E. J.
Saunders, M. N. Sherratt, R. J. Young,
Multiphase Toughening Particle Technology in Toughened Plastics I, Science and
Engineering, C. K. Riew, A. J. Kinloch
(eds) Advances in Chemistry Series
233, American Chemical Society,
Washington, DC, 1993.
US Pat. 4,963,622 (October 16, 1990),
W. Hertz (to Union Carbide).
M. Kobayashi, K. Yoshihara, N. Naka,
Japanese Pat. 60/166337 (1985); Chem.
Abstr. 1986, 104, 89796a.
J. Kushida, S. Tago, T. Aoyanage,
Abstr. 1987, 107, 1165136b.
J. Kushida, N. Yamada, S. Hagiwara,
Abstr. 1987, 107, 24324n.
US Pat. 3,427,275 (Feb. 11, 1969),
B. J. Davis, W. J. Ranson (to Reichhold).
US Pat. 5,324,461 (June 28, 1994)
M. Grohman (to GE).
US Pat. 5,278,198 (Jan. 11, 1994)
M. Grohman (to GE).
US Pat. 5,391,585 (Feb. 21, 1995)
M. Grohman (to GE).
US Pat. 5,237,004 (Aug. 17, 1993)
J.-C. Wu (to Rohm and Haas).
US Pat. 5,846,657 (Dec. 8, 1998)
J.-C. Wu (to Rohm and Haas).
15
Applications for Dipped Goods

Robert Groves, Andrew Lanham, and Karen Spenceley, Synthoner Ltd, Harlow, UK
15.1
Introduction
The dipping process is, at least in concept, a simple one. The idea of producing a thin
coating by dipping an article into a liquid coating material is well established, being
particularly useful as a method for coating irregularly shaped items, such as car body
parts or toys.
In another guise, the dipping technique can be used to produce flexible, thinwalled articles from natural or synthetic polymers. The various types of synthetic
polymer used for dipping are discussed in the next section. In the dipping process, a
suitable shape, called in the industry a mold, form or former, is dipped with an
appropriate dwell time into a liquid containing the polymer. The coated former is
then heated to dry and cure the polymer as necessary. Finally, the article is removed
from the former, whose shape it retains. The dipping process therefore provides the
means to make seamless thin-walled items with predetermined, perhaps complex,
shapes.
The thin walled, flexible products normally associated with this process are gloves,
condoms, balloons, catheters and feeder teats and soothers for babies. The polymers
from which they are made often include additives to produce the desired physical
properties. One example of this is the use of curing agents to produce elastomeric
properties, where the final article exhibits the ability to recover its original dimensions after the removal of an applied stress.
This book is concerned with synthetic emulsion polymers, and it has to be said
that at the start of the 21st century their use in the production of dipped goods is relatively limited. The area is dominated by the use of natural rubber for gloves and
condoms. Matching the strength, modulus, tear resistance and dipping characteristics of natural rubber has provided a formidable challenge to the synthetic polymer
chemist.
Balloons and catheters remain the domain of natural rubber, with the very minor
exception of the use of some high modulus synthetic emulsion polymer as a reinforcing material for catheters.
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384
15 Applications for Dipped Goods
For condoms, no synthetic aqueous emulsion polymer is used. Currently, the alternative to natural rubber is provided by polyurethane dipped from organic solvent.
It is in the area of hand protection that synthetic emulsion polymers have made inroads into the dominance of natural rubber. Accurate market figures are difficult to
obtain, but it is believed that currently some 12 % of the estimated 400 000 dry tonne
worldwide market for polymeric gloves (excluding household gloves) is with synthetic emulsion polymers, while about 15 % uses non-aqueous synthetic products.
The protective glove market can be subdivided as follows.
Disposable
Medical
Surgical
Examination
Light industrial
(approx. 12 g per piece)

Unsupported
Household
Industrial
Fabric-supported

(20 to 100 g per piece)
(Fabric glove coated with 3080 g polymer)
Disposable and unsupported gloves consist of a film of a chosen polymer with a

thickness appropriate to the end use. Fabric-supported gloves are made by pulling a
woven fabric liner on to a former, and applying a polymer coating to the fabric by
dipping.
Synthetic polymers have found their main use in light industrial, unsupported industrial and fabric supported gloves. The reasons have been associated with specific
technical benefits, as described in the next section.
15.2
Polymers Used by the Dipping Industry
Although natural rubber dominates the dipping sector, synthetic polymers can offer
significant technical benefits for some applications. The main benefits for synthetics
that have so far emerged are:
the ability to produce gloves with a much higher degree of resistance to non-polar
organic solvents than is possible with natural rubber;
to produce skin-contact items that are completely free of proteins, where an alternative material to natural rubber is desirable because of potential protein allergy
problems;
to make gloves which have a lower surface electrical resistance than natural rubber, a useful property in gloves that are used in electronic assembly because of the
reduced risk of damaging sensitive components by static electricity;
with the correct polymer design, to achieve greater mechanical protection (puncture and abrasion resistance) than is possible with natural rubber.
15.3 Principles of Dipping
Several synthetic polymers are used by the glove industry. Clearly, for dipping, the
polymer must be provided in a liquid form. For poly(vinyl chloride) the liquid is a
plastisol, which is a dispersion of the polymer in an organic liquid, most of which is
a plasticizer for the polymer. Heat treatment causes the plastisol to gel and the plasticizer to dissolve in the polymer, giving the final flexible composition. Gloves made
from this composition are commonly termed vinyl.
Polyurethane and styrene-butadiene-styrene block copolymers dissolved in organic solvent have been used to produce gloves and, in the case of polyurethane, also
condoms. However, for the producers of dipped articles, a water-borne polymer system is often highly desirable for health, safety and environmental reasons. Some
attempts have been made to convert polymers that have been synthesized in organic
solvent into aqueous emulsions suitable for dipping. So far these attempts have been
largely unsuccessful at the commercial scale, because of the cost involved in the
multistage process and because the relatively large quantity of surfactant added to
achieve emulsification increases the difficulty of controlled gellation during the dipping process.
There are only two commercially important water-borne polymers currently used
by the dipping industry and both are used to manufacture hand-protection articles.
These polymers are:
Copolymers of butadiene, acrylonitrile and a third monomer that contains a carboxylic acid group (usually methacrylic acid). Gloves made from this copolymer
are often termed nitrile. The particular advantages of this polymer are resistance
to many solvents and excellent mechanical protection (abrasion and puncture resistance). Nitrile also has a significantly lower surface electrical resistivity than natural rubber, and therefore finds use in gloves for use in areas where static electricity might be a problem.
Homopolymers of 2-chloro-1,3-butadiene (chloroprene). Gloves made from this
polymer are known as polychloroprene or Neoprene (Neoprene is a trademark of
E I DuPont de Nemours and Co). The key attributes of this material are a similar
stress-strain response (feel) to natural rubber, resistance to oils and fats and excellent light and ozone resistance.
Nitrile and polychloroprene latices are made by the industrial process of emulsion
polymerization, in which the polymerization reaction and the formation of an aqueous emulsion occur simultaneously. In this process, reaction temperature and control of the polymer molecular weight are important in order to obtain the desired final glove properties. In the case of the nitrile latex, the ratio of the three monomers
can also be used by the polymer chemist as an important tool in tailoring the final
product properties.
15.3
Principles of Dipping
The basic concept of producing a coating or a thin-walled article by the dipping

