153,99 €
Mehr erfahren.
- Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
- Kategorie: Fachliteratur
- Sprache: Englisch
A practical guide to polymer coatings that covers all aspects from materials to applications
Polymer Coatings is a practical resource that offers an overview of the fundamentals to the synthesis, characterization, deposition methods, and recent developments of polymer coatings. The text includes information about the different polymers and polymer networks in use, resins for solvent- and water-based coatings, and a variety of additives. It presents deposition methods that encompass frequently used mechanical and electrochemical approaches, in addition to the physical-chemical aspects of the coating process. The author covers the available characterization methods including spectroscopic, morphological, thermal and mechanical techniques.
The comprehensive text also reviews developments in selected technology areas such as electrically conductive, anti-fouling, and self-replenishing coatings. The author includes insight into the present status of the research field, describes systems currently under investigation, and draws our attention to yet to be explored systems. This important text:
• Offers a thorough overview of polymer coatings and their applications
• Covers different classes of materials, deposition methods, coating processes, and ways of characterization
• Contains a text that is designed to be accessible and helps to apply the acquired knowledge immediately
• Includes information on selected areas of research with imminent application potential for functional coatings
Written for chemists in industry, materials scientists, polymer chemists, and physical chemists, Polymer Coatings offers a text that contains the information needed to gain an understanding of the charaterization and applications of polymer coatings.
Sie lesen das E-Book in den Legimi-Apps auf:
