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- Herausgeber: Vincentz Network
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
- Veröffentlichungsjahr: 2014
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Vincentz Network GmbH & Co KG
Thomas Brock
Michael Groteklaes
Peter Mischke
European Coatings Handbook
2nd revised edition
Brock, Groteklaes, Mischke: European Coatings Handbook
© Copyright 2010 by Vincentz Network, Hannover, Germany
ISBN 978-3-86630-889-3
Cover: Evonik Tego Chemie GmbH
Bibliographische Information der Deutschen Bibliothek
Die Deutsche Bibliothek verzeichnet diese Publikation in der Deutschen Nationalbibliografie ; detaillierte bibliografische Daten sind im Internet über http://dnb.ddb.de abrufbar.
Thomas Brock, Michael Groteklaes, Peter Mischke
European Coatings Handbook, 2nd Edition
Hannover: Vincentz Network, 2010
European Coatings Tech Files
ISBN 3-86630-889-2
ISBN 978-3-86630-889-3
© 2010 Vincentz Network GmbH & Co. KG, Hannover
Vincentz Network, Plathnerstraße 4c, 30175 Hannover, Germany
This work is copyrighted, including the individual contributions and figures.
Any usage outside the strict limits of copyright law without the consent of the publisher is prohibited and punishable by law. This especially pertains to reproduction, translation, microfilming and the storage and processing in electronic systems.
The information on formulations is based on testing performed to the best of our knowledge.
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ISBN 3-86630-889-2
ISBN 978-3-86630-889-3
eBook-Herstellung und Auslieferung: readbox publishing, Dortmundwww.readbox.net
European Coatings Tech Files
Thomas Brock
Michael Groteklaes
Peter Mischke
European Coatings Handbook
2nd revised edition
Brock, Groteklaes, Mischke: European Coatings Handbook
© Copyright 2010 by Vincentz Network, Hannover, Germany
ISBN 978-3-86630-889-3
Foreword
Anyone working in the coatings sector, whether in manufacturing or processing, knows – or will soon observe if they are new to the business – that an extremely broad knowledge base is a prerequisite for mastering this unique protective and finishing material. Coating chemistry in its widest sense, and especially polymer science, is of central importance. However, today’s coatings specialist also requires a knowledge of process engineering in relation to the use of production or application equipment, an understanding of materials science in regard to substrate materials and more generally in terms of the quality of the paint system, and finally a familiarity with environmental and safety aspects.
Very few teaching institutions are able to offer a training programme that is specially designed to cover such an extensive field of knowledge. The Niederrhein University of Applied Scienes in Krefeld, Germany, is one of these – an institution with a long tradition and good reputation, whose name comes up repeatedly in discussions with leading figures in the coatings sector. A good many of them proudly and gratefully acknowledge that the framework for their career was built in Krefeld.
For this reason the publishers and editors are extremely grateful to the current teaching faculty, represented here by Peter Mischke, Michael Groteklaes and Thomas Brock, for deciding to make a large part of the Krefeld curriculum available to practitioners in the field. The authors have produced a contemporary handbook of coating technology. Each was responsible for around a third of the content, based on his own specialist subject areas and written in roughly the above sequence. The work merits the title of handbook for two reasons: firstly because of its solid theoretical basis, augmented by “in-depth” explanations (shown on a grey background) where necessary, and secondly because of its consistently relevant use of practical references to exemplify its themes. These features are underpinned by a constant awareness of emerging developments in the coatings sector, which remains as dynamic as ever.
The book covers the principles of raw materials, manufacture, application and testing of coatings; as a handbook, however, its principal aim is to illustrate and to create connections. Naturally only the essential themes could be addressed within the stated limits of the book. It does not wish or claim to be complete; the authors felt that it was more important to explain the foundations and principles as clearly as possible. For this reason also, the book does not contain all of the material taught to budding coating engineers at Krefeld; this would far exceed the scope of a single-volume handbook.
This work is intended to fill a gap in the current specialist literature: as an accompanying handbook it is intended on the one hand to provide a trainee or student with the basic knowledge to form a solid foundation for a closer study of coating technology; on the other hand it is designed to help people from other disciplines – scientists, engineers, business people – to find out more about this subject which, in its fascinating diversity, is difficult to assimilate. Experienced coating specialists may use it to refresh or to extend their knowledge. It may also enable them to take a glance over the “garden fence” into neighbouring disciplines, into the raw materials used every day or into the application and usage of coating materials.
The authors hope that also the second edition of the book will meet the expectations of the reader and stimulate him (or her) to take it out of the shelves very often.
No book is ever perfect. – There will certainly be specialists amongst our readers who can offer changes or improvements to particular topics; the authors will be grateful for any constructive suggestions!
Krefeld, August 2009
Peter Mischke, Michael Groteklaes and Thomas Brock
Brock, Groteklaes, Mischke: European Coatings Handbook
© Copyright 2010 by Vincentz Network, Hannover, Germany
ISBN 978-3-86630-889-3
Contents
1 Introduction
1.1 Historical perspective
1.2 The economic importance of paints and coatings
1.3 Classification and material structure of coatings
1.4 Technology of paints and coatings
2 Raw materials for coatings
2.1 Film formers
2.1.1 General polymer science
2.1.1.1 Basic concepts
2.1.1.2 Degree of polymerisation, molecular weight, molecular weight distribution
2.1.1.3 Secondary and aggregate structures of polymers
2.1.1.4 Crosslinked polymers
2.1.1.5 General information about polymer solutions
2.1.1.6 Solubility and solubility parameters
2.1.1.7 Incompatilities
2.1.1.8 Viscosity of polymer solutions
2.1.1.9 Acqueous systems
2.1.1.10 Mechanical behaviour of polymers – viscoelasticity
2.1.1.11 Measuring viscoelasticity
2.1.1.12 Temperature dependency of polymer behaviour, glass transition temperature
2.1.2 Natural film formers
2.1.3 Modified natural substances
2.1.4 Synthetic film formers
2.2 Solvents
2.2.1 Classification and definitions
2.2.2 Characterisation of solvents
2.2.2.1 Hydrogen bridge linkage parameter
2.2.2.2 Solvents with weak hydrogen bridge linkage
2.2.2.3 Solvents with moderately strong hydrogen bridge linkage
2.2.2.4 Solvents with strong hydrogen bridge linkage
2.2.3 Properties
2.2.3.1 Volatility