process is straightforward. A former of the desired shape is dipped into a liquid mix
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386
that contains the material of which the final product is to be made. The process is
arranged so that on withdrawal, a thin deposit of the mix is left on the former. The
process continues by heating the coated former to solidify, dry and cure the deposited mix. Finally the thin, flexible film is removed from the former to yield the desired
product. Further information on the dipping process has been published by various
authors, including Carl [1], Blackley [2] and Lanham and Eidam [3].
There are several ways in which the deposition of the mix can be controlled, in order to produce the desired wall thickness in the final article. The first is simply by adjusting the viscosity and solids content of the liquid, and is applicable to both solution and dispersion mixes. This process is called simple or straight dipping and is
the method usually employed for making condoms from natural rubber latex.
Straight dipping usually yields thin films. For the manufacture of condoms, the final
film is normally built up by two or more separate dips.
Coagulant dipping is the method most often used to deposit thicker films in a single dip, for example to make gloves or balloons. In this process, the mold or former
is first dipped into a coagulant liquid, such as an aqueous solution of calcium nitrate.
After partial drying of the coagulant, the former is dipped into the liquid mix, which
must be provided as a colloidal dispersion. The coagulant causes a localized destabilization and viscosity rise in the dispersion at the surface of the former, thus enhancing the amount of mix deposited. The thickness of the deposit can be controlled
by the concentration and drying of the coagulant solution and the colloidal stability
and total solids of the dispersion.
A third method used to control deposition on to the former is to use additives in
the mix that cause destabilization and/or a viscosity increase at elevated temperature.
Deposition of the mix is therefore facilitated if a hot former is used. This method has
been used mainly in the production of thicker items, for example babies teats. Heat
sensitizing additives that have been used with natural rubber include polyvinylmethyl ether and polypropylene glycol. Obviously, with this system especially, good
control over the temperatures of the dipping mix and former is necessary.
15.4
Dipping Synthetic Polymer Emulsions in Practice
Inevitably, refinements and modifications have to be added to the basic principles to

yield a viable, commercial dipping process. This section describes some of the
methodology used in achieving practical systems. Since at present the only significant use of synthetic emulsion polymers is with nitrile and polychloroprene latices
for glove manufacture, the following notes are necessarily directed towards this area.
15.4.1
Former Design
Obviously the main requirement of a former for unsupported glove production, is to

provide the shape of the desired final product. In addition, however, the mix or coag-
15.4 Dipping Synthetic Polymer Emulsions in Practice
ulant must easily wet the former, otherwise an irregular or incomplete deposit results. The design of the former (Fig. 15-1) should be such that air bubbles are not entrained on the former surface as it enters the mix. The design should also minimize
the tendency for the thin film to shrink in the length direction of the former during
drying. The formers should be easy to clean.
Fig. 15-1 Former designs for

(left) thin multi-purpose gloves
(ambidextrous); (center) for
fabric supported gloves (hand
specific) and (right) for industrial unsupported gloves (hand
specific).
Of the many materials tried, unglazed porcelain is favored for formers for unsupported glove manufacture, since it accepts coagulant readily and its micro-roughness
helps to limit length-direction shrinkage of the drying polymer film. For thicker
gloves and thin surgical gloves, specific left and right hand formers are used. For
thin disposable gloves, the same former shape is used for both left and right hands.
The production of fabric supported gloves requires special formers. Since these
gloves are relatively difficult to stretch, the former is often designed with a moveable
joint at the base of the thumb (or even a detachable thumb) to ease the task of removing the final product. Clearly, many of the features required by formers for unsupported gloves are unnecessary for fabric supported work, where only the fabric
liner should contact the dipping mix.
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388
15.4.2
Mix Design
Although the mix consists mainly of the polymer dispersion, it is usual to use several additives to achieve the desired performance. A typical mix for producing a glove is
shown in Tab. 15-1 and the various additives are discussed below.
Tab. 15-1
Typical latex-based formulation for dipped gloves.
Ingredient
Parts active per hundred dry rubber
Carboxylated nitrile rubber

Antioxidant dispersion
Potassium hydroxide solution
Zinc oxide dispersion
Sulfur dispersion
Accelerator dispersion
Titanium dioxide dispersion
Pigments
Thickeners
100
01.0
0.5
0.55.0
0.52.0
0.52.0
00.5
Trace
00.4
Antioxidant is normally included in the latex by the polymer manufacturer, but if

not it can be added to the mix by the compounder.
The alkali (in the example of Tab. 15-1, potassium hydroxide) is normally added to
the latex first, as it tends to stabilize the compound to the addition of the other components. The alkali also affects the pick-up on to the former and hence the final polymer film thickness. It is added in dilute form, since concentrations above 5 % can
cause the latex to flocculate. A fugitive alkali, such as aqueous ammonia, can be used
but gives a greater tendency for skin formation on the mix surface. A typical pH for
a dipping mix would be approximately 9.0, but this value will vary according to the
particular grade of latex being used.
Zinc oxide is an interesting ingredient. It is used in fairly large quantities (510
parts per hundred of dry polymer) in polychloroprene compounds as a cross-linking
agent, reportedly functioning by acting as a hydrochloric acid acceptor [4]. In nitrile
compounds, zinc oxide is also found to act as a curing agent, having a profound effect on the physical properties of the final film. In this case it is reasonably certain
that the mechanism is one of interaction of zinc cations with the carboxyl groups
present in the nitrile copolymer [5]. Levels of ZnO used with nitrile polymers are in
the range 0.55.0 parts.
The zinc oxide also reduces the colloidal stability of the mix and so influences the
amount deposited on the former during coagulant dipping.
For both polychloroprene and nitrile polymers the zinc oxide, together with the
other accelerators, also activates the sulfur vulcanization. However, for carboxylated
nitrile products, the sulfur curing is thought to be of less significance than the effect
conferred by the interactions between zinc cations and carboxyl groups [3]. Some ac-
celerators that are commonly used to increase the rate of sulfur curing are listed in
Tab. 15-2.
Tab. 15-2
Commonly used accelerators for nitrile and neoprene latices.
Chemical Type
Benzothiazoles
2-Mercaptobenzothiazole
2,2-Dithiobisbenzothiozole-2-sulfenamide
Benzothiazolesulfenamides
N-Cyclohexylbenzothiazole-2-sulfenamide
N-t-Butylbenzothiazole-2-sulfenamide
2-Morpholinothiobenzothiazole
N-Dicyclohexylbenzothiazole-2-sulfenamide
Dithiocarbamates
Tetramethylthiuram monosulfide
Tetramethylthiuram disulfide
Zinc diethyldithiocarbamate
Amines
Diphenylguanidine
Di-o-tolylguanidine
Common abbreviation
MBT
MBTS
CBS
TBBS
MBS
TMTM
TMTD
ZDEC
DPG
DOTG
The choice of accelerator depends on the curing profile and final properties desired. Care has to be exercised in the use of dithiocarbamates, since these materials
can give rise to discoloration in the presence of trace amounts of copper.
Previously, accelerators such as thiurams, thiazoles and carbamates were used,
but their use has declined because of problems with skin allergies. This issue is discussed in detail by Estlander et al. [6]. In addition to the problems of contact dermatitis, it may be necessary to consider the formation of N-nitrosamines by accelerators. Dithiocarbamates and thiuram sulfides have the potential to decompose to
give N-nitrosamine precursors [3]. N-nitrosamines are believed to be carcinogenic,
although conclusive evidence for human carcinogenicity is scant, as discussed recently by Loadman [7].
Titanium dioxide, in the form of an aqueous dispersion, is added as an opacifying
agent. It also enhances the color imparted by the pigment. Titanium dioxide is used,
despite its expense, because its high refractive index gives it a high opacifying efficiency and it can therefore be used in relatively small quantities with minimal impact on the physical properties of the product.
A thickener is often used to control the mix viscosity, which in turn affects pick-up
on to the former. Table 15-3 lists a few of the thickener materials that have been used
in dipping compounds.
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390

Tab. 15-3. Thickeners for dipping compounds.
Chemical type
Used in
Comments
Polyacrylates
Unsupported,
heavier weight gloves
Polyacrylates are often supplied as an emulsion,

becoming effective on raising their pH.
They usually give a pseudoplastic rheology.
Polyvinyl alcohol
Fabric supported gloves Solutions of PvOH can be difficult to prepare.