Seitenzahl: 1160
Veröffentlichungsjahr: 2018
Ähnliche
Table of Contents
Cover
Dedication
Preface
Acknowledgments
List of Most Important Symbols and Abbreviations
Chapter 1: Introduction
1.1 Scope
1.2 The Importance of Polymer Coatings
1.3 The General Constitution of Polymer Coatings
1.4 Coating Requirements
1.5 Outline and Approach
References
Further Reading
Chapter 2: Polymers and Network Characteristics
2.1 Polymers
2.2 Polymer Formation
2.3 Polymer Networks
2.4 Final Remarks
References
Further Reading
Chapter 3: Thermoset Resins
3.1 Petro‐based Thermoset Resins
3.2 Epoxy Systems
3.3 Acrylates and Acrylics
3.4 Isocyanates
3.5 Polyurethanes
3.6 Polyesters
3.7 Renewable Raw Materials
3.8 Drying Oils
3.9 Alkyds
References
Further Reading
Chapter 4: Basic Coating Formulations
4.1 Coating Compositions in General
4.2 Solventborne Formulations
4.3 Waterborne Formulations
4.4 Radiation Curing Formulations
4.5 Final Remarks
References
Further Reading
Chapter 5: Additives and Particulates
5.1 Types of Additives
5.2 Thickeners
5.3 Surface Active Agents
5.4 Surface Modifiers
5.5 Leveling and Coalescing Agents
5.6 Catalytically Active Additives
5.7 Special Effect Additives
5.8 Particulates
References
Further Reading
Chapter 6: Application Methods
6.1 Conventional Deposition Techniques
6.2 Laboratory and Industrial Methods
6.3 Powder Coating
6.4 An Example: Automotive Coatings
6.5 Network Formation Assessment
References
Further Reading
Chapter 7: Physical–Chemical Aspects
7.1 Intermolecular and Mesoscopic Interactions
7.2 Polymer Solubility
7.3 Interfacial Aspects
7.4 Dispersions
7.5 Emulsions
7.6 Coagulation Kinetics
7.7 Self‐assembly
7.8 Final Remarks
References
Further Reading
Chapter 8: Chemical and Morphological Characterization
8.1 The Need for Characterization
8.2 IR and Raman Spectroscopy
8.3 NMR
8.4 Functional Group Analysis
8.5 XPS, SIMS, and LEIS
8.6 SEC
8.7 MALDI–MS
8.8 XRD
8.9 Optical Microscopy
8.10 Electron Microscopy
8.11 Surface Probe Microscopy
8.12 Thickness and Beyond
8.13 Final Remarks
References
Further Reading
Chapter 9: Thermal and Mechanical Characterization
9.1 Thermal Characterization
9.2 Permeability–Diffusivity–Solubility Analysis
9.3 Mechanical Constitutive Behavior
9.4 A Brief Review of Experimental Data
9.5 Mechanical Characterization
9.6 Hardness
9.7 Internal Stress Analysis
9.8 Adherence
9.9 Final Remarks
References
Further Reading
Chapter 10: Rheological Aspects
10.1 The Importance of Rheology
10.2 Rheological Characterization
10.3 Rheological Control of Paints
10.4 Viscosity of Paints During Curing
References
Further Reading
Chapter 11: Appearance
11.1 Defects
11.2 The Characterization of Color
11.3 The Characterization of
Feel
or Haptic Property
References
Further Reading
Chapter 12: Electrically Conductive Coatings
12.1 Typical Applications
12.2 Electrical Conductivity Measurements
12.3 Intrinsically Conductive Polymers
12.4 An Example: P3HT/PCBM Photovoltaics
12.5 Conductive Composites
12.6 Some Examples of Conductive Composite Coatings
References
Further Reading
Chapter 13: Marine Anti‐fouling Coatings
13.1 Marine Biofouling
13.2 Evolution of Marine Coatings toward Green Anti‐fouling Approaches
13.3 Principles for Preventing Adhesion or Promoting Detachment of Biofoulants
13.4 Nontoxic, Non‐biocide‐release Anti‐fouling Coatings
13.5 Recent and Future Approaches
13.6 Final Remarks
References
Further Reading
Chapter 14: Self‐replenishing and Self‐healing Coatings
14.1 Self‐healing and Self‐replenishing self-replenishing!functionalities"?>: Scope and Limitations
14.2 Damage Recovery on Different Length Scales: Preemptive Healing
14.3 Approaches to Self‐healing Coatings
14.4 Industrial Practice
14.5 Approaches to Self‐replenishing Coatings
14.6 Self‐replenishing Low Surface Energy Coatings
14.7 Scenarios for Further Options
14.8 Final Remarks
References
Further Reading
Chapter 15: What's Next
15.1 Generic Problems and Challenges
15.2 What Else?
15.3 What's Next?
References
Appendix A: Units, Physical Constants, and Conversion Factors
Basic and Derived SI Units
Physical Constants
Conversion Factors for Non‐SI Units
Prefixes
Greek Alphabet
Standard Values
Appendix B: Data
Index
End User License Agreement
List of Tables
Chapter 2
Table B.1 Dipole moment
μ
and polarization volume
α
′
= α
/4π
ε
0
for some compounds.
Table B.2 Viscosity
η
for some compounds.
Table B.3 Physical data for some solvents at 20 °C.
Chapter 1
Table 1.1 Coating formulation characteristics.
Table 1.2 Typical binder compounds. Source: Lambourne and Strivens 1999 [5]. Adapted with permission of Elsevier.
Table 1.3 Typical pigment properties.
Chapter 2
Table 2.1 Values for characteristic ratio
C
for various polymers.
Table 2.2 Kinetic window for
a
s
< 0.05 and
a
c
> 0.90 after 10 min.
Chapter 3
Table 3.1 Typical epoxy–amine resin formulations.
Table 3.2 Composition of various drying oils and their I
2
number.
Chapter 4
Table 4.1 Typical and extreme values for the Mark–Houwink slope
α
and fractal dimension
d
f
.
Chapter 5
Table 5.1 Types of thickeners for (organic) solventborne coatings.
Table 5.2 Flow leveling agents.
Table 5.3 Effect of MEKO on drying.
Table 5.4 Rutile and anatase physical–chemical properties.
Chapter 7
Table 7.1 Van der Waals interactions between small molecules.
Table 7.2 Permittivity
ε
, refractive index
n
, and characteristic frequency
ν
for various materials.
Table 7.3 Solubility parameters for various solvents and polymers.
Table 7.4 Surface energies according to the Hamaker–Israelachvili model
.
Table 7.5 Surface energy of spinel MgAl
2
O
4
.
Table 7.6 Probing liquids for CA measurements and
γ
cri
for several solids.
Table 7.7 Dispersion and polar contributions to
γ
LV
and
γ
cri
(mJ m
−2
).
Table 7.8 Surface tension and donor–acceptor contributions for several liquids (mJ m
−2
).
Table 7.9 Commercial surfactant families and a specific member.
Table 7.10 Calculation of the HLB value for sodium oleate and Span 60.
Table 7.11 Group contributions to the HLB value.
Chapter 8
Table 8.1 Characteristic vibrations for several groups.
Chapter 9
Table 9.1 Creep and relaxation function for the Maxwell and Kelvin elements.
Table 9.2 Surface energies
γ
for typical polymers and solvents used in coating technology.
Table 9.3 Fracture energy
R
and work of adhesion
W
for the polymers of Figure 9.46.
Chapter 10
Table 10.1 Typical maximum shear rates
for different coating processes.
Chapter 11
Table 11.1 The colors of the (visible) electromagnetic spectrum and the color temperatures of various light sources.
Table 11.2 Refractive index
n
of binders and white pigments.
Chapter 12
Table 12.1 Percolation characteristics.
Chapter 13
Table 13.1 Physical properties of polymers investigated for AF surfaces.
Table 13.2 Results of water contact angle and protein resistance measurements on hydrophobic methylated silica surfaces (HMS) modified with different end groups.
Table 13.3 Results of water contact angle (CA) and root mean square roughness (RMS) measurements of superhydrophobic surfaces with single (nano) and dual (nano and micro) scale roughness.
Chapter 14
Table 14.1 Selection of intrinsic self‐healing polymer systems that have been (or have the potential to be) implemented in polymeric coatings.
Table 14.2 Self‐replenishing efficiency (SRE) based on water advancing CA and F/C atomic ratio measurements (
experimental
) or calculations (
simulation
), before and after damage.
Chapter 15
Table 15.1 Resistance toward various processes for various types of compounds.
List of Illustrations
Chapter 1
Figure 1.1 World population and coatings. (a) Growth of the world population [3] and (b) growth of the coating market [4].
Figure 1.2 Typical polymer coating design. (a) Schematic of the buildup of several layers involved in typical automobile coating and (b) actual layer sequence on a car side panel showing (1) UV clear coat, (2) waterborne base coat, (3) filler, (4) wash primer, and (5) steel substrate.
Figure 1.3 Examples of modern pigments. (a) CdSe nanoparticle suspensions, showing a color change with size variation,
D
≈ 2.1 nm → 4.2 nm. (b) Left: individual gold nanoparticles in a citrate solution. Right: agglomerated gold nanoparticles after adding a NaCl solution.
Figure 1.4 Various coating properties as a function of PVC [6, 7].
Figure 1.5 Optical effects. (a) Mechanism of coloration for fluorescent pigments and (b) the electromagnetic spectrum with the (enlarged) optical region.
Figure 1.6 Defects in coatings. (a) Sagging and (b) popping.
Figure 1.7 Changes due to solvent evaporation. (a) Amount of solvent evaporated as a function of time for a pure solvent and a solvent–resin mixture, showing multistage behavior, and (b) change in viscosity and surface tension of a solvent mixture as a function of percentage evaporation.