2.2.3.2 Polarity
2.2.3.3 Surface tension
2.2.3.4 Density
2.2.3.5 Viscosity
2.2.3.6 Other physical properties
2.2.3.7 Physiological properties
2.2.4 Solvents in coating materials
2.2.4.1 Influences of solvents on the properties of coatings and coating systems
2.2.4.2 Solvents in low solid and medium solid coatings
2.2.4.3 Solvents in high solid coatings
2.2.4.4 Solvents in water-borne coatings
2.3 Pigments and fillers
2.3.1 Definitions and classification of pigments
2.3.2 Physical principles
2.3.2.1 Pigment morphology
2.3.2.2 Appearance of pigments
2.3.2.3 Interactions between pigment and surrounding medium
2.3.3 White pigments
2.3.3.1 Titanium dioxide pigments
2.3.3.2 Other white pigments
2.3.4 Black pigments
2.3.4.1 Classification
2.3.4.2 Pigment blacks
2.3.5 Inorganic coloured pigments
2.3.5.1 General properties
2.3.5.2 Oxide and oxide-hydroxide pigments
2.3.5.3 Cadmium pigments
2.3.5.4 Chromate pigments
2.3.5.5 Bismuth vanadate pigments
2.3.5.6 Iron-blue pigments
2.3.5.7 Ultramarine pigments
2.3.6 Organic coloured pigments
2.3.6.1 General properties
2.3.6.2 Classification of organic pigments
2.3.6.3 Optical properties of organic pigments
2.3.6.4 Fields of application for organic pigments
2.3.7 Lustre pigments
2.3.7.1 Metallic pigments
2.3.7.2 Pearlescent and iridescent pigments
2.3.7.3 Incorporating special effect pigments into coatings
2.3.7.4 Formation of the special effect
2.3.8 Functional pigments
2.3.8.1 Anti-corrosive pigments
2.3.8.2 Conductive pigments
2.3.9 Fillers
2.3.9.1 Definition and classification of fillers
2.3.9.2 Manufacture of fillers
2.3.9.3 Some commonly used fillers
2.3.9.4 Nanoparticles
2.3.10 Dyes
2.4 Additives
2.4.1 Classification and definition
2.4.2 Interface-active additives
2.4.2.1 Defoaming and deaerating agents
2.4.2.2 Surface-active additives
2.4.3 Rheological additives
2.4.3.1 General introduction
2.4.3.2 Thickeners
2.4.3.3 Thixotropic agents
2.4.4 Light stabilisers
2.4.5 Biocides
2.4.6 Wetting and dispersing agents
2.4.7 Catalysts and driers
2.4.8 Flatting agents
3 Coating systems, formulation, film-forming
3.1 Composition of coating materials
3.2 Basic formulating parameters
3.3 Pigment volume concentration and film properties
3.4 Solvent-based coating materials
3.4.1 Low solid and medium solid systems
3.4.2 High solid systems
3.5 Aqueous coating materials
3.5.1 Water-soluble and emulsifiable systems
3.5.2 Emulsion paints
3.6 Radically-curing coating materials
3.7 Powder coatings
3.7.1 Film formers
3.7.2 Additives
3.7.3 Pigments
3.8 Inorganic coating materials
3.8.1 Water glass paints
3.8.2 Alkyl silicate paints
3.9 Formulating the mill base
3.9.1 General introduction
3.9.2 High solid systems
3.9.3 Aqueous systems
3.10 Film-forming
3.10.1 General introduction
3.10.2 Physically drying
3.10.2.1 Drying of dis solved binders
3.10.2.2 Drying of primary dispersions
3.10.2.3 Drying of polyurethane dispersions
3.10.3 Curing of liquid coating materials
3.10.3.1 General principles
3.10.3.2 High solids
3.10.3.3 Crosslinking of waterborne film formers
3.10.3.4 Radiation curing
3.10.4 Curing of powder coatings
4 Manufacture of paints and coatings
4.1 Preliminary comment
4.2 General introduction to the manufacture of paints and coatings – layout of a coating
4.3 Process stages in the manufacture of coatings
4.4 Production “from scratch” and from pastes – formulation example
4.5 Configuration of equipment for the manufacture of coatings
4.6 Manufacture of powder coatings
4.7 Further information about mixing and dissolving
4.8 Kneading
4.9 Dispersion, dispersing units
4.9.1 General introduction to dispersion
4.9.2 Stress mechanisms during dispersion
4.9.3 Dispersion using dissolvers
4.9.4 Dispersion using triple roll mills
4.9.5 Dispersion using attrition mills
4.9.5.1 Dispersion mechanism in the presence of grinding media
4.9.5.2 Design and operating parameters for attrition mills
4.9.5.3 Residence time distribution in an attrition mill
4.9.5.4 Continuous and circulating processes
4.9.6 Dispersion in the extruder in the manufacture of powder coatings
4.10 Filtration
4.11 Further information about the manufacture of water-borne paints and coatings
5 Substrates and pretreatment
5.1 General introduction
5.2 Principles of adhesion
5.3 Metal substrates
5.3.1 Metals and their surfaces
5.3.2 The most important metal substrates
5.3.2.1 Steel
5.3.2.2 Zinc, galvanised steel
5.3.2.3 Aluminium
5.3.2.4 Other metal materials
5.3.3 Removal of adherent coatings
5.3.3.1 Mechanical processes, abrasive blasting
5.3.3.2 Flame cleaning
5.3.3.3 Pickling
5.3.4 Cleaning, degreasing
5.3.5. Application of conversion coatings
5.3.6 Manual preparation of metal substrates
5.4 Plastic substrates
5.4.1 Plastics, plastic surfaces and their coatability
5.4.2 Pretreatment of plastics
5.5 Wood and wood products as substrates
5.5.1 Wood
5.5.2 Wood products
5.5.3 Pretreatment of wood and wood products
5.5.3.1 Facing and smoothing
5.5.3.2 Notes on the protection of wood
5.6 Mineral substrates
5.6.1 Composition and properties
5.6.2 Pretreatment of mineral substrates
6 Application and drying
6.1 Methods of application and criteria for use
6.2 Manual application by brushing, rolling, trowelling, wiping
6.3 Curtain coating
6.4 Roller coating
6.5 Dipping, flow coating and related processes
6.6 Electrodeposition coating
6.6.1 Principles of electrochemistry
6.6.2 Plant engineering and bath control
6.6.3 Developmental trends and fields of application
6.7 Spray application processes
6.7.1 Atomisation methods without electrostatic charging
6.7.1.1 Pneumatic atomisation
6.7.1.2 Hydraulic (airless) atomisation
6.7.1.3 Recent process variants
6.7.2 Electrostatic atomisation
6.7.3 Rapid-rotation atomisation
6.7.4 Film-forming after spray application
6.7.5 Two-component plant engineering for spray application
6.7.6 Range of applications
6.8 Powder coating
6.8.1 Powder sintering processes
6.8.2 Electrostatic processes
6.9 Spray techniques
6.9.1 Booth ventilation techniques
6.9.2 Waste air purification
6.9.3 Supply systems
6.9.4 Automated coating processes
6.9.5 Conveyor systems
6.10 Drying installations
6.10.1 Stoving conditions
6.10.2 Overview of drying processes
6.10.3 Circulating air (convection) drying processes
6.10.4 Infra-red drying
6.10.5 Radiation curing
7 Painting and coating processes
7.1 Paints and coatings: market and fields of application
7.2 Automotive assembly line coating
7.3 Automotive refinishing coatings
7.4 Industrial plastics coating systems
7.5 Painting of rail vehicles
7.6 Coil coating
7.7 Electrical insulation systems
7.8 Other metal coating systems
7.9 Coating of wood and wood-based materials
7.10 Building protection / coating of mineral substrates
7.11 Separating, preparing and recycling paint and coating residues
7.12 Removal of coatings
7.13 Quality management, process safety and quality assurance
8 Test methods and measuring techniques
8.1 Rheology and rheometry
8.1.1 Rheological principles
8.1.2 Practical relevance of viscosity behaviour
8.1.3 Measuring flow behaviour
8.1.4 Viscoelasticity
8.2 Characteristics of solvents and liquid products
8.2.1 Composition and purity of liquids
8.2.2 Safety data
8.2.3 Application-related data