PvOH usually gives a thixotropic rheology.
Casein
Unsupported gloves
Expensive. Casein also acts as a colloid stabilizer.

It is susceptible to infection problems.
Other additives are also frequently employed in the dipping mix. Additional surfactant may be added to adjust the colloidal stability and thus the thickness or quality of the dipped film. Materials to discourage foaming in the mix or the formation of
a thin film of wet mix between the fingers of a glove (webbing) can also be added.
15.4.3
Coagulant
The usual coagulants employed for glove dipping are calcium salts that are soluble in
water, in particular calcium nitrate and calcium chloride. The advantages of these
materials include their efficiency in coagulating anionic emulsion polymers, their
relatively low cost, low toxicity and low environmental impact. The aqueous coagulant solution is usually held at high temperature (about 60 C), to accelerate its rate of
drying on the former surface. A surfactant is often added to the coagulant solution to
ensure adequate wetting of the former.
A technique sometimes employed is to dissolve the coagulant in a mixture of water and alcohol. The main advantages are an improved drying rate and improved wetting of the former. Because of its faster drying rate, alcoholic coagulant is used at a
lower temperature than the aqueous type, but of course the use of alcohol raises
problems from a health, safety and environmental standpoint.
It is quite common for the coagulant solution also to contain 1 to 5 % of a parting
aid. This is an inert powder, for example talc or calcium carbonate, which reduces
the adhesion between the final dipped film and the former, thus making the removal
of the finished glove easier.
15.4.4
The Dipping Process
Many aspects of the dipping process can be adjusted to suit the particular type of
glove being produced. In the following sections, some process details are given for
each of the three main types of gloves that are made using synthetic latex.
Disposable gloves
These products are often referred to as thin gloves and find use mainly in the healthcare sector, where their primary function is to prevent transfer of infectious agents
between medical workers and patients. A secondary function can be to provide protection against pharmaceutical preparations. Disposable gloves are also used in industrial applications, for example electronics, where the purpose of the glove is to
prevent assembly workers contaminating clean items, such as silicon wafers or disk
drive surfaces.
The most usual manufacturing process for disposable gloves is the continuous or
chain process. Here, individual or pairs of formers are attached at intervals to an
endless chain that moves at constant speed, enabling the formers to visit each processing station in turn. At stations where dipping occurs, the track bends downwards
then upwards, carrying the formers in and out of the liquid. Entry and exit is therefore not vertical. This operation gives high volume output for relatively low cost.
However, the process is rather inflexible and is best suited to large runs of one type
of glove.
A schematic diagram of the process is given in Fig. 15-2 and the various steps are
explained below.
Former
Cleaning
Fig. 15-2
Stripping
Coagulant
Bath
Latex Bath
Beading
Drying & Vulcanisation
Leaching
Anti-tack
Bath
Continuous
dipping
process.
The process starts with cleaning of the formers, an essential step without which
poor quality films will result. Cleaning is accomplished by passing the formers
through a bath of mineral acid or alkali containing surfactant, by brush scrubbing,
by ultrasonic treatment or a suitable combination of these methods. Cleaning is followed by a thorough rinse with clean water. As required, formers are taken out of the
process for a more extensive cleaning, perhaps with sulfuric or chromic acid.
The next step is to dip the former into the coagulant solution. The solution
strength is typically in the range 1025 % by weight, the concentration being monitored by specific gravity. The coagulant picked up by the former is dried before the
next step.
At the following station, the coagulant-coated former comes into contact with the
latex and the polymer deposit starts to build up on the former surface, increasing in
thickness with dwell time in the latex bath. In this central step of the process, the for-
391
392
mer temperature, speed and smoothness of former entry and exit are important factors in the production of an even, defect-free film.
On leaving the latex dip tank, the formers are lifted to the horizontal and rotated,
to avoid ungelled latex on the outside of the film flowing to the bottom of the former.
The latex layer continues to consolidate after removal from the latex bath, forming a
firm, gelled coating.
The polymer at the cuff of the glove is then rolled on to itself by the action of mechanical rollers or brushes, a process known as beading. The tack of the polymer at
this stage of processing is sufficient for the bead to be held in place. The purpose of
the bead is to give the cuff of the thin glove adequate tear-resistance.
Following beading, the glove is leached, a washing process carried out by immersing the glove in warm (4050 C), clean water. Long leaching times are preferred
from a technical standpoint, to achieve the maximum removal of water-soluble materials. However, in practice, leach duration is limited by time, space and cost constraints and is normally of the order of 510 min. Care must be exercised in the
leaching process, since high leach water temperatures can promote excessive length
direction shrinkage of synthetic latices.
The glove is then dipped into an anti-tack compound, which may be a silicone
emulsion or a slurry of calcium carbonate. The purpose of applying this material is
to reduce the rubber-rubber friction when the glove is ultimately peeled from the former, thus easing its removal, and to prevent the interior surfaces of the glove sticking together on storage.
The penultimate stage of the process is drying and vulcanization. Sophisticated
cure ovens will allow the curing to be phased, for example to bring the temperature
gradually to around 120 C to avoid blistering. A slightly cooler temperature may be
programmed for the final oven stage, to make glove removal easier. For the curing of
disposable gloves, approximately 20 min at 120 C is required. Undercured gloves
tend to have low tensile strength and high elongation, making them difficult to strip.
Incomplete drying can lead to problems of glove surfaces sticking to one another on
storage.
The removal of the glove from the former (stripping), is the only fully manual
part of the process, in which teams of three or four workers line each side of the
chain to pull off and briefly check the gloves for holes. Occasionally compressed air
jets are used to assist with the stripping process.
Disposable gloves can be further dried offline, by tumbling in heated ovens. Following tumbling, gloves are usually chlorinated by immersion in an aqueous dilute
chlorine solution (a technique also used for natural rubber disposable gloves). The
chlorine reacts with the surface layer of polymer molecules, giving a marked reduction in surface tack that makes the gloves easier to don. Finally, the gloves may be
washed, re-dried, QC tested and packed.
Unsupported heavier weight gloves
Thicker walled gloves, capable of being used on multiple occasions, find use in both
industrial and domestic situations. They are often made with a lining of small fibers
(floc lined), which improves comfort by absorbing perspiration.
Industrial gloves will probably be destined for use as protective equipment and
will therefore be required to meet specific safety standards. These standards cover areas such as resistance to chemical penetration, puncture resistance and abrasion resistance. Further information on protective gloves is given in the book edited by
Mellstrm et al. [6].
Household gloves are normally made from natural rubber and have been regarded
as price-driven commodity items. However, recent concern over protein allergy has
led to the increased use of sophisticated synthetic polymers in this area also.
Heavier weight gloves may be made by the continuous process in a similar manner to that described above, but they are more commonly produced by the batch
process, outlined as follows.
Jigs to which perhaps 20 or 30 formers are fixed are moved sequentially on guide
rails from station to station. Operations such as dipping into a liquid bath are
achieved using hydraulic equipment. Within limits, the time spent at each station
can be independently varied, so more control is possible than with the continuous
process, where the speed of movement round the track is constant.
A schematic diagram of the batch process for thicker unsupported gloves is given
in Fig. 15-3.
Fig. 15-3
Former
Cleaning
Coagulant
Bath
Stripping
Chlorination
Bath
Latex Bath
Leaching
Bath
Drying & Vulcanisation
Flock
Adhesive
Flocking
Booth
Batch dipping
process.
The various steps in this process are described below and the similarities and differences in the production conditions compared to those used for disposable gloves
are highlighted.
The process again begins with the cleaning of formers, using similar methods to
those employed in the thin glove process.
The coagulant solution is of a higher concentration and dip times are much longer
than those used for disposable gloves. The most common coagulant solution is aqueous calcium nitrate at 3040 % by weight. With the batch process, the formers enter
and leave the coagulant at right angles to the solution surface, only moving in the
vertical plane. After withdrawal from the coagulant, the formers are usually inverted
to achieve a more uniform distribution of the solution over the surface.
After drying the coagulant, the former is dipped into the latex bath. As for thin
gloves, the critical factors of entry and exit rate and former temperature have to be
393
394
optimized to produce an even polymer film. For thicker gloves, dwell times in the latex bath may be in excess of 2 min and for very heavy gloves a second dip may be employed. Note that film thickness is not only a function of dwell time in the latex, but
also of the coagulant strength and temperature, the latex mix viscosity and the latex
stabilizing system.
When the polymer film has gelled sufficiently it is leached in warm, clean water.
This stage is essential to remove surfactants and coagulant that would otherwise result in surface tack on the finished gloves. It is advisable to use as long a leach time
as practicable, and thicker gloves certainly require more time than disposable ones.
Typical leach conditions used for heavier weight gloves are 10 to 15 min with water
temperature in the range 4570 C.
If the gloves are to be flock lined, the next step is the application of a flock adhesive, again by dipping. The adhesive should form a good bond with both the glove
polymer and the flock fibers and should not be coagulated by any residual coagulant
that might be on the polymer surface at this stage of the process. To achieve a good
bond, it is common to use an adhesive that is based on the main glove polymer.
The flock normally consists of cotton fibers. The fibers are made airborne by compressed air or electrostatic methods in a booth, into which the gloves are moved.
Flock contacts, and adheres to, the wet adhesive and conditions are adjusted so that
the fibers are wetted by the adhesive, but not immersed in it. The electrostatic
method is useful in this regard, since it can be used to encourage an orientation of
the fibers perpendicular to the glove surface.
The drying and curing of heavy gloves is slower than for disposable gloves. As well
as having more water to evaporate, the drying rate of heavy gloves has to be limited to
prevent escaping water vapor ballooning the glove. In addition, industrial gloves
tend to need a higher degree of crosslinking to give chemical resistance. Curing
times of up to 45 min are quite usual.
The chlorination step is similar to that employed with thin gloves. For heavier
gloves, one side may be chlorinated on machine and the other off-line.
Stripping is a manual process and, for thicker gloves especially, it can be a fairly
demanding one, since highly cross-linked polymers can offer significant resistance
to the manipulation required for removal from the former. The best manufacturing
units use both former design and machine layout to ease this process.
After stripping, the gloves may be chlorinated or given a further heat treatment before being inspected and packed.
Fabric-supported gloves
Fabric-supported or coated fabric gloves are a small but important part of the market.
They are primarily used where a high degree of mechanical protection, combined
with water and chemical resistance, is required. The construction is based on a textile liner which has been coated with a polymeric layer. The liner fabric gives a benefit in user comfort and may be made from cotton, polyester, nylon or even Kevlar.
The liners are formed by cutting and sewing the chosen fabric into the desired
shape, or they are knitted in one piece. While the cut and sewn type predominates
15.5 The Testing of Synthetic Gloves
because of its ease of production, the knitted liner is finding increasing popularity
because of the reduced material wastage, lower labor cost and increased comfort.
The dipping of supported gloves is carried out successfully by only a few companies worldwide and the technology is generally proprietary. As there are many types
of supported glove and production methods vary, no attempt will be made to describe their manufacture here in any detail. It can be said, however, that the key issue
is to control the application of the polymer coating, so that good coverage and good
adhesion are achieved but without excessive penetration of fabric liner by the mix. In
addition to fabric design, compound low-shear viscosity, compound surface energy
and the depth and duration of dipping are some of the factors that can be used to
achieve a successful over-dip.
The presence of a fabric liner creates some practical problems in the dipping
process. With the correct control of latex compound rheology, straight dipping can,
of course, be used. If a coagulant method is chosen, a significant amount of the coagulant may be absorbed into the liner, requiring removal from the finished glove by
thorough washing. The use of a heat-sensitized dipping compound is complicated by
the difficulty of achieving a controlled temperature at the liner surface and the difficulty of controlling the mix viscosity close to the liner in the presence of a hot former.
In general, the coagulant and straight dipping methods are the most favored.
15.5
The Testing of Synthetic Gloves
An increasing number of standards concerned with the performance of gloves are