Chapter 2
Figure 2.1 Microstructural features of polymers.
Figure 2.2 The
cis
and
trans
conformations in ethane and the t, g
+
, and g
−
conformation in butane, as shown by the Newman projection.
Figure 2.3 Amorphous structure, orientation, and crystallinity in polymers.
Figure 2.4 Orthorhombic packing for the 2/1 helix (a) and hexagonal packing for the 9/5 helix (b) of polyoxymethylene as seen along the axis of the helix.
Figure 2.5 The fringed micelle and regular fold model of lamellae in polymer crystals.
Figure 2.6 The structure of a lamella and a spherulite.
Figure 2.7 Gelling with
m
1
the mass of the monomers,
m
j
the mass of the oligomers, and
m
gel
the mass of the gel. (a) Step‐growth polymerization. (b) Chain‐growth polymerization.
Figure 2.8 Polyesters and polyurethanes. (a) Typical diols with (b) a typical diacid or isocyanate that can be branched with (c) TMP to, respectively, a polyester and a polyurethane.
Figure 2.9 Alkyds. (a) Glycerol (A
3
) and penta (A
4
). (b) A typical fatty acid (B
1
) and acid anhydride (B
2
).
Figure 2.10 Mobility and molecular networks. (a) Molecular mobility as a function of temperature for a thermoplast and a thermoset, showing a
rubber plateau
. (b) A schematic of a polymer network where one
elastically active knot
(EAK), one
elastically active network
(EAN) chain, a
dangling end
, and a
loop
are indicated.
Figure 2.11 Kinetics for two competitive reactions. (a) Arrhenius plot with two different values for
E
act
but equal values for
k
0
. (b) Arrhenius plot with equal values for
E
act
but different values for
k
0
. (c) Arrhenius plot with two different values for both
k
0
and
E
act
.
Chapter 3
Figure 3.1 Epoxy basic components. (a) Epichlorohydrin (ECH); (b) Glycidyl ether; (c) Glycidyl ester.
Figure 3.2 (a) Schematic of nucleophilic ring opening and (b) example of a glycidyl ether reacting with an acid.
Figure 3.3 The formation of a 100% epoxy network via a Lewis acid or a nucleophile.
Figure 3.4 The reaction of a primary amine with an epoxy to a secondary amine and the subsequent reaction with an epoxy yielding a tertiary amine and a typical diamine crosslinker (tetra‐propyleneglycol‐diamine, TPGDA).
Figure 3.5 The reaction of bisphenol‐A (BPA) and epichlorohydrin (ECH).
Figure 3.6 The reaction of bisphenol‐A diglycidyl ether (DGEBPA) and bisphenol‐A (BPA).
Figure 3.7 Important components for acrylic resins.
Figure 3.8 Nonfunctional monomers as used for the formation of acrylic resins.
Figure 3.9 Functional monomers as used for the formation of acrylic resins.
Figure 3.10 Components as used for polyvinylacetate and polyvinylidenedifluoride‐
co
‐vinyl ether.
Figure 3.11 Diacrylates or triacrylates used as reactive diluents.
Figure 3.12 Isocyanate formation, reaction of an isocyanate with a nucleophile and a blocking/deblocking reaction.
Figure 3.13 Reaction of isocyanates with alcohols, amines, and water.
Figure 3.14 Formation of isocyanurate rings from isocyanates.
Figure 3.15 Formation of an OH‐functional polyurethane from diisocyanates and an excess of diols.
Figure 3.16 Examples of polyols and isocyanates as used for polyurethanes.
Figure 3.17 The polycondensation of alcohol and acid to a polyester.
Figure 3.18 Examples of polyols and polyacid monomers often used.
Figure 3.19 Polycondensation of alcohol and acid to a polyester. (a) Schematic figure of a polycondensation reaction system and (b) example of the influence of processing time on the acid number and viscosity.
Figure 3.20 (a) Abietic acid and (b) cellulose.
Figure 3.21 (a) Conversion of
D
‐glucose to isosorbide via hydrogenation and (b) hydrolysis of furfuryl alcohol to levulinic acid.
Figure 3.22 Examples of bio‐derived monomers for polyesters.
Figure 3.23 Isosorbide‐glycerol‐succinic acid‐based polyester.
Figure 3.24 (a) Epoxidized fatty acid and (b) bisfurfuryl acetone (BFA).
Figure 3.25 Acrylics and itaconics.
Figure 3.26 Examples of bio‐derived monomers for polyurethanes.
Figure 3.27 Triester showing a single unsaturated bond in the first chain, a methyl reactive center in the second chain, and two methyl active centers in the third chain.
Figure 3.28 The various fatty acids as present in various types of drying oils.
Figure 3.29 Autoxidative drying. (a) Peroxide formation on a diene; (b) Decomposition of the peroxides; (c) Crosslinking to peroxide bonds.
Figure 3.30 A simplified alkyd structure.
Figure 3.31 The glyceride‐oil process. (a) Alcoholysis of triglycerides and (b) alkyd polycondensation.
Figure 3.32 A possible transition to bio‐based raw materials for alkyds.
Chapter 4
Figure 4.1 The organosol or plastisol process for food jar caps.
Figure 4.2 The coil coating process. (a) Coils with a typical width 1.5 m, a length 2 km, and a weight 2000 kg. (b) The deformation to realize profiled plates. (c) A schematic of the equipment used.
Figure 4.3 Examples of blocked isocyanates. (a) Caprolactam‐blocked IDPI trimer and (b) MEK‐oxime‐blocked HDT trimer.
Figure 4.4 Typical viscosity change of a high solids coating as a function of the setting and curing time.