8.3 Analytical values for solids
8.4 Testing of liquid paints and coatings
8.4.1 Optical properties
8.4.2 Emissions
8.4.3 Film-forming, flow and crosslinking
8.4.4 Ring circuit stability
8.5 Specific tests for powder coatings
8.6 Features of coatings after application
8.6.1 Film thickness measurement
8.6.2 Optical film properties, colour and colorimetry
8.6.3 Mechanical engineering film properties
8.6.4 Light stability and weather resistance
8.7 Damage to coatings and coating systems
9 Environmental protection and safety at work
9.1 Air pollution control
9.2 Water pollution control
9.3 Waste legislation and waste management
9.4 Safe handling of paints and coatings
9.5 Transportation
9.6 REACH
9.7 Eco-audits: information and limits
Authors biographies
Index
Appendix: nomenclature
1Introduction
1.1Historical perspective
The earliest known use of paint dates back around 30,000 years. People used mixtures of coloured earth, soot, grease and other natural substances to ornament their bodies and to decorate their homes and places of worship, one such example being the cave paintings discovered in southern France and northern Spain.
In ancient times …
The advanced civilisations of the Egyptians (from 4000 years BC), Greeks and Romans used sophisticated painting techniques to decorate or to identify vessels, statues, tools and buildings. Raw materials included vegetable gums, starches, hide glue, milk (products), beeswax, charcoal and various minerals. Natural dyes such as indigo, purple and madder were used to dye textiles, fibres, wood, paper and leather.
In contrast to the decorative or colour-giving use of paints described so far, the art of lacquerwork was developed in China from around 2000 years before Christ, to produce smooth and glossy surfaces. The lacquers were based on the sap of the Chinese rhus tree and, in addition to their decorative effect, they also had a protective function. Raw materials such as balsams and resins, vermilion and ultramarine, came predominantly from India. The word “lacquer” itself stems from the term “Laksha”, from the pre-Christian, sacred Indian language Sanskrit, and originally referred to shellac, a resin produced by special insects (“lac insects”) from the sap of an Indian fig tree.
Seafaring brought with it another important area of application for coatings. The fourth century before Christ saw a wave of migration spreading from Asia Minor as far as England and Scandinavia – some of it by land and some by sea. The wooden ships that carried the migrants were made watertight with mixtures of non-drying (non-curing) oils and tree resins or rock asphalt.
Leaping further forward in time, around the year AD 1100 the German goldsmith and monk Roger von Helmarshausen (Theophilus) described the manufacture of a coating by boiling linseed oil with molten amber. This process, known as paint boiling, continued to develop and by the 17th century there were numerous recipes for coatings made from a variety of natural resins, linseed oil and spirit.
In modern times ...
In the 18th century the Industrial Revolution brought about a dramatic rise in the demand for paints and coatings. In particular, the increasing numbers of goods and buildings produced from rust-prone iron needed to be treated to protect them against weathering. Furthermore, countries with a strong seafaring economy required large quantities of marine paints. The first paint factories, which appeared in England in 1790, grew out of the larger paint workshops. They were followed by factories in Holland and later in Germany and other countries.
With the exception of a few synthetic pigments already produced on an industrial scale (Berlin blue, cobalt blue, mineral green, chromium yellow), the raw materials for coatings were all of natural origin even in the 19th century. A distinction was made between “volatile paints”, “varnishes” and “long-oil paints”. This last group were manufactured by boiling resins with drying oils in “brewing kettles”, adding pigments if required. The addition of pigments became increasingly mechanised – first using cone mills then, from the early 20th century, cylinder mills. One weak point of these products was their extended drying time; it could take several weeks to paint an entire coach or car.
Brock, Groteklaes, Mischke: European Coatings Handbook
© Copyright 2010 by Vincentz Network, Hannover, Germany
ISBN 978-3-86630-889-3
In the 20th century ...
Huge innovations took place after the turn of the century. In terms of coating technology, the following advances were particularly important:
•the development of synthetic polymer chemistry
•the invention of the production line by Henry Ford (1913) and the mass production of cars arising from it.
In response to the demand for faster coating technologies, the spraying of coatings based on cellulose nitrate (nitrocellulose) was introduced.
In 1907 the first entirely synthetic resins, phenol-formaldehyde condensates (“Bakelite”) were launched on the market. These were followed in rapid succession by vinyl resins, urea resins and, from the 1930s onwards, alkyd resins, acrylic resins, polyurethanes and melamine resins. Epoxy resins were introduced in the late 1940s. Titanium dioxide established itself as the leading white pigment when it went into mass production in 1919.
These developments in coating chemistry were paralleled (finally) by advances in coating technology. The various methods of brush application and spraying were supplemented by electrodeposition, electrostatic coating and powder coating techniques. Ambient air drying was joined by infrared and radiation drying methods (UV, electron beam), and the automation of coating processes continued to advance. It is also worth mentioning environmental technologies for the control of air and water pollution and for waste reduction.
Measuring techniques for coatings can be regarded as the pillar supporting modern coating technology. The reproducible quantifiability of flow properties, optical characteristics, drying behaviour, adhesion, anti-corrosion action and many other properties of coating materials and/or coatings is the precondition for selective product development and the practical usage of products. Many companies now sell instruments for performing the various measuring techniques – most of them governed by standards – for coatings and related products.
At the start of the 21st century, there do not appear to have been any clear-cut revolutionary innovations in the coatings sector, but rather a great many individual developments have been aimed at improving and attaining highly specific functional properties and effects. The primary development goal of the last two decades, namely enhanced environmental compatibility of products, now seems to be taking a backseat (see section 1.2), aside from a general tendency to substitute renewable materials for mineral-oil-based products, wherever possible, in the long term.
To recap and to summarise, we can see that:
The production and use of paints and coatings has developed from a prehistoric art form via an empirical craft into the multi-disciplinary, highly complex coating technology of today.
