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- Herausgeber: John Wiley & Sons
- Kategorie: Fachliteratur
- Sprache: Englisch
The definitive guide to organic coatings, thoroughly revised and updated--now with coverage of a range of topics not covered in previous editions Organic Coatings: Science and Technology, Fourth Edition offers unparalleled coverageof organic coatings technology and its many applications. Written by three leading industry experts (including a new, internationally-recognized coatings scientist) it presents a systematic survey of the field, revises and updates the material from the previous edition, and features new or additional treatment of such topics as superhydrophobic, ice-phobic, antimicrobial, and self-healing coatings; sustainability, artist paints, and exterior architectural primers. making it even more relevant and useful for scientists and engineers in the field, as well as for students in coatings courses. The book incorporates up-to-date coverage of recent developments in the field with detailed discussions of the principles underlying the technology and their applications in the development, production, and uses of organic coatings. All chapters in this new edition have been updated to assure consistency and to enable extensive cross-referencing. The material presented is also applicable to the related areas of printing inks and adhesives, as well as areas within the plastics industry. This new edition * Completely revises outdated chapters to ensure consistency and to enable extensive cross-referencing * Correlates the empirical technology of coatings with the underlying science throughout * Provides expert troubleshooting guidance for coatings scientists and technologists * Features hundreds of illustrative figures and extensive references to the literature * A new, internationally-recognized coatings scientist brings fresh perspective to the content. Providing a broad overview for beginners in the field of organic coatings and a handy reference for seasoned professionals, Organic Coatings: Science and Technology, Fourth Edition, gives you the information and answers you need, when you need them.
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Table of Contents
Cover
Title Page
Preface
Chapter 1: Introduction to Coatings
1.1 DEFINITIONS AND SCOPE
1.2 TYPES OF COATINGS
1.3 COMPOSITION OF COATINGS
1.4 COATING HISTORY
1.5 COMMERCIAL CONSIDERATIONS
REFERENCES
Chapter 2: Polymerization and Film Formation
2.1 POLYMERS
2.2 POLYMERIZATION
2.3 FILM FORMATION
GENERAL REFERENCES
REFERENCES
Chapter 3: Flow
3.1 SHEAR FLOW
3.2 TYPES OF SHEAR FLOW
3.3 DETERMINATION OF SHEAR VISCOSITY
3.4 SHEAR VISCOSITY OF RESIN SOLUTIONS
3.5 VISCOSITY OF LIQUIDS WITH DISPERSED PHASES
3.6 OTHER MODES OF FLOW
GENERAL REFERENCES
REFERENCES
Chapter 4: Mechanical Properties
4.1 INTRODUCTION
4.2 BASIC MECHANICAL PROPERTIES
4.3 FRACTURE MECHANICS
4.4 ABRASION, SCRATCH, AND MAR RESISTANCE
4.5 MEASUREMENT OF MECHANICAL PROPERTIES
4.6 TESTS OF COATINGS ON SUBSTRATES
GENERAL REFERENCES
REFERENCES
Chapter 5: Exterior Durability
5.1 PHOTOINITIATED OXIDATIVE DEGRADATION
5.2 PHOTOSTABILIZATION
5.3 DEGRADATION OF CHLORINATED RESINS
5.4 HYDROLYTIC DEGRADATION
5.5 OTHER MODES OF FAILURE ON EXTERIOR EXPOSURE
5.6 TESTING FOR EXTERIOR DURABILITY
5.7 SERVICE LIFE PREDICTION
GENERAL REFERENCES
REFERENCES
Chapter 6: Adhesion
6.1 MECHANISMS OF ADHESION
6.2 MECHANICAL STRESSES AND ADHESION
6.3 ADHESION TO METAL SURFACES
6.4 CHARACTERIZATION OF SURFACES
6.5 ORGANIC CHEMICAL TREATMENT OF SUBSTRATES TO ENHANCE ADHESION
6.6 COVALENT BONDING TO GLASS AND METAL SUBSTRATES
6.7 ADHESION TO PLASTICS AND TO COATINGS
6.8 TESTING FOR ADHESION
GENERAL REFERENCES
REFERENCES
Chapter 7: Corrosion Protection by Coatings
7.1 CORROSION BASICS
7.2 CORROSION OF UNCOATED STEEL
7.3 CORROSION PROTECTION OF METALS
7.4 CORROSION PROTECTION BY INTACT COATINGS
7.5 CORROSION PROTECTION BY NONINTACT FILMS
7.6 EVALUATION AND TESTING
GENERAL REFERENCES
REFERENCES
Chapter 8: Acrylic Resins
8.1 THERMOPLASTIC ACRYLIC RESINS
8.2 THERMOSETTING ACRYLIC RESINS
8.3 WATER‐REDUCIBLE THERMOSETTING ACRYLIC RESINS
REFERENCES
Chapter 9: Latexes
9.1 EMULSION POLYMERIZATION
9.2 ACRYLIC LATEXES
9.3 VINYL ESTER LATEXES
9.4 THERMOSETTING LATEXES
GENERAL REFERENCES
REFERENCES
Chapter 10: Polyester Resins
10.1 HYDROXY‐TERMINATED POLYESTER RESINS FOR CONVENTIONAL SOLIDS COATINGS
10.2 POLYESTER RESINS FOR HIGH SOLIDS COATINGS
10.3 CARBOXYLIC ACID‐TERMINATED POLYESTER RESINS
10.4 CARBAMATE‐FUNCTIONAL POLYESTER RESINS
10.5 WATER‐REDUCIBLE POLYESTER RESINS
10.6 POLYESTER RESINS FOR POWDER COATINGS
REFERENCES
Chapter 11: Amino Resins
11.1 SYNTHESIS OF MELAMINE–FORMALDEHYDE RESINS
11.2 TYPES OF MF RESINS
11.3 MF–POLYOL REACTIONS IN COATINGS
11.4 OTHER AMINO RESINS
REFERENCES
Chapter 12: Polyurethanes and Polyisocyanates
12.1 REACTIONS OF ISOCYANATES
12.2 KINETICS OF REACTIONS OF ISOCYANATES WITH ALCOHOLS
12.3 ISOCYANATES USED IN COATINGS
12.4 TWO‐PACKAGE (2K) SOLVENTBORNE URETHANE COATINGS
12.5 BLOCKED ISOCYANATES
12.6 MOISTURE‐CURABLE URETHANE COATINGS
12.7 WATERBORNE POLYURETHANE COATINGS