becoming available. They come from a variety of sources (regulatory bodies), including:
International
USA
UK
France
Germany
Europe
Former USSR
International Standard Organization

American National Standards Institute
American Society for Testing and Materials
British Standards Institution
Association Franaise de Normalization
Deutsches Institut fr Normung
European Standards
State Committee for Standards
(ISO)
(ANSI)
(ASTM)
(BSI)
(NF)
(DIN)
(EN)
(GOST)
Note that various professional organizations have also developed standards which
can be useful for glove testing.
15.5.1
Non-safety-critical Gloves
There is a number of standards specifying the general performance of polymeric materials which might be used in the manufacture of gloves. For example, both the
395
396
ASTM and BSI have issued methods for testing the physical properties of rubbers
and the effects on rubbers of accelerated aging.
The ASTM has issued a standard for household or beauticians gloves, which sets
out specifications aimed at assisting in the achievement of performance consistency.
Tests specified include tensile strength and elongation (before and after aging),
physical dimensions and freedom from holes. This standard refers to general methods for testing elastomeric materials, such as those mentioned in the preceding paragraph.
Gloves that are used in electronic assembly are designed primarily to protect the
product under manufacture, rather than protect the worker. Some standards relating
to glove material cleanliness and to the testing of static electrical properties of materials are available and used in this area.
15.5.2
Safety-critical Gloves
The hand is perhaps exposed to more hazards than any other part of the body. These
hazards include physical damage, chemical contact and contact with biological
agents. Clearly, one means of minimizing the risk of these hazards actually causing
harm, is to select an appropriate glove.
There are many standards that specify tests and performance for protective gloves.
The general tests relating to the physical properties of glove materials, referred to
above, may be used. The European Union has detailed a number of requirements for
protective glove manufacturers in the Personal Protective Equipment Directive
89/686/EEC. Gloves meeting these requirements carry the CE mark, which allows
them to be marketed throughout all European Community countries.
There are individual standards for assessing protection from mechanical, chemical, biological and radioactive hazards, as well as protection from heat and cold. Particular standards dealing with surgical and examination gloves exist, some of which
are material specific, and for gloves designed to give protection against electrical
hazards.
Some of the standards that have found use in the protective glove area are listed in
Tabs. 15-4, 15-5 and 15-6.
15.5 The Testing of Synthetic Gloves