Figure 4.5 Examples of options for keeping the network structure (left) or the telechelic functionality per chain constant (right), while reducing the molecular weight of a classic resin (top).
Figure 4.6 Examples of options for lowering the molecular weight with equal number of functional groups (left) or keeping the overall pending functionality constant (right).
Figure 4.7 Options for reactive diluents.
Figure 4.8 Hyperbranched systems. (a) Linear, branched, and hyperbranched polymers and dendrimers. (b) Viscosity behavior for linear and lightly branched polymers (L), hyperbranched polymers (H), and dendrimers (D).
Figure 4.9 Polycondensation of TMP and DMPA for hyperbranched polymers.
Figure 4.10 Hyperbranched systems. (a) Schematic of the monomer and branched chain and (b) dimethylolpropionic acid (DMPA).
Figure 4.11 Schematic representation of the various units in dendritic polymers.
Figure 4.12 Dendritic growth using aziridine via ring‐opening polymerization (ROP).
Figure 4.13 Dendritic growth using TMP and glycidol via ring‐opening polymerization (ROP).
Figure 4.14 Growth of hyperbranched polymers based on β‐hydroxyalkylamides.
Figure 4.15 Molecular weight control.
Figure 4.16 Schematic representation of the various branching units for HB polymers.
Figure 4.17 Growth of hyperbranched polymers based on DIPA and cyclic anhydrides via polycondensation.
Figure 4.18 SEC. (a) Schematic of the setup and (b) effect of branching on globule size.
Figure 4.19 Polymeric salts. (a) The formation of a polymeric salt and (b) the viscosity of a polymeric salt solution without and with cosolvent.
Figure 4.20 Schematic representation of film formation using emulsions.
Figure 4.21 AFM images of latexes. (a) Axonometric view of more or less regularly ordered packed latex spheres and (b) top view of packed latex spheres.
Figure 4.22 Schematic representation of film formation using secondary dispersions, showing the initial stage with an O/W dispersion, followed by the inversion to a W/O dispersion and coalescence.
Figure 4.23 Cosolvents and surfactants. (a) Examples of cosolvents for film formation on waterborne systems and (b) external and built‐in surfactants used for the stabilization of dispersions.
Figure 4.24 Thermoset latex systems. (a) Using nonvolatile crosslinkable compounds (+) dispersed in the thermoplast droplet and leading to a network of the crosslinked components within the thermoplast matrix. (b) Using polymers equipped with reactive groups (–♦) and a crosslinker (–•) in the water phase leading to a crosslinked network including the polymer.
Figure 4.25 Thermoset latex systems. A‐ refers to a reactive group linked to a polymer. B refers to a dissolved crosslinker, B‐ to a crosslinker attached to a polymer, and [B] and [B‐] to a blocked crosslinker. (a) Using nonvolatile crosslinkable compounds and (b) using polymers equipped with reactive groups and crosslinker molecules in the water phase.
Figure 4.26 OH‐polyesters with high functionality neutralized with DMEA.
Figure 4.27 Epoxy dispersions. (a) Sodium sulfoisophthalic acid as used in a cationic process and (b) the anionic process using amines.
Figure 4.28 Acrylic dispersions. (a) Diamine as used in the cationic process, (b) diol as used in the anionic process, and (c) an anionic group.
Figure 4.29 The ketone process for self‐dispersible polyurethane dispersions.
Figure 4.30 The prepolymer mixing process for polyurethane dispersions.
Figure 4.31 The open time challenge for waterborne systems.
Figure 4.32 The use of waterborne coatings as illustrated by indoor wood protection, industrial coating of panels, and their use in automotive parts.
Figure 4.33 Type I and type II Norrish processes.
Figure 4.34 An example of a cationic photoinitiator, the sulfonium salt of tetrafluoroboride.
Figure 4.35 Photocuring. (a) The effect of oxygen inhibition on the rate of curing using an atmosphere pure O
2
, air, and N
2
and (b) schematic image of the optimal domain for PIs in terms of PI concentration
c
and coating thickness
b
.
Figure 4.36 Acrylate photocuring. (a) The three constituents of acrylate photocuring, (b) schematic image of the
zipper
network structure, and (c) a monofunctional(2‐ethylacrylate), difunctional(1,6‐hexanedioldiacrylate), and trifunctional(trimethylolpropane triacrylate or TMP triacrylate) acrylate.
Figure 4.37 Radical scavengers. (a) 4‐Methoxy‐phenol and
t
‐butylhydroquinone and (b) Triphenyl phosphine.
Figure 4.38 The inside‐out polyurethane acrylate process.
Figure 4.39 The outside‐out polyurethane acrylate process.
Figure 4.40 Cationic polymerization using epoxy vinyl ether reactions.
Figure 4.41 The fumarate/vinyl ether process suitable for radiation curing of powder coatings.
Figure 4.42 The chemistry to realize hybrid powder coatings.
Figure 4.43 Crosslinking in polyester powder coating. (a) TGIC, (b) primid, and (c) the hydroxyl alkylamide esterification pathway.
Figure 4.44 The use of uretdiones. (a) Internal blocking by associating two isocyanates and (b) oligomers containing uretdiones units.
Figure 4.45 The UV powder coating process showing the separated control of flow (by, e.g. IR heating) and cure (by UV radiation).
Figure 4.46 The optical glass fiber drawing and coating process. (a) Schematic image of a drawing tower and (b) schematic of an optical glass fiber and the sequence of coatings applied.
Chapter 5
Figure 5.1 Clay structure. (a) Crystallographic structure of montmorillonite. (b) SEM image of partially exfoliated clay platelets.