12.8 HYDROXY‐TERMINATED POLYURETHANES
REFERENCES
Chapter 13: Epoxy and Phenolic Resins
13.1 EPOXY RESINS
13.2 AMINE CROSS‐LINKED EPOXY RESINS
13.3 OTHER CROSS‐LINKING AGENTS FOR EPOXY RESINS
13.4 WATER‐REDUCIBLE EPOXY/ACRYLIC GRAFT COPOLYMERS: EPOXY/ACRYLIC HYBRIDS
13.5 EPOXY RESIN PHOSPHATE ESTERS
13.6 PHENOLIC RESINS
GENERAL REFERENCES
REFERENCES
Chapter 14: Drying Oils
14.1 COMPOSITIONS OF NATURAL OILS
14.2 AUTOXIDATION AND CROSS‐LINKING
14.3 SYNTHETIC AND MODIFIED DRYING OILS
GENERAL REFERENCES
REFERENCES
Chapter 15: Alkyd Resins
15.1 OXIDIZING ALKYDS
15.2 HIGH SOLIDS OXIDIZING ALKYDS
15.3 WATERBORNE OXIDIZING ALKYDS
15.4 NONOXIDIZING ALKYDS
15.5 SYNTHETIC PROCEDURES FOR ALKYD RESINS
15.6 MODIFIED ALKYDS
15.7 URALKYDS AND OTHER AUTOXIDIZABLE URETHANES
15.8 EPOXY ESTERS
GENERAL REFERENCES
REFERENCES
Chapter 16: Silicon Derivatives
16.1 SILICONES
16.2 REACTIVE SILANES
16.3 ORTHOSILICATES
GENERAL REFERENCES
REFERENCES
Chapter 17: Other Resins and Cross‐Linkers
17.1 HALOGENATED POLYMERS
17.2 CELLULOSE DERIVATIVES
17.3 UNSATURATED POLYESTER RESINS
17.4 (METH)ACRYLATED OLIGOMERS
17.5 2‐HYDROXYALKYLAMIDE CROSS‐LINKERS
17.6 ACETOACETATE CROSS‐LINKING SYSTEMS
17.7 POLYAZIRIDINE CROSS‐LINKERS
17.8 POLYCARBODIIMIDE CROSS‐LINKERS
17.9 POLYCARBONATES
17.10 NON‐ISOCYANATE TWO‐PACKAGE BINDERS
17.11 DIHYDRAZIDES
REFERENCES
Chapter 18: Solvents
18.1 SOLVENT COMPOSITION
18.2 SOLUBILITY
18.3 SOLVENT EVAPORATION RATES
18.4 VISCOSITY EFFECTS
18.5 FLAMMABILITY
18.6 OTHER PHYSICAL PROPERTIES
18.7 TOXIC HAZARDS
18.8 ATMOSPHERIC PHOTOCHEMICAL EFFECTS
18.9 REGULATION OF SOLVENT EMISSIONS FROM COATINGS
GENERAL REFERENCES
REFERENCES
Chapter 19: Color and Appearance
19.1 LIGHT
19.2 LIGHT–OBJECT INTERACTIONS
19.3 HIDING
19.4 METALLIC AND INTERFERENCE COLORS
19.5 THE OBSERVER
19.6 INTERACTIONS OF LIGHT SOURCE, OBJECT, AND OBSERVER
19.7 COLOR SYSTEMS
19.8 COLOR MIXING
19.9 COLOR MATCHING
19.10 GLOSS
GENERAL REFERENCES
REFERENCES
Chapter 20: Pigments
20.1 WHITE PIGMENTS
20.2 COLOR PIGMENTS
20.3 INERT PIGMENTS
20.4 FUNCTIONAL PIGMENTS
20.5 NANO‐PIGMENTS
GENERAL REFERENCES
REFERENCES
Chapter 21: Pigment Dispersion
21.1 DISPERSION IN ORGANIC MEDIA
21.2 FORMULATION OF NONAQUEOUS MILL BASES
21.3 DISPERSION IN AQUEOUS MEDIA
21.4 DISPERSION EQUIPMENT AND PROCESSES
21.5 EVALUATION OF DISPERSIONS
GENERAL REFERENCES
REFERENCES
Chapter 22: Effect of Pigments on Coating Properties
22.1 PVC AND CPVC
22.2 RELATIONSHIPS BETWEEN FILM PROPERTIES AND PVC
REFERENCES
Chapter 23: Application Methods
23.1 BRUSHES, PADS, AND HAND ROLLERS
23.2 SPRAY APPLICATION
23.3 DIP AND FLOW COATING
23.4 ROLL COATING
23.5 CURTAIN COATING
GENERAL REFERENCES
REFERENCES
Chapter 24: Film Defects
24.1 SURFACE TENSION
24.2 LEVELING
24.3 SAGGING AND DRIP MARKS
24.4 CRAWLING, CRATERING, AND RELATED DEFECTS
24.5 FLOATING AND FLOODING: HAMMER FINISHES
24.6 WRINKLING: WRINKLE FINISHES
24.7 BUBBLING AND POPPING
24.8 FOAMING
24.9 DIRT
GENERAL REFERENCES
REFERENCES
Chapter 25: Solventborne and High Solids Coatings
25.1 PRIMERS
25.2 TOP COATS
GENERAL REFERENCES
REFERENCES
Chapter 26: Waterborne Coatings
26.1 WATER‐REDUCIBLE COATINGS
26.2 LATEX‐BASED COATINGS
26.3 EMULSION COATINGS
GENERAL REFERENCES
REFERENCES
Chapter 27: Electrodeposition Coatings
27.1 ANIONIC ELECTRODEPOSITION COATINGS
27.2 CATIONIC ELECTRODEPOSITION COATINGS
27.3 EFFECT OF VARIABLES ON ELECTRODEPOSITION
27.4 APPLICATION OF ELECTRODEPOSITION COATINGS
27.5 ADVANTAGES AND DISADVANTAGES OF ELECTRODEPOSITION
27.6 AUTODEPOSITION COATINGS
GENERAL REFERENCE
REFERENCES
Chapter 28: Powder Coatings
28.1 BINDERS FOR THERMOSETTING POWDER COATINGS
28.2 BINDERS FOR THERMOPLASTIC POWDER COATINGS
28.3 FORMULATION OF THERMOSETTING POWDER COATINGS
28.4 MANUFACTURE OF POWDER COATINGS
28.5 APPLICATION METHODS
28.6 ADVANTAGES AND LIMITATIONS
GENERAL REFERENCES
REFERENCES
Chapter 29: Radiation Cure Coatings
29.1 UV CURING
29.2 FREE RADICAL‐INITIATED UV CURE
29.3 CATIONIC UV CURE
29.4 HYBRID FREE RADICAL/CATIONIC POLYMERIZATION
29.5 EFFECTS OF PIGMENTATION
29.6 ELECTRON BEAM CURE COATINGS
29.7 DUAL UV/THERMAL CURE
29.8 SELECTED APPLICATIONS
29.9 ADVANTAGES, DISADVANTAGES, AND SELECTED ADVANCES
REFERENCES
Chapter 30: Product Coatings for Metal Substrates
30.1 OEM AUTOMOTIVE COATINGS
30.2 APPLIANCE COATINGS
30.3 CONTAINER COATINGS
30.4 COIL COATING
30.5 COATINGS FOR AIRCRAFT
GENERAL REFERENCES
REFERENCES
Chapter 31: Product Coatings for Nonmetallic Substrates
31.1 COATINGS FOR WOOD
31.2 COATING OF PLASTICS
GENERAL REFERENCES
REFERENCES
Chapter 32: Architectural Coatings
32.1 EXTERIOR HOUSE PAINTS AND PRIMERS
32.2 FLAT AND SEMIGLOSS INTERIOR PAINTS
32.3 GLOSS ENAMELS
GENERAL REFERENCES
REFERENCES
Chapter 33: Special Purpose Coatings
33.1 MAINTENANCE PAINTS
33.2 MARINE COATINGS
33.3 AUTOMOBILE REFINISH PAINTS
33.4 TRAFFIC STRIPING PAINTS
REFERENCES
Chapter 34: Functional Coatings
34.1 SUPERHYDROPHOBIC AND SUPERHYDROPHILIC COATINGS
34.2 ICE‐PHOBIC COATINGS
34.3 SELF‐HEALING COATINGS
34.4 ENVIRONMENTALLY SENSING COATINGS
34.5 ANTIMICROBIAL COATINGS
REFERENCES
Index
End User License Agreement
List of Tables
Chapter 01
Table 1.1 Breakdown of Major Resin Types for the US Coatings Market