1.2The economic importance of paints and coatings
The coatings industry is a medium-sized sector, albeit with a growing tendency towards internationalisation. In 2005 some 250 paint factories in Germany employed around 20,500 people. In 2007 they produced over 2.4 million tonnes of coatings, paints and thinners, with an overall worth of approximately 5 thousand million euro. In terms of value this equates to about 1 % of Germany’s commodities production. The tonnage produced is the equivalent of 4000 fully laden trains.
The economic benefit of these products only becomes clear if we look at their applications. The overwhelming majority of coatings and paints have, in addition to their optical or aesthetic function, a protective and hence value-retaining function. 2.0 million tonnes of paint could cover and therefore protect against corrosion, weathering and/or mechanical damage an area of around 3,000 km2 (roughly the size of Oxfordshire) with a 200 μm thick (dry) coat.
The overall quantity of coatings produced covers a vast range of product types:
•emulsion paints and renderings:
•solvent-based coatings:
•powder coatings:
•electrodeposition coatings and water-thinnable industrial coatings
•other miscellaneous coatings:
approx. 45 %
approx. 21 %
approx. 3 %
approx. 2 %
approx. 29 %
Figure 1.1: Evolution in production of environmentally friendly coatings 1995–2006 in Germany. (source “besser lackieren!” Jahrbuch 2008, Vincentz Network 2007)
In the breakdown above, the proportion of powder coatings seems too low, since one part by weight of powder coating is equivalent to two to three parts of wet paint.
We will end with a look at the three environmentally friendly coating classes: water-based coatings, powder coatings and high solid coatings (see Figure 1.1). Annual production of high solid coatings and especially powder coatings increased steadily during the 1990s, whereas water-based volumes stagnated. The current overall trend is negative, with production of water-based coatings seemingly having collapsed altogether. In view of manufacturers’ efforts to be able to supply water-based products, this observation comes somewhat as a surprise. It would also appear that more and more attention has been paid since 2000 to coating properties, such as new optical and haptic effects, enhanced scratch resistance and easy-to-clean properties, all grouped together under the fashionable term “performance”, frequently in combination with the buzzword “nanotechnology”. For the sake of completeness we should add that there are other low-solvent or solvent-free products, e.g. radiation-curing coatings, solvent-free two-component systems and paint-like emulsion coatings.
1.3Classification and material structure of coatings
The title of EN ISO 4618 is “Paints and varnishes – Terms and definitions”. In Germany, this standard has been supplemented by DIN 55945 (2007-03) “Paints and varnishes – Additional terms and definitions to EN ISO 4618”.
A paint is defined in the standard as a product in liquid or paste form that is applied primarily by brushing, rolling or spraying.
A product based on organic binders (modified natural substances, synthetic resins), which when applied to a substrate produces a cohesive, virtually water-impermeable (non-absorbent), protective and possibly decorative film, is called a coating material. The coating itself is properly termed a coating system; it comprises the coating film.
Products not covered by this definition include (polymer) emulsion paints, silicon emulsion paints and distempers. Printing inks are naturally also excluded.
A coating powder is a powder coating which produces a film after it has been applied to and fused onto the substrate. (Since coating powders are not in liquid or paste form, they do not by definition belong to the category of paints). The term “paint” in the trade sense refers to a pigmented coating (“paint”) or alternatively to a pigmented varnish (“gloss paint”).
Coating material
non-volatile matter
volatile matter
pigments
fillers
film-formers
non-volatile additives
solvents or dispersants
volatile additives
(any elimination products from stoving)
Other materials covered by the standard include fillers, synthetic resin renderings and floor coating compounds.
All coating materials are based on the structure shown in the table below. Not every coating material necessarily contains all the components listed. (A clear varnish does not contain any pigments or fillers, whilst a powder coating contains no solvents).
Pigments
Very finely dispersed colouring and/or corrosion-inhibiting powder that is practically insoluble in the application medium.
Examples include titanium dioxide, carbon black, pearlescent pigments, zinc phosphate.
Fillers
Powders that are practically insoluble in the application medium and which impart or improve particular technological properties and give the coating material greater volume (body).
Examples include chalk, talcum, cellulose fibres.
Film formers
Macromolecular or macromolecule-forming substances responsible for film formation.
Examples include chlorine rubber, alkyd resin, polyester/polyisocyanate blends (two-component systems), polyester acrylate (radiation-curable).
Additives
Substances that are generally added in small quantities and which have particular chemical or technological effects.
Examples include hardening accelerators (catalysts), thickeners, dispersants, flow control agents, flatting agents, preservatives.
Solvents
Liquids or blends of liquids that are able to dissolve the film former(s).
Examples include butyl acetate, butyl glycol, white spirit, water.
Also known as thinning agents or thinners when used to adjust processing characteristics (viscosity).
Dispersants
Liquids that do not dissolve the film former(s) but instead hold them in a fine, microheterogeneous dispersion (or emulsion).
Examples include water and, in non-aqueous dispersions, hydrocarbons.
One further term, which is frequently used incorrectly, is “binder”. According to the standards, the binder is the non-volatile part of the coating material, excluding pigments and fillers but including non-volatile additives such as plasticisers and driers. In common usage, however, binder is frequently used to mean film former.
1.4Technology of paints and coatings (“Coating technology”)
In broad terms the whole teaching of coatings (and paints) – as is the case in this book – can be regarded as “coating technology”. In more precise terms, however, coating technology – as opposed to coating chemistry – refers to the process technology of the manufacture and processing of coatings and paints, where processing can be subdivided into the processes of application (spraying, dipping, brushing, etc.) and of drying or curing (air drying, stoving, radiation curing).
A typical problem in coating technology, which is representative of many others, is the balance in a coating between spreading and dripping. After a coating has been applied it should normally form a uniform surface. In order to achieve this, any irregularities arising from its application, such as brush strokes, build-up of droplets from spraying or roller marks, should even out naturally if the coating is still sufficiently flowable, i.e. not too dry. On the other hand, however, the flowable coating must not drip when applied to vertical surfaces, since this would lead to “running”, “sagging” and other unattractive forms of curtaining. We can see that two conflicting properties are expected of the coating, and these can only be balanced by means of skilful formulation and adjustment of application conditions.
The following parameters are specifically involved in this problem:
•roughness of the substrate
•form and degree of the initial unevenness of the wet film
•evaporation behaviour of the solvent or solvent blend
•change in viscosity during evaporation
•rheological behaviour (Newtonian, pseudoplastic, thixotropic)
•surface tension (size and uniformity)
•slope of the surface in question.
This example not only illustrates the complexity of coating technology but also shows that the development of coatings and paints requires the properties of the material to be precisely adjusted to the particular technological conditions existing in individual coating workshops.