Figure 5.2 Thickening mechanism by a layered type of thickener. (a) Formation of a hydrogen‐bonded network of sheets via water molecules. (b) The configuration of water molecules around a sheet.
Figure 5.3 Rheological behavior. (a) Pseudoplastic flow behavior. (b) Thixotropic flow behavior.
Figure 5.4 Dispersion of clay particles, depending on the amount of polymers present. (a) With a limited amount of polymer, the ions originally present are exchanged by polymers. (b) The
original
clay morphology with ions present between the various platelets. (c) With a substantial amount of polymers leading to individual dispersed platelets.
Figure 5.5 Clay platelet encapsulation. (a) A schematic showing an organically modified platelet further encapsulated by emulsion polymerization. (b) A SEM and TEM image of a dumbbell particle containing exfoliated platelets.
Figure 5.6 Stabilization of emulsion droplets. (a) A schematic picture showing, respectively, stabilization by surfactants (1), by particles (2) and by platelets (3). (b) A SEM image of clay platelet stabilized emulsion droplets.
Figure 5.7 Schematic of associative thickening. (a) Network between binder particles and thickeners. (b) Schematic of a thickener and a surfactant with as only essential difference that a thickener contains a hydrophobic functional group at both ends (indicated by the black block), while a surfactant contains one such a block.
Figure 5.8 Examples of (organic) solventborne thickeners. (a) Hydrogenated castor oil. (b) Polyamines. (c) Sulfonated salts.
Figure 5.9 Schematic of the influence of shape (upper row) on aggregation (middle row) and agglomeration (lower row).
Figure 5.10 Defects in coatings. (a) Foaming. (b) Pinholing or cratering. (c) (Non)‐bubble formation in the absence and bubble formation in the presence of a surfactant. (d) Using a defoamer that breaks up the surfactant stabilized interface.
Figure 5.11 Organosilanes showing the backbone and typical end groups Y and X.
Figure 5.12 Matting. (a) Typical mat surface. (b) Cross section of mat film showing the particles embedded.
Figure 5.13 Defects of coatings. (a) Orange peel effect. (b) Bénard cell effect. (c) Schematic of the Bénard cell effect.
Figure 5.14 Drying without dryers making use of radicals and peroxide formation.
Figure 5.15 Oxidative drying. (a) Hydrogen abstraction leading radical formation. (b) Peroxide formation in which the metal acts as catalyst. (c) Possible crosslink reactions. (d) Regenerating new radicals via the metal. (e) Possible side products via β‐scission.
Figure 5.16 Alternatives. (a) A feeder dryer used to release metal ions after metal ion consumption due to degradation. (b) Mn‐based dryers for solventborne systems. (c) The system Fe
2+
/H
2
O
2
/ascorbic acid for waterborne systems.
Figure 5.17 Melamine crosslinking. (a) Melamine where R = H or C
n
H
2n + 1
with n = 1–4. (b) The reaction with functionalized polymers. (c) Self‐condensation of melamine.
Figure 5.18 Blocked p‐TSA. (a) Mechanism and structures of blocked p‐TSA, via ionic and covalent bonding. (b) Storage behavior of polyester polyol + HMMM showing the effect of adding p‐TSA on the viscosity increase versus time. (c) Hardness change as a function of curing temperature with curing time for 20 min for the same system showing the increase in hardness.
Figure 5.19 Alternatives. (a) Urethane formation, (b) urea formation, and (c) crosslinkers are often used, respectively, HDI, IPDI, and polyisocyanurate. Also shown is the catalyst DBTDL.
Figure 5.20 Blocked PU. (a) Blocking mechanism with BH as blocking agent. (b) Deblocking by elimination–addition. (c) Deblocking by transesterification.
Figure 5.21 Blocking agents as used for blocking polyurethanes.
Figure 5.22 UV absorbers. (a) Structural change in two absorbers. (b) Corresponding absorption spectrum.
Figure 5.23 Radical scavengers. (a) Mechanism where
R
= -H, -CH
3
, -OC
n
H
2
n
+1
, … (b) HALS‐4; Effect of HALS‐4 on the gloss retention.
Chapter 6
Figure 6.1 Planar coating processes. (a) Doctor blade coating; (b) Roll method.
Figure 6.2 Spin coating. (a) Principle; (b) Processes involved.
Figure 6.3 Dip coating. (a) Laboratory dip coating; (b) Continuous dip coating. (1) Reel with substrate; (2) substrate; (3) bath; (4) paint of coating formulation; (5) guiding rolls; (6) oven; (7) wipers; (8) excess paint; (9) coated substrate.
Figure 6.4 Powder coatings. (a) Schematic representation of the leveling process; (b) Image of the spraying process; (c) Electrical field lines enabling covering of edges; (d) Schematic representation of a powder coating setup.
Figure 6.5 Flow and cure during heating. (a) Schematic representation showing the flow and cure window; (b) DMA result showing
G
′ for a resin and various amounts of crosslinking catalyst DMBA.
Figure 6.6 Encapsulated crosslinker for powder coatings. (a) Overview showing the capsules obtained; (b) Detail showing two broken capsules illustrating their core–shell nature.
Figure 6.7 Orange peel effect. (a) Image of the surface showing long and short wavelength ondulations; (b) Reflection of a lamp on a coating showing with the orange peel up (lower reflection) while still being glossy (upper reflection).
Figure 6.8 Schematic representation of the powder coating production process.
Figure 6.9 Automotive coating. (a) Simplified schematic image of coating a car; (b) Photograph of visual inspection of the downside of a car after painting.
Figure 6.10 Automotive coating. (a) Schematic image of the electrodeposition process, where one electrode charges the paint particles and the car carcass acts as the opposite electrode; (b) Schematic image of the layer sequence of automotive coatings.