Chapter 02
Table 2.1 Glass Transition Temperatures (°C) for Homopolymers of Various Monomers
Table 2.2 Polyester Formulation
Table 2.3 Kinetic Parameters as a Function of Cure Temperature
Chapter 03
Table 3.1 Effects of Molecular Weight and Functional Group Content on Viscosity
Chapter 04
Table 4.1 Modulus of Various Engineering Materials
Table 4.2 Mechanical Properties of Floor Coatings
Table 4.3 Mohs Hardness Values for a Variety of Materials
Chapter 08
Table 8.1 Percentage of Nonfunctional Molecules Statistically Predicted for S/BA/HEA (30 : 50 : 20 by wt%) Copolymers
Chapter 09
Table 9.1 Laboratory Procedure for Preparation of a MMA/EA/MAA Copolymer Latex
Chapter 10
Table 10.1 Starting Formulation for a Conventional Polyester Resin
Table 10.2 High Solids Polyester Formulations (Equivalents)
Table 10.3 Water‐Reducible Polyester Formulation
Chapter 12
Table 12.1 Tensile Modulus (psi) (% Elongation to Break)
Table 12.2 Viscosities (100% Solids, mPad·s at 23°C) and Gel Times of Substituted Polyaspartic Acid Ethyl Esters
Chapter 13
Table 13.1 Broad Classifications of Commercial BPA epoxy resins
Chapter 14
Table 14.1 Typical Fatty Acid Compositions of Selected Oils
Chapter 16
Table 16.1 Properties of High‐Methyl versus High‐Phenyl Silicone Resins
Chapter 17
Table 17.1 Composition of Nitrocellulose Types
Chapter 18
Table 18.1 Small’s Molar Attraction Constants, (MPa)
1/2
(cm
3
mol
−1
) at 25°C
Table 18.2 Three‐Dimensional Solubility Parameters (MPa)
1/2
Table 18.3 Solvent Blends, Weight Percents
Table 18.4 Volume‐Based Relative Evaporation Rates at 25°C
Table 18.5 Viscosities at 25°C of Solutions of a High Solids Acrylic; Solvent Concentration 400 g l
−1
Solution
Table 18.6 MIR Values of Selected Solvents,
m
(
g
ozone
/
g
solvent
)
Table 18.7 MIR Limits (g l
−1
) for Selected Aerosol Coatings
Chapter 23
Table 23.1 Typical Baseline Transfer Efficiencies
Chapter 24
Table 24.1 Critical Film Thickness for Popping
Chapter 28
Table 28.1 Classes of Thermosetting Powder Coatings
Chapter 29
Table 29.1 Relationship of PI absorbance (
A
) and percent of incident light absorbed (
I
A
/
I
0
× 100) throughout a film, the top 1% and bottom 1%
Chapter 32
Table 32.1 Exterior White House Paint
Table 32.2 Ultra Low VOC Interior Eggshell Paint
List of Illustrations
Chapter 01
Figure 1.1 The value of coatings used in 2014.
Figure 1.2 Ten‐year trend in coating shipments in the United States (both gallons and dollar value).
Chapter 02
Figure 2.1 Degree of polymerization distribution plots calculated for three types of chain‐growth polymers.
= 1.07 is for an ideal anionic polymerization,
is 1.5 for an ideal free radical polymerization with termination by combination, and
is 3.0 for a typical free radical polymerization.
is 12 for all plots, and
is 12.84, 18, and 36, respectively.
Figure 2.2 (a) Molecular weight distribution of a typical polyester resin. (b) Molecular weight distributions of three alkyd resins, as measured by GPC with a UV detector.
Figure 2.3 Specific volume as a function of temperature (a) for a crystalline material and (b) for an amorphous material; (c) shows free volume within an amorphous material as a function of temperature. Units of specific volume are volume per mass (usually cubic centimeter per gram).
Figure 2.4 (a) Weight fraction distribution
w
P
of molecules in a linear step‐growth polymer for several extents of reaction
p
. (b) Number, or mole fraction, distribution
n
P
.
Figure 2.5 Arrhenius plots for competing reactions: (a)
A
(1) =
A
(2),
E
a
(1) >
E
a
(2); (b)
A
(3) >
A
(1),
E
a
(1) =
E
a
(3); (c)
A
(4) >
A
(1),
E
a
(4) >
E
a
(1).
Chapter 03
Figure 3.1 Model of shear flow of an ideal liquid. (In current usage, the symbol for shear stress is
τ
and its units are Pa; the symbol for shear rate is
γ
and the units of
η
are Pa∙s.) .
Figure 3.2 Plots of the flow of various types of liquids. (a) Newtonian; (b) shear thinning; (c) plastic; (d) shear thickening.
Figure 3.3 Casson plot of viscosity as a function of shear rate showing the dependence
τ
0
with constant
η
and
η
∞
.
Figure 3.4 Schematic plots of systems exhibiting thixotropic flow. (a) The curve to the right is based on readings taken as shear rate was being increased, and the curve to the left is based on readings taken as shear rate was then being decreased. (b) The viscosity drops as shear continues and then increases as the shear rate is decreased.
Figure 3.5 Schematic Casson plots of a sheared and unsheared thixotropic coating. The degree of divergence gives an estimate of the degree of thixotropy.
Figure 3.6 Ostwald capillary viscometer.
Figure 3.7 Schematic representation of cone and plate viscometer geometry.
Figure 3.8 Schematic drawing of a disk viscometer.
Figure 3.9 Determination of viscosity with a bubble tube.
Figure 3.10 Schematic diagram of a Ford No. 4 efflux cup.
Figure 3.11 Schematic diagram of a paddle viscometer.
Figure 3.12 Viscosity reduction of a hydroxy‐functional UV‐curable oligomer with xylene, MEK, and methyl alcohol compared with predicted viscosity if the viscosity reduction were a log‐linear additive relationship by weight.