Tab. 15-4
North American standard test methods.
ASTM D120 E1
ASTM D412
ASTM D573
ASTM D624
ASTM D991
ASTM D1418
ASTM D3577
ASTM D3578
ASTM D4679
ASTM D5151
ASTM D5250
ASTM D5712
ASTM D6319
ASTM E595
Tab. 15-5
Standard Specification for Rubber Insulating Gloves

Standard Test Methods for Vulcanized Rubber tension
Standard Test Method for Rubber deterioration in an air oven
Standard Test Method for Tear Strength of Conventional Vulcanized Rubber
and Thermoplastic Elastomers
Standard Test Method for Rubber Property volume resistivity
of electrically conductive and antistatic products
Standard Practice for Rubber and Rubber Latices nomenclature
Standard Specification for Rubber Surgical Gloves
Standard Specification for Rubber Examination Gloves
Standard Specification for Rubber Household or Beautician Gloves
Standard Test Method for Detection of Holes in Medical Gloves
Standard Specification for Polyvinyl Chloride Gloves for Medical Application
Standard Test Method for Analysis of Protein in Natural Rubber
and its Products
Standard Specification for Nitrile Examination Gloves for Medical Application
Standard Test Method for Total Mass Loss from Outgassing in a Vacuum
Environment
European standard test methods.
BS/EN 368
BS/EN 369
BS/EN 374-1
BS/EN 374-2
BS/EN 374-3
BS/EN 388
BS/EN 407
BS/EN 420
BS/EN 421
BS/EN 455-1
BS/EN 455-2
BS/EN 464
BS/EN 511
BS 903 :A2
BS 903: A9
BS 903: C1
BS 2782: Part 2
BS 2782:
Method 231A
BS 7506:1
Protective Clothing for Use against Liquid Chemicals penetration

of liquids
Protective Clothing for Use against Liquid Chemicals permeation
of liquids
Protective Gloves against Chemicals and Microorganisms
terminology and performance requirements
determination of resistance to penetration
determination of resistance to permeation by chemicals
Protective Gloves against Mechanical Risk
Protective Gloves against Thermal Risks (heat and/or fire)
General Requirements for Gloves
Protective Gloves against Ionizing Radiation and Radioactive
Contamination
Medical Gloves for Single Use specification for freedom from holes
Medical Gloves for Single Use specification for physical properties
Protective Clothing Protection against Liquid Chemicals gas leak test
Protective Gloves Against Cold
Physical Testing of Rubber determination of tensile stressstrain properties
Methods of Testing Vulcanized Rubber determination of abrasion resistance
Methods of Testing Vulcanized Rubber determination of surface resistivity
Methods of Testing Plastics electrical properties
Methods of Testing Plastics determination of surface resistivity
Measurement in Electrostatics guide to basic electrostatics
397
398

Tab. 15-6
Professional standard test methods
UK Dept of Health
M.D.D. TSS/D/300.010
Institute of Environmental
Sciences and Technology (USA)
IES-RP-CC005.2
Specification for non-sterile NR latex examination gloves

Gloves and finger cots used in clean rooms and
other controlled environments
These lists are not intended to be exhaustive, but are included to give the reader
some idea of the breadth of standards available. Clearly, as new technologies evolve,
standards will be updated and others newly issued.
References
1 J. C. Carl, Neoprene Latex Principles
of Compounding and Processing,

E. I. Dupont De Nemours, Wilmington,
Delaware, USA, 1962.
2 D. C. Blackley, Polymer Latices Science
and Technology, 2nd edn, Vol. 3, Chapman and Hall, London, UK, 1997.
3 A. Lanham, N. Eidam, in: Wrige Polymerdispersionen, D. Distler (ed.), WileyVCH, Weinheim, Germany, 1999.
4 D. M. Bratby, in: Polymer Latices and their
Applications, K. O. Calvert (ed.), Applied
Science, London, UK, 1982.
5 L. Ibarra, M. Alzorriz, Polym. Int. 1999,
48, 580.
6 T Estlander, R Jolanki, L Kanerva, in:
Protective Gloves for Occupational Use,

G. A. Mellstrm, J. E. Wahlberg,
H. I. Maibach (eds), CRC Press,
Boca Raton, Florida, USA, 1994.
7 M. J. R. Loadman, Proc. Int. Rubber
Conf., Manchester, UK, 1996.
Index
a
abrasion cohesion test Esso (ACTE) 323
abrasion resistance 115, 332
accelerators 389
acorn structure 5
acrylates 90
acrylic adhesive 220
acrylic dispersions 6, 12, 90, 108, 130 f., 142,
154, 193 ff., 217, 273 f., 285, 291, 358
acrylic esters 90, 94
additives 78, 132, 240, 332 f., 355
adhesion 191 ff., 299, 330, 332, 338 f., 339
adhesion level 210
adhesion-elongation 238
adhesive raw materials 192
adhesives 191 ff., 334
agglomeration number 28
aggregates 332
aging resistance 299
American Standards (ANSI) 335
analytical ultracentrifuge 51
antifoam agents 6, 114, 136, 202
antifreeze agents 235
anti-sag 334
apparel leather 284, 293
applications tests 97 f., 114 f., 142 ff., 147 f.,
151, 156 f., 159 f., 168 ff., 210 ff., 221 f.,
228 ff., 232, 237 f., 240, 246 f., 249, 261,
275 ff., 296 ff., 304 ff., 321, 335 ff., 368,
395 ff.
aqueous 1
aqueous flexo news ink 121
aqueous ink 104
aqueous phase analysis 57
asphalt binder 304
asphalt composition 310
asphalt consumption 301
asphalt emulsion 302, 303, 313 ff.
anionic 315
application 314
cationic 315
cured 318
ductility 317
elastic recovery 317
latex modified 318
medium-setting 313
modification 301
penetration 317
properties 309
rapid-setting 313
slow-setting 313
softening point 317
specification 304
tests 317
torsion recovery 317
automotive coating 163 ff., 176 f., 183
appearance 169
basecoat 167
clearcoat 167
crosslinking 183
electrocoat 167
emulsion polymers 176
formulation 168
function of ingredients 168
function 167
layer 167
main ingredients 168
microgels 177
miniemulsions 177
performance 169
primer 167
standard tests 169
automotive leather 284, 294
average degree of polymerization 195
b
back-coating of carpets 259, 262
bally flexometer 297
barrier coatings 7
basecoat 173 ff., 287, 344
399
400
Index
bending beam rheometer 306, 308
bimodal 5
binder 78, 84 ff., 127, 253, 291, 332
natural 90 f.
paints 127
sole binder 90
styrene-acrylate 96 f.
styrene-butadiene 95, 97
synthetic 90 f.
binding strength 87, 92 ff.
biocides 6, 135, 203
biodegradability 6
blistering 93 ff.
block resistance 116
board 92
branching 18
brightness 84, 86, 93
butadiene 9, 90, 94 f.
butadiene-styrene copolymers 11, 90, 256 ff.,
273 f., 285, 291, 303 ff.
butadiene-acrylonitrite copolymers 385 ff.
butyl acrylate 90
c
calcium carbonate 86 f.
calender 85 f.
capillary hydrodynamic fractionation 53
capillary water absorption 345
carboxylated styrene/butadiene (XSB)
dispersions 6, 90, 256 ff., 273 f.
carboxylic acid 26
carboxymethylcellulose 88, 90
carpet 253
carpet backcoating 259
carpet backing 253
carpet backing binders 253, 256, 258
carboxylated styrene-butadiene 256
cold SB (styrene-butadiene) 256
high solids styrene-butadiene latex
(HSL) 256
hot SB (styrene-butadiene) 256
natural latex 256
carpet laminating 259, 263 f.
adhesive scrim coat 263
pre-coat 263
unitary backing 264
carpet production 255
carpet terminology 260
cement 333
cementitious topcoats 345
centrifugation 51
ceramic tile adhesives 238 ff., 332 ff.
chain entanglement 21
chain transfer 18
chain transfer agent 32, 178, 198