Figure 6.11 Electrodeposition. (a) Anionic deposition in which negatively charged particles are decharged at the anode, thereby releasing oxygen and dissolving metal; (b) Cationic deposition in which positively charged particles are decharged at the cathode, thereby releasing hydrogen and hydroxyl ions.
Figure 6.12 The telegraphing effect in which surface unevenness is perfectly followed by the coating.
Chapter 7
Figure 7.1 The structure of the interfacial region between a surface and an ionic solution. (a) The Stern layer, located between the inner Helmholtz plane (IHP) through the centers of immobile ions specifically adsorbed at the surface and the outer Helmholtz plane (OHP) through the centers of hydrated counterions at the distance of their closest approach to the surface, and the diffuse layer beyond the OHP. Even for a highly charged surface, the surface density of the charges remains fairly low, typically 0.01 Å
−2
; (b) Sketch of the potential
ψ
across the Stern and diffuse layer.
Figure 7.2 Surfaces approaching each other. (a) Configuration with nonoverlapping and overlapping charge distributions; (b) Force between two flat surfaces for constant charge and constant potential. The calculation was done for a particle with radius
a
= 3 µm and a flat surface in water at 1 mM monovalent salt using the nonlinear Poisson–Boltzmann equation and the Derjaguin approximation for the potentials and charge densities indicated.
Figure 7.3 Zeta potential
ζ
as a function of pH for several oxides. The
isoelectric point
(IEP) refers to the pH where
ζ
= 0.
Figure 7.4 Liquid confined between two flat surfaces. (a) Schematic of the force as a function of distance where the numbers 1, 2, …, indicate the number of “layers” of molecules between the plates; (b) Experimental results for a silicon nitride AFM tip with a radius of about 50 nm approaching a mica surface in 1‐propanol at room temperature.
Figure 7.5 Polymers attached to a surface. (a) Disjoining pressure between two plates as a function of coverage Γ and radius of gyration
R
g
. A Kuhn length
l
= 0.4 nm and a chain length of
n
= 100 monomers was used. At low grafting density (Γ = 4 × 10
16
m
−2
) Eq. (7.31a) was used with the characteristic decay length
R
g
= 1.6 nm. At intermediate grafting density (Γ = 2 × 10
17
m
−2
) Eq. (7.31b) was used with
R
F
=
ln
3/5
= 6.3 nm. At high grafting density (Γ = 1 × 10
18
m
−2
), Eq. 7.32 was used with
L
0
=
nl
5/3
Γ
1/3
= 22 nm; (b) force between a silicon nitride tip of radius ≅ 50 nm and a silica surface (oxidized silicon) covered with a PS brush in toluene.
Figure 7.6 Schematic phase diagram showing an UCST where at
T
1
the liquid separates in two components with volume fractions
φ
1
and
φ
2
, respectively. In a similar way, above an LCST the liquid also separates in two components.
Figure 7.7 Solubility space according to Hansen. (a) Solubility sphere for component S
0
centered at the coordinates (2
δ
d
,
δ
p
,
δ
h
). The factor 2 is introduced for empirical reasons; (b) Cross section through the solubility sphere in the (
δ
p
,
δ
h
) plane showing two incompatible (S
1
and S
2
) and one compatible component (S
3
).
Figure 7.8 Schematic of a silica surface showing free (i), vicinal (ii), and geminal (iii) silanols. Silanols are present at a concentration of ≅8 ± 1 µmol m
−2
(≅5 silanols per nm
2
), the majority of which are vicinal pairs. Isolated and geminal silanols are generally more reactive than the hydrogen‐bonded vicinal variety. Siloxane bridges (iv) are considered to be inert in terms of reactivity.
Figure 7.9 Schematic of a liquid surface. (a) Density profile over the interface of a liquid; (b) Configuration in the bulk and at the surface of a liquid.
Figure 7.10 Contact configurations between a liquid droplet and solid surface.
Figure 7.11 Schematic of a liquid surface. (a) Three‐phase contact line; (b) Cross section of a droplet on a surface.
Figure 7.12 Dynamic contact angles. (a) Advancing contact angle; (b) Receding contact angle.
Figure 7.13 Dynamic Wilhelmy experiment. (a) Configuration used; (b) Schematic of the measured force as a function of the displacement. The numbers indicate the stages as shown in (a). The points A and R indicate the force from which
θ
A
and
θ
R
can be calculated, while the slope of curves 3 and 4 are due to buoyancy.
Figure 7.14 Schematic of a liquid drop on a rough surface. (a) Wenzel state; (b) Cassie–Baxter state.
Figure 7.15 Fluorocarbon side chain orientation. (a) Contact angles (1) after treatment with purified water and (2) after heating in air to 130 °C; (b) Schematic diagram of the orientation of the fluorocarbon side chains in (1) the low wetting state and (2) the high wetting state.
Figure 7.16 Anisotropic droplets due to an anisotropic surface topology introduced by uniaxial grinding with drop volume ≅5 mm
3
. (a) Front view,
θ
F
= 149.5°; (b) Side view,
θ
S
= 126.5°.
Figure 7.17 Interaction between two particles. (a) Schematic showing the contributions of attraction and repulsion, leading to a secondary minimum; (b) Potential curve according to DLVO theory for two spherical particles of radius
a
= 100 nm and Hamaker constant
H
= 10
−19
J as a function of the interparticle distance of closest approach
D
. Fast coagulation occurs for a low barrier, while colloidal stability is provided with a high barrier.