Figure 3.13 The effect of increasing volume fraction of noninteracting spherical particles on the viscosity of a dispersion.
Figure 3.14 Effect of cluster formation on viscosity.
Figure 3.15 (a) Conventional compared to (b) normal force direction flow of liquids on stirring.
Figure 3.16 Fiber development in roll coating a high extensional viscosity paint.
Chapter 04
Figure 4.1 Tensile force,
F
, applied to a material of cross‐sectional area,
A
, leads to an extension and a resultant strain,
ε
.
Figure 4.2 Shear deformation of a material. A force,
T
, parallel to a surface causes a shape change, quantified by the angular change,
γ
, the shear strain.
Figure 4.3 Two‐dimensional Poisson’s effects in materials. When stretched in one direction, the material will contract in the other direction(s).
Figure 4.4 Typical stress–strain curve for a ductile polymer. The initial slope,
E
, is the modulus, the local maximum stress is the yield stress,
σ
y
, and the ultimate breaking stress is
σ
u
.
Figure 4.5 Loading and unloading paths for a polymer, which is plastically deformed and then unloaded. The plastic strain is denoted as
ε
p
.
Figure 4.6 Specific volume of a semicrystalline polymer as a function of temperature. Note the step change at the melting temperature,
T
m
, and the slope change at the glass transition temperature,
T
g
.
Figure 4.7 Modulus as a function of temperature for a thermoplastic polymer.
Figure 4.8 Creep behavior of a polymer and a metal. Note continuous extension of polymer over time.
Figure 4.9 Stress relaxation of a metal and polymer. Note the decrease in stress as time progresses for the polymer.
Figure 4.10 Effects of (a) rate of application of stress and (b) temperature on stress–strain response.
Figure 4.11 Master curve generation via the use of time–temperature superposition of creep curves taken at varying temperatures and shifted along the time axis.
Figure 4.12 Stress response for a viscoelastic material tested with a dynamic sinusoidal strain input, such as in a DMA experiment.
Figure 4.13 Storage modulus and tan
δ
for a polyester–melamine clear coat. The maximum in tan
δ
is taken as
T
g
. The minimum in the
E
′ can be used for cross‐link density calculations.
Figure 4.14 Non‐contacting profilometer view of (a) mar made by a 14N normal force and (b) fracture scratch made by a 24N normal force in an automotive clear coat.
Figure 4.15 TMA plot of probe displacement against temperature for an undercured and well‐cured acrylic coil coating.
Figure 4.16 T‐bend test for coil coated metals.
Chapter 05
Scheme 5.1
Scheme 5.2 Oxidation of aldehydes and ketones (peracid formation).
Scheme 5.3
Scheme 5.4
Scheme 5.5
Scheme 5.6
Scheme 5.7
Figure 5.1 Panel exposure racks in south Florida. (a) 45° exposure, (b) 5° exposure.
Figure 5.2 Fresnel reflector accelerated outdoor weathering device.
Figure 5.3 Spectral power distribution (SPD) of sunlight and xenon arc light filtered by typical filter combinations. All SPDs normalized to 0.8 W m
−2
at 340 nm.
Chapter 06
Figure 6.1 Geometries of surface interactions between a coating and a substrate. (a) Smooth interface between a coating and the substrate; (b) rough surface on a microscopic scale; and (c) rough surface with incomplete penetration of a coating.
Figure 6.2 Contact angle.
Scheme 6.1
Figure 6.3 Layout of a modern automotive zinc phosphate system.
Figure 6.4 Left: SEM micrograph of zinc phosphate surface. Right: EDX elemental composition spectra of the zinc phosphate surface. Note Zn, Mn, and P peaks from the conversion coating and the Fe peak from the underlying cold rolled steel.
Scheme 6.2
Chapter 07
Figure 7.1 Effect of oxygen concentration on corrosion of mild steel in slowly moving distilled water, 48 h test, 25°C. .
Figure 7.2 Effect of sodium chloride on corrosion of iron in aerated solutions at room temperature (composite of data from several investigations).
Figure 7.3 Effect of pH on corrosion of iron in aerated soft water at room temperature.
Figure 7.4 Effect of temperature on corrosion of iron in water containing dissolved oxygen.
Figure 7.5 Filiform corrosion on a painted aluminum panel after a cyclic corrosion test.
Chapter 08
Figure 8.1 Viscosity dependence on concentration for a 10 mol% acrylic acid copolymer, 75 EN with DMAE, dissolved in
t
‐butyl alcohol and then diluted with water. Also shown are curves for dilution of the same resin with
t
‐butyl alcohol and a typical viscosity–solids dilution curve for a latex, with water.
Figure 8.2 Viscosity as a function of weight percent resin when neutralized with varying levels of DMAE. The resin has 10 mol% of acrylic acid; dilution started at 54 wt% solids.
Chapter 09
Figure 9.1 Schematic diagram of a semicontinuous batch process production unit.
Figure 9.2 Schematic representation of an apparatus for semicontinuous latex polymerization using linear power feed addition.
Chapter 10
Figure 10.1 (a) MALDI‐ToF‐MS spectrum of a polyester resin made from 1,4‐butanediol, adipic acid (AA), and isophthalic acid (IPA) in a 1 : 0.375 : 0.375 mol ratio. (b) Expanded spectrum focused on molecules composed of seven diol and six diacid monomer units.
Chapter 11
Scheme 11.1 Chemistry of methylolation reactions.
Scheme 11.2 Possible mechanisms of etherification reactions of methylolated amino groups containing no N–H moieties, including doubly methylolated amino groups.
Scheme 11.3 Possible mechanism of etherification of singly methylolated amino groups.
Figure 11.1 High performance liquid chromatograms (HPLC) of a typical class I high HMMM resin. (a) An SEC chromatogram and (b) a gradient HPLC chromatogram.
Chapter 12
Scheme 12.1 Possible mechanism for uncatalyzed reaction of an isocyanate with an alcohol.
Scheme 12.2 Possible mechanism for amine‐catalyzed reaction of an isocyanate with an alcohol.
Scheme 12.3 Suggested mechanism for tin‐salt‐catalyzed reaction of an isocyanate with an alcohol.
Scheme 12.4 Possible pathways for reaction of a blocked isocyanate with an alcohol.
Scheme 12.5 Products of diethyl malonate‐blocked cyclohexyl isocyanate reacting with hexyl alcohol.
Scheme 12.6 Unblocking of a uretdione.
Chapter 13
Scheme 13.1 Chemistry of the taffy process for synthesis of BPA epoxy resins.
Scheme 13.2 Probable mechanism of catalysis by a weak acid of reaction of an amine with an epoxy resin.
Chapter 15
Figure 15.1 Effect of temperature and processing time on viscosity.
Figure 15.2 Effect of temperature and processing time on acid value of a typical medium oil linseed alkyd.
Figure 15.3 Size exclusion chromatogram of an alkyd resin. Note the very broad molecular weight distribution and the irregularities in the high molecular weight portion.