characterization 41 ff.
chelating agent 34
chemical bonding 273
chemical reacting adhesives 192
chemical resistance 116
china clay 86
chip seal 316, 321
application test 321
coagulant dipping 386
coagulants 390
coagulation 3
coagulum 37
coagulum grit 42
coating 205
coating color 81, 85, ff.
co-binder thickeners 87
pigments 86
sheet-fed offset 86
coating layers 166
coating of carpets 261
coating support materials 205
coating weight of adhesives 207
co-binder 84, 87 ff.
coefficient of friction 116
colloid mill 313
color 65
concrete 242, 346 ff.
maintenance 347
rehabilitation 349
repair 347 f.
construction adhesives 224
construction industries 191
contaminants 36
conversion 22
conversion process 363
melt rheology 363
conversion-time curve 23
core-shell modifiers 373
core-shell structure 4 f.
core-shell impact modifier 376
core-shell particle 71
corona discharge 118
corona-pretreated film 218
corrosion inhibitor 114
CPVP 126
cracking 336
crinkle resistance 116
critical micelle concentration
(CMC) 19, 27
critical PVC 126
critical surface tension 65
cross-linking 4, 9, 21, 33, 70, 113, 167, 183 f.,
220
Index
cup and plate inks 120
curtain coater 289 f.
d
decorative coatings 123 ff., 137, 139
defoamer 6, 114, 136, 202
degradation time 360
delaminating 336
delamination resistance 221
density 43
diafiltration 58
dialysis 58
differential scanning calorimetry 60
dilatancy 45
dipped gloves 388
dipped goods 383
dipping 384 ff.
forms 386
mix design 388
polymers 384
practical aspects 386
principles 385
process 383, 390 ff.
direct print corrugated inks 119
disc centrifuge 53
dispersing aids 133, 235
dispersion 1
dissolution 66
double-sided adhesive tapes 209
Dougherty-Krieger equation 47
dry adhesion 299
dry mix mortars 333, 352
dry mortar technology 332
pre-mixed 332
pre-packed 332
redispersible powders 332
drying test 116
dwell time 212
dynamic light scattering 49
dynamic mechanical analysis 63 f.
dynamic shear rheometry (DSR) 306
electric double layer 26

electrical tapes 208
electrocoat 170 ff.
electrokinetics 56
electrolytes 33
electrophoretic mobility 56
elongation at break 6, 63
elpo 170
embrittlement 299
emission measurement 230
chamber method 230
emulsified asphalts 302
emulsifier coverage 55
emulsifiers 9
emulsion polymerization 3, 16, 17, 20, 330,
356
at atmospheric pressure 16
at high pressures 16
mechanism 17
emulsion 1
emulsion polymers 15
synthesis 15
emulsion vehicle 109
engineering resins 375
environmental impact 325
equipment 39
ethene 8, 10
ethylene/vinyl acetate copolymers 6, 90,
330 ff.
extenders 132
extensibility 361
exterior decorative coating 146 ff.
application tests 148
exterior exposure testing 148
formulations 147
performance tests 147
standard application tests 147
exterior insulation and finish systems
(E.I.F.S.) 332
exterior insulation systems 341
exterior thermal insulation compounds
(E.T.I.C.S.) 332
e
E.I.F. systems 342
e-coat 170
eco-efficiency analysis 323
efflux time 44
elastic modulus 62
elastic recovery 237
elasticity 6
elastomeric roof coatings 247
elastomeric wall coating 149 f.
formulation 150
f
fastness 299
fatigue cracking 306
Fikentschers K-value 195, 360
fillers 86, 202
film formation 128 f.
coalescing agent 129
latex 128
film forming emulsion polymer 117
film morphology 70
film whitening 67
401
402
Index
finish systems 341
finishing 287
finishing coats 287
flexibility 332, 336, 338
mortar 338
flexible 217, 330, 336
packaging 217
flexing endurance 297
flexographic 103
ink formulation 107
printing press 105
flexural strength 332
flocculation techniques 57
flock lining 394
floor-covering adhesives 224
flow behavior 44
flow curve 44
flow, Newtonian 45
flow, pseudoplastic 45
foam backing 257
foam impregnation 274
foaming 6
foaming behavior 48
fogging test 300
foil duct tapes 208
folding carton inks 118
food packaging 7
form 386
dipping 386
form cleaning 391
dipping 391
formulation 86 f., 107, 117 ff., 141, 147 ff.,
150, 152 f., 156 f., 168, 171, 199 ff., 203 f.,
219, 224, 227 f., 233, 236, 239, 243, 245, 249,
263 f., 274, 388
free radical 18
free-radical polymerization 25
freeze-thaw 116, 245, 336
stability 48
functional monomers 26
furniture automotive 222
furniture leathers 295
fusion promotion 359
g
gas chromatography 56
gas permeation 68
gel effect 21
gel fraction 67
gel permeation chromatography 69
glass transition temperature 1, 6, 60, 94,
128, 154, 195, 288, 338, 357
gloss 65, 93, 99, 112
gloss enamel 142
glossy film lamination 219