Figure 7.18 Emulsions. (a) Oil‐in‐water (O/W) emulsions in which the hydrophobic tail of the surfactant points into the oil droplet; (b) Water‐in‐oil (W/O) emulsion in which the hydrophobic tail of the surfactant points into the continuous oil matrix. The schemes also reflect that at a concentration
c
>
c
CMC
(
critical micelle concentration
), micelles are present, while for
c
≫
c
CMC
“super” micelles, that is, micelles constructed out of regular micelles, can be present.
Figure 7.19 The effective chain length
m
eff
for the CH
2
, PO, and EO groups as a function of the number functional groups
m
according to Guo et al.
Figure 7.20 Droplet radius
a
(
t
) of an O/W emulsion as function of time
t
for various initial droplet radii
a
0
at 25 °C in H
2
O using a concentration
n
0
= 1 g l
−1
of particles with a mass density
ρ
= 1 g cm
−3
in water with viscosity
η
= 1 mPa s.
Figure 7.21 Shaking an oil–water mixture leads to forms as shown on the left‐hand sides of figures (a) and (b). One may regard the process illustrated (from left to right in each panel) as a sketch of the emulsification process, where the emulsion type observed depends on the relative coalescence rates. (a) Leading to an O/W emulsion; (b) Leading to a W/O emulsion.
Figure 7.22 Examples of lattices used in SCF theory. (a) Spherical lattice for micelles; (b) rectangular lattice incorporating a flat wall.
Figure 7.23 Block scheme describing the implementation of the SF–SCF theory.
Figure 7.24 The surfactants Tween 20 (a) and Tween 80 (b) with an HLB value of, respectively, 16.7 and 15.
Figure 7.25 The concentration of surfactants (o) at the interface between water and benzene. (a) Profiles for Tween 20; (b) Profiles for Tween 80.
Figure 7.26 Span 20. (a) The structure of Span 20 with a HLB value of 8.6; (b) The concentration profile of Span 20 near the interface between water and benzene.
Figure 7.27 The normalized surface tension
γb
2
/
kT
of Span 20, Tween 20, and Tween 80 as a function of segment volume fraction
φ
, where
b
denotes the lattice spacing.
Figure 7.28 Density profiles for partially fluorinated PMMA (
r
= regular,
b
= block, M = methyl methacrylate, F = 1,1‐dihydroperfluoroheptyl methacrylate. (a)
r
‐M
55
F
5
; (b)
b
‐M
27
F
5
M
28
; (c)
b
‐M
55
F
5
.
Chapter 8
Figure 8.1 Synthesis of polycarbonate using TMP and TMC [3].
Figure 8.2 Baseline‐corrected ATR FTIR spectrum of polycarbonate showing the C-H stretching (2955 cm
−1
), the >C
O stretching (1782 cm
−1
), and the asymmetric C-O vibration (1188 cm
−1
).
Figure 8.3 GA‐FTIR mapping. (a) Spectra of biaxially oriented polypropylene (BOPP) and BOPP coated with different PUUs; (b) C
O stretch signal after deposition of PUU1 on BOPP, showing mainly PUU1 signal; (c) C
O stretch signal delamination of laminated BOPP, showing both areas with PUU1 signal and without PUU1 signal (lower area). For both (b) and (c), the field of view is 250 µm
2
.
Figure 8.4 High‐resolution chemical identification of polymer blend thin films of PMMA and SAN using tip‐enhanced Raman mapping after annealing at 250 °C for, respectively, 2 and 5 min. Coarsening during annealing is clearly observed, while the interface width is determined to be about 200 nm, in good agreement with the width as predicted by Flory–Huggins theory. Source: Xue et al. 2011 [8]. Reproduced with permission of American Chemical Society.
Figure 8.5 (a)
1
H NMR spectrum of ethanol in D
2
O showing the TMS peak at
δ
= 0 ppm and the CH
3
triplet, CH
2
quadruplet, and OH singlet and (b) typical
δ
‐ranges for various functional groups.
Figure 8.6
1
H NMR spectrum of polycarbonate as obtained in CDCl
3
obtained at 400 MHz.
Figure 8.7
13
C NMR spectrum of polycarbonate in CDCl
3
obtained at 125 MHz.
Figure 8.8 Silica in rubber showing 2D
29
Si{
1
H} HETCOR NMR spectra recorded using a MAS frequency of 10.0 kHz and a CP time of 4.0 ms. (a) Sol–gel synthesized silica and (b) high‐density silica. (c) Schematic drawing of the silicon tetrahedra denoted as Q
n
, with
n
= 2, 3, and 4, corresponding to the number of Si-O-Si bonds. The gray shading represents bulk silica corresponding to Q
4
silicon atoms.
Figure 8.9 Functional group analysis. (a) Determination of monoglyceride (MG) and diglycerides (DG) in diacylglycerol oil in pyridine–chloroform solution by 202.2 MHz
31
P NMR using cyclohexanol as internal standard after derivatization by dioxa‐chlorophospholane and (b) normal phase gradient polymer elution chromatography (GPEC) of an acid functional polyester showing the signal as obtained by an evaporative light scattering detector (ELSD) and a UV detector.
Figure 8.10 XPS results on films prepared from solventless liquid oligoesters (SLOs) and partially fluorinated isocyanates cured at 80 °C. (a) Spectra for a film with a fluorine content of 1 wt%. The labels
C
F
3
and
C
F
2
indicate the response for tri‐ and di‐fluorinated carbon atoms. Takeoff angles: (a) 75°, (b) 45°, and (c) 15°. (b) Surface F/C atomic ratio as a function of the added fluorine content in the films from SLO and F6‐N3300.
Figure 8.11 SEC chromatogram of polycarbonate showing an apparent monomodal distribution.