Chapter 18
Figure 18.1 Two‐stage release of solvent; MIBK in Vinylite® VYHH at 23°C, initially at 20 wt% polymer.
Figure 18.2 Changes in remaining solvent concentration during wet and dry stages of solvent evaporation at 23°C from films of an acrylic resin (Elvacite® 2013), from nitrocellulose, and from resin‐free solvent, each initially in 60 : 40 IBAc to BAc.
Scheme 18.1 Simplified equations involved in formation of ozone in the atmosphere.
Chapter 19
Figure 19.1 Sensitivity of the eye, photomultiplier tube, and silicon photodiode as a function of wavelength.
Figure 19.2 Relative spectral power distributions of CIE standard illuminants A and D65.
Figure 19.3 Spectral power distribution of a cool white fluorescent lamp (IES 1981).
Figure 19.4 Spectral power distribution of a variety of white LED light sources.
Figure 19.5 External and internal reflection and refraction of light by a nonabsorbing film (refractive index,
n
1
, thickness,
x
) with optically smooth parallel surfaces.
Figure 19.6 Fraction of light reflected from a smooth surface as a function of the angle of incidence,
i
, with various differences in refractive index.
Figure 19.7 Transmission spectra of idealized magentas: (a) path length =
x
; (b) path length = 2
x
.
Figure 19.8 Scattering as a function of refractive index difference; particles have higher refractive indexes than the media on the right‐hand part of the curve and lower values on the left.
Figure 19.9 Scattering coefficients as a function of particle size for rutile TiO
2
and CaCO
3
.
Figure 19.10 Experimental plots of scattering coefficients versus PVC for selected pigments in a dry acrylic lacquer. BCWL is basic carbonate of white lead.
Figure 19.11 Kubelka–Munk equations and assumptions.
Figure 19.12 Idealized diagram of the reflection of light in a metallic coating.
Figure 19.13 CIE color matching functions
,
,
, for equal energy spectra.
Figure 19.14 Light source effects and metamerism.
Figure 19.15 CIE chromaticity diagram showing the location of various hues.
Figure 19.16 Topographical diagram of a three‐dimensional color space with illuminant
C
.
Figure 19.17 Transmission (or reflectance) spectra of cyan, magenta, and yellow colorants, together with their complementary colors.
Figure 19.18 Two‐dimensional slice through a BRDF. The diffuse, directionally diffuse, and specular reflections add to give a complex BRDF.
Figure 19.19 Simplified representation of a goniophotometer: (a) side view and (b) top view.
Figure 19.20 Schematic representation of the photocurrent reflected as a function of viewing angle.
Figure 19.21 Surface roughness measurements from a Wavescan instrument showing higher roughness values in the low wavelength regions, Wa and Wb for coating (
a
), while appearance is equivalent to coating (
b
) at longer wavelengths.
Figure 19.22 Gloss meter.
Figure 19.23 Transition of gloss readings.
Figure 19.24 DOI meter.
Chapter 20
Figure 20.1 Reflectance spectra of rutile and anatase pigments in TiO
2
coatings.
Figure 20.2 Examples of organic yellow pigments.
Figure 20.3 Examples of organic red pigments.
Figure 20.4 Representative phthalocyanine pigments.
Chapter 21
Figure 21.1 Calculations of the effect of PVC on the viscosity of two formulations, both at 70 NVV, but differing in thickness of the layer of adsorbed polymer solution. See text for assumptions.
Figure 21.2 Daniel flow point plot: milliliters of solutions of an alkyd resin in mineral spirits per 20 g TiO
2
as a function of NVW resin in solution.
Figure 21.3 Schematic drawing of a high‐speed impeller disk.
Figure 21.4 Diagram of a high‐speed impeller disperser showing correct positioning of disk and optimum dimension ratios.
Figure 21.5 Schematic drawing of the cascading pattern in a ball mill.
Figure 21.6 Schematic drawing of a media mill.
Figure 21.7 Sketch of a grind gauge and scraper for measuring “fineness of grind” of pigment dispersions.
Chapter 22
Figure 22.1 Schematic description of tan
δ
as a function of
T
for a pigmented coatings (P) and a non‐pigmented (NP) coatings.
Figure 22.2 Storage elastic modulus (
E
′) as a function of temperature (
T
) for a polyacrylate coating with different PVC (
φ
) of TiO
2
.
Figure 22.3 Relative tensile strengths (ratio of pigmented film strengths to strength of unpigmented film) dependence on PVC for an acrylic system containing (⚫) CaCO
3
, (∇) microtalc, (Δ) TiO
2
, and (□) barytes.
Figure 22.4 Thermal coefficient dependence on PVC at 21°C and 0% RH for TiO
2
pigmented epoxy coatings.
Chapter 23
Figure 23.1 A schematic cross section of an air spray gun and a schematic of spray gun nozzle (Delta Spray
TM
, Graco, Inc.): (a) Wings or horns; (b) Angular converging holes; (c) Side‐port holes; and (d) Annular ring around the fluid tip.
Figure 23.2 Bell electrostatic spray equipment.
Figure 23.3 Disk electrostatic spray equipment.
Figure 23.4 Direct roll coater.
Figure 23.5 Cavitation and misting in roll application.
Figure 23.6 Reverse roll coater for coating both sides of coil stock.
Figure 23.7 Schematic diagram of a curtain coater.
Chapter 24
Figure 24.1 Schematic diagram of a cross section of brush marks.
Figure 24.2 Alternate leveling (a–c) results after applying a coating to a rough surface.
Figure 24.3 Typical orange peel pattern (15X).
Figure 24.4 Crawling of a top coat applied over a low surface energy primer (7X).
Figure 24.5 Schematic diagram of a crater.
Figure 24.6 A typical crater.
Figure 24.7 Schematic diagram of Bénard cell formation.
Chapter 25
Figure 25.1 Effect of pigmentation on viscosity as a function of volume solids for an unpigmented coating and for two pigmented coatings based on the same binder with pigment loadings sufficient to give 20% PVC and 45% PVC in the dry films. See Hill and Wicks (1982) for the assumptions made in the calculations.
Figure 25.2 Viscosity as a function of temperature for a conventional and a high solids resin solution. The high solids solution is of a 1500 molecular weight polyester at 90% solids in ethylene glycol monoethyl ether acetate. The conventional solution is of a 20 000 molecular weight polyester at 25% solids in methyl ethyl ketone and ethylene glycol monoethyl ether acetate.
Chapter 27
Scheme 27.1
Scheme 27.2
Figure 27.1 Schematic of Nagoya box used to determine E‐coat throwing power. Current flows through holes in the bottom of the front panels. Sides of the panels are labeled A (facing the anode), B the back of the panel closest to the anode, and so forth.
Figure 27.2 Cationic electrocoat deposition layout for an automotive E‐coating line.
Chapter 28
Figure 28.1 Florida outdoor exposure data on different types of powder coatings.