Sources and references for Chapter 1
[1]G. Benzing et al.: Pigmente und Farbstoffe für die Lackindustrie. 2nd edn., Expert-Verlag, Ehningen 1992
[2]H. Biegel: Industrielacke (Die Bibliothek der Technik, vol. 39). Verlag moderne Industrie, Landsberg/Lech 1990
[3]Brockhaus Enzyklopädie, vol. 22, 19th edn., F. A. Brockhaus GmbH, Mannheim 1993
[4]www.colour-europe.de/textMenue_II_VDL-Statistik.html (August 2008)
[5]www.colouring.de/Lackindustrie/... (August 2008)
[6]www.destatis.de/... (Statistisches Bundesamt, August 2008)
[7]DIN 55945 (2007-03)
[8]EN ISO 4618 (2007)
[9]H. Kittel (Ed.): Lehrbuch der Lacke und Beschichtungen. Vol. 1/Part 1, Verlag W. A. Colomb, Stuttgart - Berlin 1971
[10]D. Ondratschek (Ed.): besser Lackieren! Jahrbuch 2008. Vincentz Network, Hanover 2007
2 Raw materials for coatings
2.1 Film formers
Film formers, which are frequently also referred to imprecisely as binders (→ 1.3), are polymers or oligomers (prepolymers) that are generally organo-chemical in nature and which polymerise as the coating cures. The role of the film former is to form a cohesive coating or paint film on a given substrate and – where relevant – to hold together or to embed the other non-volatile components of the coating, particularly the pigments and fillers. The film former thus constitutes the basis for the coating material in question.
Depending on their origin, film formers can be categorised into
• natural substances
• modified natural substances
• synthetic substances.
The importance of the product types increases through the above sequence. Unmodified natural substances are used in very few coatings now and never as the sole film former. With the exception of “bio-coatings” or “natural coatings”, natural film formers are now used primarily in certain printing inks. Before exploring the chemistry and properties of individual film formers, it is important to establish a grounding in polymer science, which is covered in the section below.
2.1.1 General polymer science
2.1.1.1 Basic concepts
The following section introduces the basic concepts of polymer chemistry that are relevant to the field of coating film formers.
A monomer
is a substance consisting of small, reactive molecules that can be converted to a polymer through what is known as a polymerisation reaction (see below).
Examples:
Brock, Groteklaes, Mischke: European Coatings Handbook
© Copyright 2010 by Vincentz Network, Hannover, Germany
ISBN 978-3-86630-889-3
A polymer (macromolecular substance)
is a substance consisting of (very) long molecules (polymer or macromolecules) or extended molecule networks. Individual polymer molecules may have a molecular weight ranging from a few thousand to several million g/mol.
Examples:
A relatively low-molecular polymer, up to a molecular weight of around 2000 g/mol, is classed as an oligomer.
Polymerisation is a chemical reaction in which one or more (different) monomers are converted into a polymer.
There are three basic types of polymerisation reactions, as briefly described below.
• Addition polymerisation as a chain reaction
A polymer molecule is produced after a starting reaction, typically within a maximum of a few seconds, through the chemical bonding of numerous monomer molecules with no separation of by-products. This process can be formulated as shown below in relation to a radical polymerisation:
In chemical kinetics terms, this is a chain reaction in that one propagation step inexorably draws the next immediately after it.
Acrylic resins and polymer dispersions are examples of polymerisation products.
• Condensation polymerisation
The monomer molecules react relatively slowly in discrete, mutually independent propagation steps to form the polymer, causing small molecules (mainly water) to be separated. The macromolecules are formed successively over a long period of time, generally several hours.
Schematic reaction equation (for bifunctional monomers):
The synthesis of a polyester (see above) or a melamine resin proceeds as a condensation polymerisation with separation of water.
• Addition polymerisation as a stepwise reaction
The reaction proceeds in approximately the same way as a condensation polymerisation, but with no separation of molecules. Schematic reaction equation (for bifunctional monomers):
The crosslinking of an epoxy resin with an amine (see above) and the formation of a polyurethane from a polyol and a polyisocyanate are examples of stepwise addition polymerisation reactions.
The products of polymerisation reactions are known as polymers, polycondensates or polyadducts, according to the reaction type.
Monomer unit or basic unit is the name given to a section of a polymer molecule produced from a monomer molecule. (The monomer changes on transition into the polymer).
The term structural element (structural unit, constitutional repeating unit) refers to the smallest possible chain section of a polymer molecule; when arranged in series – up to the end groups – these constitute the complete polymer molecule. Only simple polymer molecules with very regular structures, such as homopolymers (see below), contain a structural element. Most synthetic coating film formers are random copolymers (see below) and therefore by definition do not have any structural elements.
Examples:
Linear, branched, crosslinked polymers
As Figure 2.1 illustrates, linear polymers consist exclusively of chain-like, unbranched molecules. Branched polymers consist of branched molecular chains; where possible, one should distinguish between the main chain and side chains. Crosslinked polymers consist of three-dimensional molecular networks. The average mesh width of the network can also be expressed by the term crosslink density (→ 2.1.1.4).
According to these structures, polymers can be divided into the following three types:
Figure 2.1: Linear, branched and crosslinked molecules/polymers
• Thermoplasts
These are linear or branched, soften at elevated temperatures, and are soluble in suitable solvents1)
• Elastomers
Loosely crosslinked2), rubbery-elastic (not plastic), insoluble in solvents, but readily swellable
• Thermosets
These are closely crosslinked, scarcely softening at elevated temperatures, insoluble in solvents but slightly swellable
In the case of polymers of dienes, i.e. of molecules with two conjugated double bonds, a distinction must be made between cis- and trans-polymers and between 1,2- and 1,4-polymers as shown by way of example in the formulae below for 1,3-butadiene:
Homopolymers, copolymers
Polymerisation of a single monomer produces what is known as a homopolymer. When two or more monomers are involved, we refer to a copolymer. The term terpolymer is also used to refer to a polymer produced from three monomers. Depending on the sequence of the various monomer units in a copolymer, we can distinguish between a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer:
random copolymer
A B A B A B A B A B A B A B A B A B A
alternating copolymer
A A A A A B B B B B B B A A A A B B B
block copolymer
The structural features of polymer molecules described so far are grouped together under the collective term of primary structures. Secondary and aggregate structures develop because molecules form in various ways in a space and then congregate below one another.
2.1.1.2 Degree of polymerisation, molecular weight, molecular weight distribution
Only an average value can be given for the size of the molecules of an engineering polymer, since polymerisation reactions lead to a random distribution of molecule sizes. The following two dimensions are conventionally used:
• Average degree of polymerisation ():
Average number of monomer units (basic units) per polymer molecule
• Average molecular weight ():
Average molecular weight of a polymer molecule
These two quantities are linked by the molecular weight of the monomer unit (in the case of homopolymers) or the average molecular weight of a monomer unit Mmono (in the case of copolymers):
It is more usual to quote the average molecular weight than the average degree of polymerisation.