glove dipping 391, 393
batch process 393
continuous process 391
gloves 384, 391 ff.
dipping 391
disposable 391
fabric supported 394
polymeric 391
protective 396
testing 395
unsupported 392
gradient polymer elution chromatography 69
grain impregnation 287
gravure 103
ink 106
ink formulation 107
printing press 106
roll 206
Green Label certification 227
of adhesives 227
green strength development 230
h
heat distortion temperature (HDT) 356
heat resistance 116
heat sensitivity 33
Helio test 100
high float emulsions 314
hot light aging 300
hot mix asphalt 302 f.
hydration 337
hydrodynamic particle diameter 50
hydrophobicity 332
i
impact behavior 376
impact modification 370
impact modifiers 11, 367, 373, 375
non-weatherable 375
weatherable core shell 373
impact performance 369, 372
impact resistance 367
impurities 35 f.
induction period 21
industrial maintenance coatings 155 ff.
application tests 156, 158
formulation 157
performance tests 156
salt spray testing 158
inisurf 9
initiation 18
initiator 9, 31, 178
Index
half-life 31
thermal decomposition 32
thermally dissociating 31
initiator systems 30
half-life 30
peroxides 30
persulfate 30
ink 93
absorption 93
additives 113
color strength 114
composition 106
for films 117
jet papers 81
splitting 97 ff.
in-line injection 311
interior decorative coating 139 ff.
adhesion test 144
block resistance 145
formulation 140 f.
freeze-thaw stability 142
heat age stabilitiy 142
interior flat coatings 140
performance test 145
print resistance test 145
scrub test 144
stability heat age test 142
stain resistance test 144
wall coatings enamels 140
interior enamels 140
internal surface area 3
interparticle crosslinking 67, 70
intrinsic viscosity 69
isolation technology 356 f.
j
joint filling compositions
233
k
kaolin clay
86, 87
l
laboratory reactors 15
laminating adhesives 217 f., 222
laser light scattering 49
latex 3
definition 3
paints 125
lawn and garden bag inks 118
layers 166
automotive coatings 166
leather 283, 291
binder 291
structure 283
leather articles 292
leather finishing 285 f., 296
test methods 296
leather industry 283
leather production 284
letterpress 103
life-cycle analysis 324
light-fastness 300
light transmission 49
liquid soaps 7
loaded wheel test (LWT) 322
loss modulus 63
low film forming temperature 112
low temperature cracking 306
lubrication 364
m
manufactures 12
manufacturing processes 34
batch 34
continuous 34
plug-flow continuous reactor 34
semi-batch 35
Maron plot 55
masking tapes 209
mastic products 231
mechanical characterization 62
mechanical stability 48
medical diagnosis 7
melt homogeneity 359
melt rheology 363
melt strength 361
melt viscosity 362
membrane filtration techniques 58
membranes 350 f.
waterproof 350 f.
metallic effect 186
metallic flog (MF) index 182
micellar nucleation 20
micelles 19
microgels 70, 177
microorganisms 6, 203
protection against 203
microscopic characterization 68
microsurfacing 316, 321
application test 321
pavement 320
Mie scattering 4
milk carton ink 120
milk carton wet rub 116
mineral topcoats 344
miniemulsions 177
403
404
Index
minimum film formation temperature
(MFFT) 59, 128
model system 17
modified fretting 323
modifier shell effects 372
modulus of elasticity 336
moisture vapor transmission 247
molecular weight 69, 127, 357
monomer 23 f., 94
monomers 23, 25 f.
butadiene 24
concentration 21
diene 24
fox equation 23
functional 26
major 23
polymer design 25
polymer properties 23
vinyl monomer 24
mortar 239, 241 ff., 348 ff.
mottling 93, 99
multiple wall bags 121
inks 121
n
natural adhesives 192
natural rubber latex 11, 303
needlepunched carpet 255
neoprene latex 303
newspapers 121
inks 121
non-weatherable impact modifiers 375
non-weatherable PVC formulations 374
non-woven manufacturing systems 270
non-wovens 267 ff.
applications 268
binders 273
standard test methods 276
notch sensitivity 370
o
OEM coatings 164
offset printing 82, 85, 93 ff.
rotogravure printing 93
sheet-fed 85 f.
web offset printing 93
offset test 99
oligomeric radicals 20
opacifying aids 134
hollow sphere particles 134
TiO2 134
opacity 82, 86, 93
open time 113, 230
optical characterization 65
organic pigments 107
original equipment manufacturers
(OEM) 164
coatings 164
p
P&I test 99
packaging tapes 208
paint formulations 125
paints 127
binder 127
paper coating 76, 79, 81, 84
coating colors 84
coating techniques 84
paper gloss 84
paper industry 75 f.
paper machine 78
paper products 120
inks 120
paper properties 78
paperboard coatings 75
particle morphology 70
particle size 48, 94 f.
particle size distribution 52, 94, 331
dispersion/redispersion 331
particle surface 54
patch mortar 346
paving 303, 313
peel resistance 229
measurement 229
peel strength 196, 210 ff.
peel value 197
performance grading 304 f.
permanent deformation 306
permanent paper label 203
permeability 7
permeation 66
pH 43
photon correlation spectroscopy 49
pick strength 93
see binding strength
pigments 82 ff., 109, 132, 202
coat 288
dispersion 108
dispersion stability 104
extender 132
surface treatment 109
volume content of paints (PVC) 125 f.
plastic materials 355
modification 355
plasticizer 201, 286
migration 286
plastics production 10
Index
plywood on lumber shear test 232
polyacrylate dispersions 194, 291
leather-finishing 291
polyacrylates 11
polybutadiene dispersions 291
polychloroprene adhesives 225
poly-coated board 120
polyken probe tack 214
polymer characterization 68
polymer colloids 1
polymer compositions 129
binder 129
styrene-butadiene copolymers 129
polymer corporation 131
acrylic copolymers 131
specialty monomers 131
polymer design 25
polymer dispersion 2 f., 10 ff., 41, 273
characterization 41
commercial importance 10
definition 3
manufactures 12
names 2
properties 3
suppliers 13
synthesis 15
polymer films 58
polymer isolation technology 357
polymer modified cement concrete
(PCC) 349
polymer strength 6
polymer/cement ratio 337
flexibility 337
polymeric impact modifiers 355
polymeric modifiers 358
classification 358
processing aids 358
polymeric gloves 397
standard test 397
polymerizable surfactants 30
polymer-modified asphalt 309
polymer-modified mortars 241
polyolefins 10
polystyrene 10
polystyrene dispersions 7
polyurethane adhesives 223
polyurethane dispersions 7, 170, 172, 175,
179 ff., 191, 217 f., 222 f., 285, 288, 292
polyurethanes 110
polyvinyl acetate 90
polyvinyl alcohol 88 ff., 332
polyvinyl chloride 10
porosity 93
pre-mixed 332
pre-packed 332
pre-print corrugated inks 119
pressure sensitive adhesives 193, 205, 207,
210
test methods 210
pressurized aging vessel (PAV) 304
primer 172 f.
composition 173
formulations 152 f.
polymers used 172
requirements 172
surfacer 172
primer coating 151 ff.
marker stain resistance 153
stain blocking 153
print bonding 274
printability 93
printability tests 99
printing 103
printing inks 103, 115
tests 115
printing processes 92, 103
probe tack method 214
process aids 355
process conditions 37
branching 37
crosslinking 37
monomer/polymer concentration 37
number of particles 38
temperature 38
processing aids 359 ff.
effect 366
for PVC 359
for resins 366
types 364
product resistance 116
propagation 18
propagation rate 21
propene 9 f.
protective coatings 123, 154
protective colloid 6, 9
protective films 209
protective gloves 384
pulp 77 ff.
pulp suspension 79
pump-in 311
PVC durables 373
PVC formulations 371
for building products 371
405
406
Index
q
quasielastic light scattering
quick-stick 213
49
r
raspberry structure 4, 5
rate of polymerization 19, 21
raw hide production 285
raw materials 8
reactive monomers 9
recycling 10
redispersible powders 329, 332, 339
adhesion 339
building materials 329
building/construction industry 329
dry mix mortar technology 329
premixed 329
pre-packed 329
repair mortar 241, 346, 350
residual volatiles 56
residue characterization 319
resin 104
support 110
resinated pigments 109
resistance to flow 237
re-solubility 112
reverse gravure 205
re-wetting 116
rheology control agent 181
roll coating 289 f.
rolling ball 215
roof coating 248
rosin fumarate ester 110
rosin fumarates 104
rotating thin film oven test (RTFOT) 304
rotogravure printing 82 f., 86, 94, 99
rubber milk 3
rub-fastness 298
rub test metal corrugator 116
rutting 306
s
safety 40
capacity limitation 40
design pressure 40
relief devices 40
sand 333
saturation 274
scale-up criteria 15
scrim coat 262
sealant 233 f., 236 f.
production 237
slurries 351
tensile stress values 236
types 235
seed polymer 39
seeded emulsion polymerization 20
seeded processes 29
selected conversion processes 364
self-adhesive articles 210
labels 194, 205
products 199
tapes 207
self-leveling underlayments (SLU) 345
serum separation techniques 57
shear strength 198, 210, 216, 229
measurement 216
shear thinning 45
shear value 197
shoe upper leather 292
shotcrete process 350
silane-based coupling 235
size press 79
sizing agent 78, 80
low molecular weight 80
polymeric 80
slot-die coating 207
SLU 345, 347
abrasion resistance 347
surface 347
slurry seal 316
soap titration 55
solids content 42
solubility parameters 67
solution polymers 113
solution vehicles 112
solvent based ink 103
soy protein 90 f.
spray drying 330, 357
emulsion polymerization 330
spray-dry process 331
spray dyeing 287
spray machine 289
spraying 289
stability 47
starch 79 ff., 88, 90 f.
static light scattering 51
steady shear viscosity profile 182
steam cracker products 8
storage modulus 63
storage stability 48
stress-strain measurements 62
styrene 10, 90, 94
styrene-butadiene dispersions 6, 90, 129,
204, 217, 256 ff., 273 f.
styrene-butadiene rubber (SBR) latex 227,
256 ff., 303 ff.
sub-floor mastics 231
Index
superpave binder specification 305
superpave performance grade 304
surface-active materials 27
surface print inks 118
surface sizing 76, 79 ff.
surface tension 43
surface tension of films 117
surface treatment 108, 314
of pigments 109
surfactant 27 ff., 114
physical properties 27
structural influences on properties 28
surfmer 9
swelling 66
synthetic additives 78
synthetic adhesives 192
t
tack 6, 195, 210, 213
tackifying resins 200
tack measurement method 214
tanning 283
tensile strength 63
termination 18
test methods 97 f., 114 f., 142 ff., 147 f., 151,
156 f., 159 f., 168 ff., 210 ff., 221 f., 228 ff.,
232, 237 f., 240, 246 f., 249, 261, 275 ff.,
296 ff., 304 ff., 335 ff., 368, 395 ff.
thermoset coatings 183
thick bed mortar technique 334
thickeners 7, 84 ff., 133, 235, 390
anionic 235
dipping compounds 390
thickening 201
thin bed mortar technique 334
thixotropy 45
tile adhesives 240
test methods 240
tile grouts 332, 334, 340 f.
ANSI Standards 341
EN Standards 341
titanium dioxide 84, 86, 132 f., 147, 160,
202
top coats 288, 341, 344
torque rheometry 360
toughness 63, 367
towel and tissue ink 122
traffic marking paints 158 ff.
application tests 159 f.
dry-through time 159
formulation 160
no-pick-up test 160
retro-reflectance 160
transmission electron microscopy 70
transparency 6, 65
tufted carpet 254 ff.
u
unitary coating
264
v
vario gravure 206
vinyl acetate copolymers 6, 11, 90, 130, 141,
273 f., 330 ff.
vinyl chloride 10
vinylidene chloride 7
viscosity 5 f., 45, 96, 182
dilatant 6
pseudoplastic 5
shear rate 5
thixotropic 5
viscosity, Zahn efflux cup 117
volatile organic compounds (VOC) 165, 258
w
wall coatings 139
wall mastics 231
water based ink 103
water impermeability 332
water loss of green concrete 248
water resistance 117
water uptake 67
water-borne binders 176
aqueous polyurethane dispersions 179
for automotive coating 179, 181
rheology control agents (RCA) 181
secondary acrylic dispersions 179
water-borne coatings 163
applicaton properties 185
water-borne emulsion polymers 124
waterproofing membranes 244, 250, 350
waterproofing sealing 351
waterproofing system 350
water-soluble binders 185
properties 185
water-soluble oligomers 4
wax emulsions 113
weatherability 374
weatherable impact modifiers 373
web consolidation 272
mechanical bonding 272
thermal bonding 272
web formation 271
dry-laid 271
spun-laid 271
wet-laid 271
wet adhesion 299
407
408
Index
wet finishing 286
wet pick strength 94 ff.
wet track abrasion test (WTAT)
wetting 65
wetting agents 201
wetting aids 136
white-point temperature 60
workability 332
work of fracture 63
woven carpet 254 f.
y
322
yellowing 94, 299