Figure 28.2 Non‐isothermal viscosity behavior of powder coatings during film formation, as functions of time and panel temperature. (1) Acrylic–dibasic acid type; (2) polyester‐blocked isocyanate type; (3) epoxy–dicy type.
Figure 28.3 Schematic diagram of a line for premixing, melt extrusion, and granulation.
Figure 28.4 Schematic diagram of a line for pulverization and classification.
Figure 28.5 Production equipment for electrostatic spray application of powder coating showing the collection of overspray powder.
Figure 28.6 An electrostatic fluidized bed coating apparatus. (1) Air inlet. (2) Air regulator. (3) Porous membrane. (4) Object to be coated. (5) Electrodes. (6) Fluidized powder. (7) Cloud of charged powder. (8) Ground.
Chapter 29
Scheme 29.1 Photolysis of a triphenylsulfonium salt.
Figure 29.1 Absorption by CTX of 375 nm radiation in the bottom 0.1 μm of 15 µm films with 20 PVC rutile TiO
2
over an 85% reflectance substrate as a function of CTX concentration.
Chapter 30
Figure 30.1 Cross section of a modern automotive paint system. Functions of each layer are specified. Thicknesses are approximate and depend on color and orientation (vertical or horizontal) on the vehicle.
Figure 30.2 Coil coating line.
Figure 30.3 Cross sections of coating systems on a commercial (a) aluminum‐bodied aircraft and (b) composite body. Note that for the composite body, the final body and livery top coats are applied by the airframe manufacturer, while the lower layers are applied by lower tier suppliers.
Chapter 34
Figure 34.1 Contact angles (a) and sliding angle (b) for hydrophilic, hydrophobic, and superhydrophobic surfaces.
Figure 34.2 Wenzel and Cassie–Baxter states of wetting.
Figure 34.3 Hierarchical structure of superhydrophobic surface where liquid is suspended atop papillae of microstructure.
Figure 34.4 Structures of superoleophobic coatings. Schematic (top, a and b) and surfaces produced by deposition and then etching of SiO
2
structures on Si substrates (c and d).
Figure 34.5 Propagation of a crack through a material with microcapsules designed to provide self‐healing of the binder. As crack propagates (top figure to bottom figure), microcapsules are pierces and the healing agent flows into the crack. Due to the presence of the latent catalyst in the surrounding binder, the healing agent then cross‐links to mend the crack.
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Organic Coatings
Science and Technology
Fourth Edition
Frank N. Jones
Emeritus Professor, Eastern Michigan UniversityCoatings Consulting Services, LLC
Mark E. Nichols
Ford Motor Company
Socrates Peter Pappas
Consultant
This edition first published 2017© 2017 John Wiley & Sons, Inc.
Edition HistoryJohn Wiley & Sons Inc, (1e 1994), John Wiley & Sons Inc, (2e 1999), John Wiley & Sons Inc, (3e 2007).
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Library of Congress Cataloging‐in‐Publication Data
Names: Jones, Frank N., 1936– author. | Nichols, Mark E., 1965– author. | Pappas, S. Peter (Socrates Peter), 1936– author.Title: Organic coatings : science and technology / Frank N. Jones, emeritus professor, Eastern Michigan University, Coatings Consulting Services, LLC, Mark E. Nichols, Ford Motor Company ; Socrates Peter Pappas, consultant.Description: Fourth edition. | Hoboken, NJ, USA : John Wiley & Sons, Inc, 2017. | Revised edition of: Organic coatings : science and technology / Zeno W. Wicks, Jr., Frank N. Jones, and S. Peter Pappas. 2nd ed. 1999. | Includes bibliographical references and index. | Description based on print version record and CIP data provided by publisher; resource not viewed.Identifiers: LCCN 2017011370 (print) | LCCN 2017011578 (ebook) | ISBN 9781119337157 (pdf) | ISBN 9781119337218 (epub) | ISBN 9781119026891 (cloth)Subjects: LCSH: Plastic coatings.Classification: LCC TP1175.S6 (ebook) | LCC TP1175.S6 W56 2017 (print) | DDC 667/.9–dc23LC record available at https://lccn.loc.gov/2017011370
Cover design: WileyCover image: Courtesy of Mark E. Nichols
Zeno W. Wicks, Jr., 1920–2007
Zeno was the lead author of the first three editions of this book. Two of us (Jones and Pappas) remember him fondly as an outstanding scientist, a charismatic teacher, a mentor, a marvelous colleague, and a gentleman. Zeno influenced hundreds, more likely, thousands, of students, many of whom have made careers in coatings. His favorite advice to them was “Don’t park your brains at the door.”
Being in a younger generation, Mark Nichols missed out on meeting Zeno. “My loss,” he says, and he is right.
Zeno got his Ph.D. in Chemistry at the University of Illinois. He joined Inmont Corporation, where he advanced to vice president of research and development during a 28‐year career. (Inmont was a leading coating and ink producer, acquired by BASF in 1985.) For the next 11 years, he was professor and chair of the Department of Polymers and Coatings at North Dakota State University (NDSU). He then became a consultant. Among other activities, he traveled worldwide to teach about coatings. He received the Mattiello Memorial Award, the Roy W. Tess Award, and four Roon Awards.
Zeno was the best teacher we ever saw. He could teach all day, and when he invited a class to return after dinner for optional discussion, they came. This book originated as a set of lecture notes Zeno prepared during his last year at NDSU, where he taught a full‐year course in coatings for upperclassmen and graduate students. He thought, rightfully so, that the notes might be helpful to his successors.
Preface
Coatings science and technology advance in a continuous stream of improvements with an occasional breakthrough. This year’s house paint may look the same as that of 10 years ago, but it is a lot better. Thus, it is time to revise the third edition of Organic Coatings: Science and Technology, published in 2007. Here, the third edition has been completely updated. Our purpose remains the same—to provide a reference and textbook that interrelates coatings technology with current scientific understanding.
For the fourth edition, Mark Nichols joined the team of authors. For the first time, we have a real materials scientist involved—and a very good one. As editor‐in‐chief of the Journal of Coatings Technology and Research, Mark has a broad view of contemporary coatings technology and is a leading authority on automotive coatings. His contributions are reflected in major revisions. Entire books could be written about the subject of each chapter, and many have been. To be as comprehensive as possible in the limited space available, we have summarized each topic and have provided references for readers seeking more detailed information. We have striven to enhance the usefulness of this edition both as a classroom textbook on coatings science and as a reference book. The reader will benefit from having taken college level chemistry courses through organic chemistry, but no coursework in polymer or materials science is assumed.
Some chapters include brief descriptions of coating compositions and applications, supported by references, which could be omitted in a classroom or used for outside‐of‐class assignments, such as term papers. We hope that these specific examples enhance the value of the volume as a reference book and self‐teaching text. We understand that the first three editions were widely used for this purpose. We have also defined the jargon of coatings to help newcomers to the field understand its specialized language. While this book is written specifically about coatings, many of the principles apply to the related fields of printing inks, adhesives, and parts of the plastics industry.