There are a number of differently defined average values for the molecular weight of a polymer. The two most important are explained below.
Number average:
where Ni is the number of molecules having molecular weight Mi and ΣNi is the total number of molecules in the quantity of polymer under consideration.
The number average – mathematically expressed – is the arithmetic mean of the molecular weight.
Weight average:
Since weight average considers not the number but the mass of the molecules, large molecules have a greater influence on the calculation of the average value than do the same number of small molecules. As a consequence, the weight average works out higher than the number average.
The greater the relative difference between the number average and the weight average (known as non-uniformity, U), the broader the molecular weight distribution.
Figure 2.2: Molecular weight distribution curves for a coating resin (schematic view, curves smoothed)
In practice, molecular weight distribution curves are not symmetrical but distorted, as shown diagrammatically in Figure 2.2. In polymerisation reactions in particular, the molecular weight distribution can frequently be extremely irregular, which is due to the fact that there is no temporal or spatial consistency in the reaction conditions for typical industrial polymerisations. As a consequence of this, the overall distribution is the product of an overlay of many narrower individual distributions.
Three methods are conventionally used in industry to determine average molecular weight:
• Viscometry
Viscometry utilises the relation between the molecular weight of a polymer and the viscosity of the solution in a suitable solvent; the viscosity average of the molecular weight is obtained (or other quantities such as the K-value).
• Vapour phase osmometry (vapour pressure osmometry)
This is a thermodynamic (microcalorimetric) method; it determines the number average of the molecular weight.
• Gel permeation chromatography (GPC)
GPC has established itself as the standard method. A sample of the polymer in dissolved form is allowed to migrate through a columnar gel bed of a swollen, microporous substance. The larger the molecules, the less frequently or less deeply they enter the pores and hence the more quickly they pass through the column. Various evaluation methods enable one to calculate the number average, the weight average or the molecular weight distribution.
2.1.1.3 Secondary and aggregate structures of polymers
Uncrosslinked polymer molecules, both in the undissolved state and in solution, generally take the form of coils extended to a greater or lesser degree (see Figure 2.3). The reason for this is firstly that the many atoms of a polymer chain linked together through single bonds can be twisted in virtually any direction in respect of one another, and secondly that the bonds are angled, i.e. they are not aligned with one another. In an extreme case a zigzag chain is theoretically possible, although the probability of all the bonds orienting themselves in the appropriate pattern by chance is virtually nil. (As a comparison, gas molecules like-wise fill an available space uniformly and do not voluntarily arrange themselves into a chain.)
Figure 2.3: Random coil of a linear polymer molecule (macromolecule) according to [3]
Where many such polymer coils occur together, they may either lie adjacent to one another whilst remaining largely separate (cell structure, see Figure 2.4 (a)), or they may interpenetrate with one another, forming a kind of molecular felt (network structure, see Figure 2.4 (b)). For coating films the latter is preferable because of its superior mechanical properties.
In addition to these random conditions, the intra- and intermolecular forces of attraction1) (van der Waals’ forces and hydrogen bridges) between polymer segments must be taken into account. A distinction is normally made between the following basic types of intermolecular interactions:
Figure 2.4: Aggregate structures of polymers
• Dispersion forces:
Weak; exist between all atoms and molecules (cause: temporary asymmetries in the charge distributions within the atoms or molecules).
• Polar forces:
Moderately strong; exist between polar bonds (permanent dipoles) or ions and polarisable bonds (induced dipoles).
• Hydrogen bridges:
Strong; form primarily between OH or NH bonds and free pairs of electrons of O or N atoms.
(The order of magnitude of normal chemical bonds (primary valency bonds) is ten times greater than that of hydrogen bridges).
The following general rule applies: the stronger the intermolecular forces of attraction, the stronger the mutual coherence between different polymer molecules through the layering of molecule segments. One of the mechanical effects of intermolecular interactions is increased tensile strength.
If in addition to their mutual attraction the molecules or segments are arranged in a regular structure, bundles or concentrations of molecule segments may be produced; the braid of molecules has something of the appearance of a heap of spaghetti (see Figure 2.4 (c)). These bundles can sometimes have a role to play in coating technology. They have a positive impact in polyurethane films, for example, where the stacked urethane groups are responsible for the material’s good abrasion resistance. A negative example is the poor solubility of polyesters containing too high a proportion of very symmetrical basic units (e.g. terephthalic acid).
The most extreme example of molecular bundling is where many molecule segments of different molecules form crystallites (small crystals of around 10 nm in size). The crystallites in turn arrange themselves into what are known as superstructures (textures). Figure 2.4 (d) shows in diagrammatic form the structure of a partially crystalline polymer with “fold crystallites” – regular bundles of folded chain segments. The appearance of partial crystallinity requires a very regular polymer structure (e.g. tacticity). It plays a major role in the plastics sector and has a certain importance in adhesives technology. In coating film formers, however, partial crystallinity is undesirable since:
• partially crystalline polymers are poorly soluble in coating solvents;
• partial crystallinity is accompanied by cloudiness (the crystallites have a different refractive index from the amorphous areas);
• the flow of coatings made from partially crystalline polymers would be impaired.
For these reasons we will not cover them in any further detail.
In the dissolved state, polymer molecules again occur as isolated or as varyingly interpenetrated coils. In this case, however, the molecular chains are surrounded by adhering solvent molecules, i.e. they are solvated.
2.1.1.4 Crosslinked polymers
In liquid or powdered coating materials, film formers occur as uncrosslinked, discrete molecules; this means that they are soluble or fusible. In finished, cured coating films polymers normally need to be crosslinked, since this is the only way to achieve the best mechanical and chemical properties. Chemically crosslinked structures can be obtained – in molecular terms – by a number of different routes, as briefly described below.
• First route: The film former originates in the form of linear polymers. In the chemical curing reaction the chains are crosslinked either directly or using short bridges. One example is the curing of unsaturated polyesters with styrene as reactive diluent and peroxide as initiator.
• Second route: The film former consists of highly branched polymer molecules. Continuous crosslinking is initiated by the formation of relatively few intermolecular chemical bonds. Example: the oxidative drying of alkyd resins.
• Third route: The film former consists of two low-molecular (oligomeric) components, which form a macromolecular crosslinked substance on curing. Example: the formation of polyurethane from low-molecular polyester polyol and polyisocyanate surface coating resin.
The most important general characteristic of crosslinked polymers is the crosslink density ν. This refers to the number of network chain segments – expressed in mol – per unit volume of the polymer, where a network chain segment is the chain unit stretching from one crosslink point to the next. Instead of crosslink density the average molecular weight c of a network chain segment can also be quoted. Both quantities are connected via the density ρ of the polymer:
nc: number of moles of network chain segments
The greater the crosslink density, the greater the hardness and the chemical (solvent) resistance of the polymer; its elasticity or flexibility is reduced, however.