Youngs modulus 62
z
zeta potential 56
Zosel tack measurement
215

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Polymer Dispersions and Their Industrial Applications.

Edited by Dieter Urban and Koichi Takamura

edited by Dieter Urban and

This book was carefully produced. Nevertheless, editors, authors and

A catalogue record for this book is

A catalogue record for this publication is

Printed in the Federal Republic of Germany

TypoDesign Hecker GmbH,

GmbH & Co. KG, Grnstadt

Names and Definitions 1

Synthesis of Polymer Dispersions 15

Characterization of Aqueous Polymer Dispersions 41

Applications in the Paper Industry 75

Applications for Printing Inks 103

Multiple Wall Bags 121

Applications for Decorative and Protective Coatings 123

Traffic Marking Paints 158

Applications for Automotive Coatings 163

Applications in the Adhesives and Construction Industries 191

Elastomeric Roof Coatings

Applications in the Carpet Industry 253

Non-wovens Application 267

Applications in the Leather Industry 283

Production of Selected Leather Articles 292

Applications for Asphalt Modification 301

Applications of Redispersible Powders

Applications for Modification of Plastic Materials 355

Applications for Dipped Goods 383

Dr. Christoph Hahner

7834 Covey Chase Drive

Wacker Polymer Systems, L. P.

Dr. Mary Burch

Rohm & Haas Company

Rohm & Haas Company

BASF Nederland B.V.

The Dow Chemical Company

Wacker Polymer Systems GmbH&CoKG

Rohm & Haas Company

BASF Nederland B.V.

Flint Ink Corporation

Rohm & Haas Company

Effect of coated paper on offset printing.

Effect of coated paper on rotogravure printing.

Photomicrograph demonstrating spontaneous

Names and Definitions

Commonly used names for aqueous synthetic organic polymer

1.2 Properties of Polymer Dispersions

Swedish, Turkish) and emulsions (Arabic, Chinese, English, Indonesian, Italian,

Properties of Polymer Dispersions

The aggregate state of a polymer dispersion is thermodynamically unstable. The very

What is a polymer dispersion?

1.2 Properties of Polymer Dispersions

Electron photomicrograph of a bimodal polymer

1.2 Properties of Polymer Dispersions

Polymer dispersions with a high amount of acrylic/methacrylic acid convert to

Important Raw Materials

Steam cracker products.

1.3 Important Raw Materials

Commercial Importance of Polymer Dispersions

Growth of plastics production.

1.4 Commercial Importance of Polymer Dispersions

Polymer Dispersions (dry) 4%

Production by polymer class [21].