Coatings technology evolved empirically by trial and error. Directions on how to make and apply paint have been published for at least 2000 years. Since about 1900, scientific understanding of the applicable principles has evolved. In 1905 Einstein published an equation applicable to flow of pigmented paints, and before 1920, pioneers such as H. A. Gardner, E. Ladd, C. B. Hall, and M. Toch applied scientific methods to testing. However, the coatings field is extremely complex, and scientific understanding remains incomplete. Empirical formulation and experimentation is still essential in developing and using coatings. The often conflicting needs for sustainability, reduced impact on the environment and health, reasonable cost, and improved coating performance require continuing innovation. Our conviction is that understanding the underlying science can help formulators work more effectively and that an appreciation of the formulators’ craft is essential for scientists and engineers working in the field. Knowledge should flow both ways.
A complete literature review for each chapter would fill much of the book. We only cite key references and those that support specific information. Many of the references in older editions were replaced with newer ones, but many old references remain because they describe significant contributions to the evolution of coatings technology. Various sources of additional information are available to investigators. These include refereed journals such as the Journal of Coatings Technology and Research and Progress in Organic Coatings, as well as books, trade journals, conference proceedings, academic dissertations, internal company reports, and information from suppliers and customers. Patents are sometimes overlooked, but they often include informative reviews of the “state of the art” and specific examples including formulas, test procedures, and results. Patents are also free and readily searchable online.
We thank Dean Webster and Carole Worth for their editorial assistance and helpful suggestions.
Chapter 1Introduction to Coatings
Coatings have been used since prehistoric times to protect objects and convey information, and they are ubiquitous in modern society as they serve to both protect substrates and impart aesthetic qualities to improve objects’ appearance. If you are reading this text in a traditional paper book, the paper is coated. Look up and the walls of your room are coated, as are the windows. If you are wearing glasses, the lenses are likely coated to improve the plastic’s scratch resistance and absorb UV radiation. If you are reading this text on a computer screen, the screen is coated to prevent glare and perhaps reduce fingerprints. The CPU inside your computer exists because of coatings used during the printing of nanometer‐sized circuits. If you are outside, the buildings, cars, airplanes, roads, and bridges are all coated. Objects without coatings are less common than those with coatings!
Just because coatings science is an ancient technology does not mean that innovation has ceased. Today many coatings scientists and formulators are working diligently to improve the performance of coatings, reduce the environmental impact of their manufacture and application, and create coatings that provide functionality beyond today’s coatings.
1.1 DEFINITIONS AND SCOPE
Coatings are typically thought of as thin layers that are applied to an object, which is often referred to as the substrate. Thus, one of the defining characteristics of a coating is its thinness. While the thickness of a coating depends on the purpose it serves, typical coating thicknesses range from a few microns to a few hundred microns, but of course, exceptions to this are common. Historically, the thickness of a coating was often quoted in terms of mils, where 1 mil equals one thousandth of an inch or 25.4 µm.
While coatings can be made from any material, this book is primarily concerned with organic coatings. Thus, we leave for other books coatings such as the zinc coatings used to galvanize steel, ceramic coatings that are formed from metal oxides or when metals such as aluminum are anodized, and the many other inorganic coatings used to impart hardness, scratch resistance, or corrosion protection. While these coatings are both technically and economically important, they lie mostly beyond the scope of this book.
Organic coatings are often composite materials in that they are composed of more than one distinct phase. The matrix, called the binder, holds the other components of the coating composition together and typically forms the continuous phase in the dry coating. As stated previously, we are mostly concerned with organic coatings, where the binder is typically an organic polymer.
A confusing situation results from multiple meanings of the term coating. As a noun coating is used to describe both the material (usually a liquid) that is applied to a substrate and the resultant “dry” film. As a verb, coating means the process of application. Usually, the intended meaning of the word coating can be inferred from the context. The terms paint and finish often mean the same thing as coating and also are used both as nouns and verbs. What is the difference between a coating and a paint? Not much—the terms are often used interchangeably. However, it is fairly common practice to use “coatings” as the broader term and to restrict “paints” to the familiar architectural and household coatings and sometimes to maintenance coatings for bridges and tanks. Some prefer to call sophisticated materials that are used to coat automobiles and computer components “coatings,” and others call them “paints.” Consumers are often familiar with the terms varnish or stain. These are types of coatings that are used to protect and beautify wood and are certainly within the scope of this book as they are typically made from polymeric binders with or without pigments.
Because we are limiting the scope of this book to organic coatings that are historically associated with paints, we are also choosing not to cover important materials such as coatings applied to paper and fabrics, decals, laminates and cosmetics, and printing inks, even though one could argue that these coatings share much in common with traditional paints. However, readers interested in those materials will find that many of the basic principles discussed in this text are applicable to such materials. Restrictions of scope are necessary if the book is to be kept to a reasonable length, but our restrictions are not entirely arbitrary. The way in which we are defining coatings is based on common usage of the term in worldwide business. For classification purposes, coatings are often divided into three categories: architectural coatings, original equipment manufacturer (OEM) coatings, and special purpose coatings.
As the coatings industry is a relatively mature industry, its growth rate typically paces that of the general economy. Like many other industries, growth has slowed in North America and Europe and has dramatically increased in Asia and South America as those economies have boomed. An estimate of the value of coatings used in each region is shown in Figure 1.1. The total value of the global coatings market was estimated to be approximately $112 billion in 2014 (American Coatings Association and Chemquest Group, 2015).
Figure 1.1 The value of coatings used in 2014.
Source: Reproduced with permission of American Coatings Association.
Figure 1.2 summarizes the estimated value and volume of coating shipments in the United States for a recent 10‐year period. The effect of the economic downturn in 2008–2009 is evident (Data from American Coatings Association and Chemquest Group, 2015).
Figure 1.2 Ten‐year trend in coating shipments in the United States (both gallons and dollar value).
Source: Reproduced with permission of American Coatings Association.
1.2 TYPES OF COATINGS
Architectural coatings include paints and varnishes (transparent paints) used to decorate and protect buildings, outside and inside. They also include other paints and varnishes sold for use in the home and by small businesses for application to such things as cabinets and household furniture (not those sold to furniture factories). Architectural coatings are often called trade sales paints. They are sold directly to painting contractors and do‐it‐yourself users through paint stores and other retail outlets. In 2014 in the United States, architectural coatings accounted for about 60% of the total volume of coatings; however, the unit value of these coatings was lower than for the other categories, so they made up about 49% of the total value. This market is the least cyclical of the three categories. While the annual amount of new construction drops during recessions, the resulting decrease in paint requirements tends to be offset by increased repainting of older housing, furniture, and so forth during at least mild recessions. Latex‐based coatings make up about 77% of architectural coatings. Interior paints are approximately 2/3 of all architectural coatings, exterior paints 23%, and stains 7%, with the remained split among varnishes, clear coats, and others.