Crosslink density should not be used when “degree of crosslinking” is meant. The latter is used variously to mean the gel content of the polymer, the degree of crosslinking conversion (curing conversion) and the crosslink density.
A crosslinked polymer can still contain molecules which are not bound to the network. This sol content (ws) can be extracted from the polymer sample with a suitable solvent. The non-soluble, bound fraction is called the gel content (wG). Naturally, both fractions must add up to 100 %.
Crosslinking in the narrow sense always involves the chemical joining together of individual molecules to form three-dimensional networks. However, in the extended sense, crosslinking can also be the outcome of the interaction of weaker, physical secondary bonding forces, i.e. Van der Waals forces and hydrogen bonds, as well as steric effects, called entanglements. These network bonds can generally be broken by high shearing forces or rapid shearing and/or heating. They play a major role in organic rheological additives (thickeners etc).
2.1.1.5 General information about polymer solutions
If a non-crystalline (“amorphous”) and uncrosslinked polymer, e.g. the film former in a physically drying coating (i.e. by evaporation of the solvent alone), is added to a solvent, the solvent molecules slowly diffuse into the substance and solvate (encapsulate) the polymer molecules. This causes the volume of the substance to increase and the mechanical strength of the polymer to decrease, since the intermolecular forces of attraction responsible for coherence are gradually replaced by the forces of attraction between the polymer chains and the solvent molecules. This process is known as swelling.
If the dissolving power of the solvent is strong enough, swelling continues until a polymer solution is obtained. The dissolution of a (non-crystalline) polymer thus proceeds smoothly as a continuous swelling with no distinct change of phase; there is no clear boundary between the “swollen” and “dissolved” states. Conversely, when a polymer solution is evaporated, the polymer is not precipitated as a solvent-free bottom product – like a salt, for example; instead there is a continuous transition to the solvent-free polymer.
One exception to this rule occurs when the dissolving power of a blend of a highly dissolving and a poorly dissolving solvent deteriorates in respect of the dissolved polymer – either through further addition of the “non-solvent” (also referred to as “extender”) or through the preferential evaporation of the “solvent”. Such an instance can lead to the precipitation or dissolution of the swollen polymer, i.e. to a discontinuous or multi-phase system. Such undesirable precipitation phenomena can occur in the film as the paint is drying, for example, if the solvent composition has not been correctly adjusted.
In a polymer solution the molecules occur as diffuse “gel coils” interpenetrated with solvent. The solvating part of the solvent adhering strongly to the polymer chain due to intermolecular forces of attraction is known as bonded solvent; the rest of the solvent in the solution is called free solvent. With high molecular weights the requirement for solvating (bonded) solvent can be considerable. Thus even a 5 % solution of polymethyl methacrylate with an average molecular weight w) of 500,000 g/mol in acetone still contains no free solvent. The gel coils can reach diameters of up to 100 nm.
For this reason polymer solutions represent a special category of colloid solutions, known as molecular colloids1). Technically speaking, however, true (molecularly disperse) polymer solutions are not considered to be colloids.
The distinction between free and bonded solvent is important in coating technology: bonded solvent evaporates from a coating film much more slowly than free solvent and is subject to the phenomenon known as solvent retention (retention in the film).
2.1.1.6 Solubility and solubility parameters
Attempts to predict the solubility of polymers (and other substances) in particular solvents on the basis of physico-chemical material properties have led to the term “solubility parameter”. We understand this to mean the following:
First of all we assume that a particular quantity of a substance – e.g. a solvent – is completely evaporated. In this process the amount of energy used is that necessary to separate completely all molecules from one another – in opposition to their intermolecular forces of attraction. This amount of energy is known as the cohesive energy Ec, which is the same as the evaporation energy ΔvU. If we divide this by the volume of the substance V, we obtain the cohesive energy density. The square root of the cohesive energy density is the solubility parameter δ as defined by Hildebrandt.
Table 2.1: Examples of the failure in the one-dimensional solubility parameter system
Table 2.2: Solubility parameters for selected solvents and polymers (in (J/cm3)1/2)
It is (theoretically) the case that two substances are homogeneously miscible if their solubility parameters are approximately the same (see more detailed explanation on page 31). For polymer solutions, the difference in solubility parameters above which complete solubility is no longer achieved is around 6 (J/cm3)1/2.
Three-dimensional system
Unfortunately the one-dimensional solubility parameter system described above can often lead to false predictions (see Table 2.1).
For this reason Hansen devised a refined three-dimensional version of the one-dimensional system. In this three-dimensional system there is one parameter for the dispersion forces (δD), one for the polar forces (δP) and one for the hydrogen bridges (δH), which are combined to make one overall parameter d using the following formula:
Table 2.2 shows the Hansen parameters for a number of selected solvents and polymers. From the parameter values given in the table we can see the following:
In the case of solvents, the values for the dispersion parameter vary very little; the diffuse π electron system for the aromatic toluene does have a rather higher value. As we would expect, the values for the polarity parameter increase from n-hexane up to water; ketones are higher than esters. The tendency to form hydrogen bridges is naturally lowest in the case of hydrocarbons, moderate in the case of the polar-aprotonic esters and ketones and highest in the case of the protonic alcohols and, particularly, water.
The parameter values for polymers (coating film formers) are less easy to interpret than those for solvents. Polarity, polarisability (displaceability of bonding electrons by adjacent dipolar molecules or ions) and proton donor effect (OH or NH bonds) are of key importance here too, however.
It is useful to consider the Hansen parameters as three and arranged vertically one above the other; according to the formula above, d is given by the vectorial sum of these three vectors (see Figure 2.5). The difference in the solubility parameters of two substances, e.g. of a solvent (S) and a polymer (P), is obtained according to the rules of vector algebra by the following equation:
Example:
Figure 2.5: Solubility parameters as vectors in the three-dimensional system according to Hansen
We can see that in this case the three-dimensional system, unlike its one-dimensional counterpart (see Table 2.1), delivers the correct prediction – “poorly soluble”.
Figure 2.6: Solubility parameter diagram for a melamine resin (third parameter δD kept constant)
Solubility parameter diagrams
Unfortunately, even the three-dimensional system does not always produce the correct predictions of solubility, however. This is particularly the case if a fixed, generally applicable difference in the values for the overall parameter is given for the soluble/insoluble boundary. In such a case, empirically determined solubility parameter diagrams are more reliable. A solubility parameter diagram for a polymer or coating film former is a simply cohesive region in the three-dimensional solubility parameter zone with the following characteristic: all solvents (or blends of solvents), whose solubility parameter triplet forms a point within the region will dissolve the polymer; all solvents whose parameter points lie outside the region will not dissolve the polymer. Figure 2.6 shows a two-dimensional version of a solubility parameter diagram.