OEM coatings are applied in factories on products such as automobiles, appliances, magnet wire, aircraft, furniture, metal cans, and chewing gum wrappers—the list is almost endless. In 2014 in the United States, product coatings were about 29% of the volume and 31% of the value of all coatings. The volume of product coatings depends directly on the level of manufacturing activity. This category of the business is cyclical, varying with OEM cycles. Often, product coatings are custom designed for a particular customer’s manufacturing conditions and performance requirements. The number of different types of products in this category is much larger than in the others; research and development (R&D) requirements are also high.
Special purpose coatings are industrial coatings that are applied outside a factory, along with a few miscellaneous coatings, such as coatings packed in aerosol containers. This category includes refinish coatings for cars and trucks that are applied outside the OEM factory (usually in body repair shops), marine coatings for ships (they are too big to fit into a factory), and striping on highways and parking lots. It also includes maintenance paints for steel bridges, storage tanks, chemical factories, and so forth. In 2012 in the United States, special purpose coatings made up about 11% of the total volume and 20% of the total value of all coatings, making them the most valuable class. Many of today’s special purpose coatings are the product of sophisticated R&D, and investment in further improvements remains substantial.
Coatings are used for one or more of three reasons: (1) for decoration, (2) for protection, and/or (3) for some functional purpose. The low gloss paint on the ceiling of a room not only fills a decorative need but also has a function. It reflects and diffuses light to help provide even illumination. The coating on the outside of an automobile adds beauty to a car and also helps protect it from rusting. The coating on the inside of a beverage can have little or no decorative value, but it protects the beverage from the can. (Contact with metal affects flavor.) In some cases, the interior coating also protects the can from the beverage. (Some soft drinks are so acidic that they can dissolve the metal.) Other coatings reduce the growth of algae and barnacles on ship bottoms, protect optical fibers for telecommunications against abrasion and guide the light within the fiber, retard corrosion of bridges, protect wind turbine blades from erosion due to the impact of raindrops, and so on. While the public most commonly thinks of house paint when talking about coatings, all kinds of coatings are important throughout the economy, and they make essential contributions to most high‐tech fields. As already mentioned, computer technology depends on microlithographic coatings to pattern the circuits in CPU and memory chips.
1.3 Composition of Coatings
Organic coatings are complex mixtures of chemical substances that can be grouped into four broad categories: (1) binders, (2) volatile components, (3) pigments, and (4) additives.
Binders are the materials that form the continuous film that adheres to the substrate (the surface being coated), bind together the other substances in the coating to form a film, and present an adequately hard outer surface. The binders of coatings within the scope of this book are organic polymers—some made via synthetic organic chemistry and some derived from plant oils. In some cases, these polymers are prepared and incorporated into the coating before application; in other cases, lower molecular weight organic materials (monomers or oligomers) are mixed with the other components of the coating, and final polymerization takes place after the coating has been applied. Binder polymers and their precursors are often called resins. The binder governs, to a large extent, the properties of the coating film. The major resin types used in coatings as percentages of the total are given in Table 1.1. These numbers should be taken as approximations as different coating suppliers name their resins somewhat differently, and some coating contain more than one resin type.
Table 1.1 Breakdown of Major Resin Types for the US Coatings Market
Source: Reproduced with permission of American Coatings Association.
Resin type
Percent
Acrylic
31
Vinyl
20
Urethane
14
Epoxy
8
Alkyd
7
Silane
5
Polyester
4
Amino
3
PVC
2
SBR
1
Phenolic
1
Cellulosic
1
Other
3
Volatile components are included in a large majority of coatings and are often referred to as solvents. They play a major role in the synthesis, mixing, and application of coatings. They are liquids that make the coating fluid enough for application, and they evaporate during and after application. Until about 1935, almost all of the volatile components were low molecular weight organic compounds that dissolved the binder components. However, the term solvent has become potentially misleading because many coatings have been developed for which the binder components are not fully soluble in the volatile components but instead act as a carrier to reduce viscosity, but not fully solvate the binder. Because of the need to reduce the environmental impact of coating manufacture and application, a major continuing drive in the coatings field is to reduce the use of volatile organic compounds (VOCs) by making the coatings more highly concentrated (higher solids coatings), by using water as a major part of the volatile components (waterborne coatings), and by eliminating solvents altogether.
Vehicle is a commonly encountered term. It usually means the combination of the binder and the volatile components of a coating. Today, most coatings, including waterborne coatings, contain at least some volatile organic solvents. Exceptions are powder coatings, certain solventless liquid coatings (also called 100% solids coatings), radiation‐curable coatings, and a small but growing segment of architectural coatings.
Pigments are finely divided, insoluble solid particles, ranging from a few tens of nanometers to a few hundred microns in size, that are dispersed in the vehicle and remain suspended in the binder after film formation. Generally, the primary purpose of pigments is to provide color and opacity to the coating film. Additionally, pigments can provide other functions, such as corrosion‐inhibiting pigments, which enhance the corrosion protecting properties of the coatings. Pigments also play a major role in the application characteristics and the mechanical behavior of coatings. While most coatings contain pigments, there are important types of coatings that contain little or no pigment, commonly called clear coats, or just clears. Clear coats for automobiles and transparent varnishes are examples. Coating solids typically refer to the proportion of binder and pigment and are the part of the paint that remains after the volatile components have left the coating. Pigments are distinct from dyes, which are typically soluble in their binder and/or solvent and exist as individual molecules in that vehicle. Dyes are rarely used in the types of coatings discussed in this book.
Additives are materials that are included in small quantities to modify some property of the coating. Examples are catalysts for polymerization reactions, light and heat stabilizers, rheology modifiers, defoamers, and wetting agents.
1.4 COATING HISTORY
The chemistry of most coatings used today bears little resemblance to the coatings used prior to the industrial revolution. For centuries coatings were based on naturally occurring oils and pigments. 40 000 years ago ochre was processed for use as a pigment in Africa (Rosso et al., 2016). Cave paintings in northern Spain date from over 40 000 years ago and contain depictions of animals and people. While their true purpose is impossible to ascertain, the paintings demonstrate that even in prehistoric times people were using coatings to decorate their surroundings and to convey information to others.
In Asia, a traditional coating made from urushiol, the resin from a native tree, has been used since at least 1200 B.C. to produce beautiful clear lacquers for art objects. Egg yolk was often used as the binder for paintings in the West until the fourteenth or fifteenth century, when certain plant oils, such as linseed (also known as flax) and walnut oils, were introduced to protect and beautify wood. Those oils were also used as the binder for many of the great oil paintings made by famous artists such as Michelangelo, and they continue to be favored by many artists today. During the nineteenth and early twentieth centuries, most architectural coatings employed linseed oil as the binder.
Early pigments were made from ground bones or charcoal and other minerals such as iron oxide, ochre, and calcium carbonate. Simple chemical reactions were later used to produce other pigments such as lead white (lead carbonate) and red lead (lead oxide). More chromatic pigments such as ultramarine blue were rare and expensive for centuries owing to their limited supply.