Solvent blends, latent solvents
Determining the solubility parameters for solvent blends represents a particular problem. Even for binary blends there are no simple calculation formulae which at the same time offer physico-chemical accuracy. Simple mean calculations involving the volume content Ø of components A and B according to the following formulae
do at least allow rough predictions to be made in regard to the change in dissolving power of one solvent following the addition of a second in respect of a given polymer.
Figure 2.7: Solubility parameters δpand δH for polystyrene, n-heptane, acetone and η-heptane/acetone (δD not shown for clarity)
The three-dimensional solubility parameter system can be used to provide a simple explanation of the mode of action of a “latent solvent”, for example, as follows. Latent solvents for a particular polymer are solvents that do not dissolve the polymer by themselves but become a solvent on addition of a second solvent – which may even be a non-solvent. This is explained by the fact that too low a parameter value in the latent solvent, for example, is balanced out by too high a value in the activating component, so that the resulting parameter value moves close to the corresponding value for the polymer.
Example:
Structural influences
So far we have not considered the influences of molecule size and polymer structure on solubility. The following rules apply:
• As the molecular weight increases, the solubility and hence the swellability of polymers reduce.
• Branched polymers are generally more readily soluble than linear (unbranched) polymers of the same molecular weight.
• Crosslinked polymers are insoluble. They are capable of swelling, however, their swelling capacity being heavily dependent on the swelling agent used, crosslink density and temperature, and potentially leading to the formation of voluminous gels.
The reasons are as follows: the intermolecular forces of attraction and the number of entanglements between the chains rise as the chain length increases. Branching prevents the molecules or chain segments from lying adjacent to one another, and the linear chain sections of branched molecules are also shorter than unbranched molecules of the same molecular weight. Molecules linked together by crosslinks (chemical bonds) cannot be separated by solvents into discrete particles.
At the end of this section we should recall the familiar rule that “Like dissolves in like”, which derives its theoretical interpretation from the concept of solubility parameters. According to this rule:
Slightly polar film formers dissolve primarily in hydrocarbons and esters, moderately polar types dissolve in esters and ketones and highly polar-protic (OH-containing) types dissolve in similarly OH-containing alcohols and also in some cases in esters and ketones. The best solvents (“true solvents”) can to a certain degree, to be determined by experiment, be added to weaker solvents or even to non-solvents (“diluents”). (See section 2.1.1.9 for solubility in water).
2.1.1.7 Incompatibilities
By incompatibility of (dissolved) polymers we mean the phenomenon whereby two polymers that are completely dissolved in the same solvent, mutually precipitate to form two solvent-containing polymer phases when the solutions are combined. This precipitation is normally first recognised by a cloudiness.
The cause of the incompatibility may be even slight differences in molecular structure. For example, polystyrene is incompatible with poly-α-methyl styrene and polymethyl acrylate is incompatible with polyethyl acrylate.
Copolymers of the same monomers in somewhat different proportions may also be incompatible with each other. Apart from the molecular structure, the degree of incompatibility is also governed by the solvent, the molecular weight (the higher this is, the greater the incompatibility), the concentrations or proportion of the two polymers and the temperature.
Incompatibility between different film formers and potentially between other substances in coatings is generally undesirable and must be avoided by skilful formulation. A more practicable method at times of successfully incorporating various incompatible film formers into a coating is to “boil” them first, e.g. natural resins (colophony, copal) with drying oils, or phenolic resins with drying oils or epoxy resins. The incompatible components bond together chemically in such a way that their subsequent separation into two phases is prevented and at the same time their compatibility with other components of the coating is improved.
Incompatibilities between polymers are much more noticeable in the undissolved state than in solution, since here the polymer molecules are in direct contact with one another. This incompatibility can be utilised in the area of polymer materials, namely in the form of special block or graft copolymers and “interpenetrating networks” (IPN). The basic principle here is that the separation processes lead to submicroscopic areas (domains) with differing properties, which combine to give the overall behaviour of the material. Despite ongoing research, these multi-phase technologies are not yet widely used in the coatings sector, however.
2.1.1.8 Viscosity of polymer solutions
By the (dynamic) viscosity η – expressed in Pa·s (Pascal seconds) – of a flowable substance we mean its thickness (ropiness). It can be determined by the time in which a certain volume of liquid at a given pressure difference flows through a capillary of a particular length and diameter.
The following definitions are required to discuss the viscosity of polymer solutions:
• Relative viscosity
• Specific viscosity
• Reduced viscosity
• Intrinsic viscosity
Through infinite dilution according to the definition of [η], the distances between the polymer molecules in the solution become very large, with the result that the molecules do not influence one another.
The reduced viscosity is also commonly called the Staudinger function.
Intrinsic viscosity and Staudinger index mean the same as “limiting viscosity number”. The latter can be obtained directly from the relative viscosity, instead of from the reduced viscosity:
Material influences
The relation between molecular weight and intrinsic viscosity is described by the Staudinger-Mark-Houwink equation (abbreviated to SMH equation):
where kη and a are polymer-, solvent- and temperature-dependent constants and v is the viscosity average of the molecular weight.
The central quantity in the SMH equation is the viscosity v, the molecular weight. v can be described pragmatically as follows: v is a mean of the molecular weight formed precisely to satisfy the SMH equation. It can now be demonstrated that v lies between n and w, which means that the narrower the molecular weight distribution, the closer it moves to w (see more detailed explanation).
Although of great theoretical interest, the SMH equation is important only for determining the molecular weight by viscometry. If kη and a are known from calibration measurements, then [η] and hence v can be calculated by viscometry.
The SMH equation has no direct application in industrial binder solutions or coatings, since the film former concentrations here are high and the film formers are frequently of a relatively low molecularity (oligomeric), i.e. they are not really macromolecular substances. As an example of the dependence of solution viscosity on film former concentration, Figure 2.8 shows the dependence on concentration of the reduced viscosity of a high solids blend of film formers in various solvents. Up to a concentration of around 0.3 g/ml the Martin equation applies:
or, expressed as a logarithm:
If we plot 1π(ηsp/c) against c we obtain a straight line.
If in the Martin equation we substitute ηsp with η/η0 – 1, [η] with kη · Mva and solve for η, then
Figure 2.8: Dependence on concentration of the reduced viscosity of a blend of high solid alkyd resin and melamine resin (HMMM) in various solvents
Figure 2.9: Relation between solvent viscosity and temperature
A low solution viscosity for a given film former concentration is thus obtained if the inherent viscosity η0 of the solvent, the constants kη and KM and the viscosity average Mv are low.
With regard to the influence of the solvent or solvent blend on viscosity, experiments show that, in addition to inherent viscosity, solubility parameters are also influential. For the polar and hydrogen-bridging film former in the example (high solids alkyd resin/HMMM) this means that the greater the value for δρ and/or δH in the solvent, the lower the solution viscosity. This is because the formation of viscosity-raising molecule associations (skeleton structures) due to dipole-dipole attraction and hydrogen bridges is prevented by solvents of the specified type.