Figure 8.12 MALDI–MS spectrum of polycarbonate clearly showing two distributions (from a linear and branched polymer) corresponding to the sample for which in Figure 8.11 a unimodal SEC chromatogram is shown.
Figure 8.13 X‐ray diffraction. (a) Schematic illustrating the diffraction geometry and (b) schematic illustrating Bragg's law.
Figure 8.14 PE XRD pattern. (a) Azimuthal (
φ
) and angular (
θ
) intensity distribution; (b) Angular intensity (2
θ
) distribution with the 110 and 200 reflexions indicated.
Figure 8.15 s‐PS XRD pattern. (a) Partially crystalline PS; (b) Fully amorphous PS.
Figure 8.16 Grazing angle XRD. (a) Schematic showing penetration depth as a function of the grazing angle; (b) Diffraction peak of PDMS
1000
–PCL
32
coatings on an Al substrate showing the presence of characteristic peaks for PCL crystals at 2
θ
= 21.4° and 2
θ
= 23.7°. The lowest grazing angle corresponds to a thickness of less than ≈10 nm.
Figure 8.17 Anisotropy analysis by XRD. (a) PS–PPO blend; (b) PS–PPO blend containing a volume fraction
φ
= 0.01 CNTs; (c) PS–PPO blend containing a volume fraction
φ
= 0.03 CNTs; (d) Radially averaged intensities showing a rather limited anisotropy for the CNT distribution.
Figure 8.18 (A) Image formation in a compound microscope; (B) Schematic of a phase contrast microscope.
Figure 8.19 Optical micrographs of coating cross sections. (a) Waterborne alkyd coating on teakwood with an average thickness of 57 µm; (b) Typical automotive coating.
Figure 8.20 Electron pathways in transmission electron microscopy. (a) Conventional TEM, showing Köhler illumination; (b) STEM showing scanning illumination and the various angular regimes.
Figure 8.21 Electron tomography. (a) Acquisition of images, in this case with tilting up to 60°; (b) Reconstruction of 3D object.
Figure 8.22 Raspberry silica particle composed of diameter ≅10 and ≅80 nm individual particles. (a) Reconstructed section; (b) Reconstructed 3D representation.
Figure 8.23 Electron interaction with a specimen. (a) Electron excitation resulting in characteristic X‐rays or Auger electrons; (b) The volume within a specimen from which the various types of signals originate.
Figure 8.24 AFM. (a) Schematic of operation, (b) typical sharp tip, and (c) spherical tip with diameter of about 10 µm.
Figure 8.25 AFAM on a 20% methacrylate–80% epoxide coating. (a) The topography showing methacrylate nodules containing epoxide inclusions in an epoxide matrix; (b) The CRF distribution indicating the presence of about 50% methacrylate and 50% epoxide at the surface.
Figure 8.26 CAFM and EFM. (a) Schematic of the principle of CAFM (left) and EFM (right); (b) EFM images of the same area at (1)
U
t
= −2 V and (2)
U
t
= −6 V; (3) Topography of measured area; (4) Cross‐sectional AA′ at
U
t
= −2 V (1),
U
t
= −4 V (2),
U
t
= −6 V.
Chapter 9
Figure 9.1 Schematic of DSC setup.
Figure 9.2 DSC preliminaries. (a) Calibration curves at different heating rates. (b) Effect of sample size on the melting point response (
T
melt
= 155.8 °C).
Figure 9.3 Ideal DSC measurements with endothermic response pointing downward. (a) Heating curve. (b) Cooling curve.
Figure 9.4
T
g
measurements for blends. (a) Miscible PBD‐PI blends having a ratio
M
w
/
M
n
≅ 1.01–1.12 and measured at +15 °C min
−1
, showing a single
T
g
. (b) Immiscible SAN‐PC blend measured at +15 °C min
−1
, showing two separate
T
g
peaks corresponding to the
T
g
of the components.
Figure 9.5 Conversion measurements for an epoxy–amine coating. (a) The decreasing exothermic peak measured using a rate of +10 °C min
−1
as a function of curing time at 160 °C. (b) The fractional conversion increases as a function of time at various temperatures.
Figure 9.6 Relation between
T
g
and curing for an epoxy–amine coating showing the increase in
T
g
as function of conversion using data obtained at various temperatures.
Figure 9.7 Modulated DSC. (a) The temperature change as a function of time. (b) The total heat flow and the nonreversing and reversing heat flows for a quenched polyterephthalate.
Figure 9.8 Modulated DSC. (a) Improper modulation showing distortion of the signal. (b) The total heat flow and the reversing and nonreversing heat flows for poly(ethylene terephthalate), measured using a heating rate of 5 °C min
−1
.
Figure 9.9 TGA analysis. (a) The determination of the amount of water in nylon. (b) The determination of the amount of glass filler in an epoxy.
Figure 9.10 TGA analysis of pure PBT, PBT with
φ
= 0.04 CNTs, and PBT with
φ
= 0.04 graphene.
Figure 9.11 Sorption in polymers. (a) Type I isotherm (Henry's law), typical for hydrophobic polymers, and type II and type III isotherms as usually observed for hydrophilic and slightly hydrophilic polymers, respectively. (b) Schematic of absorbed molecules at low concentration in a hydrophobic polymer matrix (left) and in hydrophilic polymers (right).
Figure 9.12 PDS analysis for various gases in rubber. (a) Diffusivity
D
(10
10
m
2
s
−1
) and solubility
S
(10
2
cm
3
(STP) cm
−3
(pol.) bar
−1
). (b) Resulting permeability
P
(barrer).
Figure 9.13 Permeability
P
for several polymers as a function of their Lennard‐Jones diameter
σ
.
Figure 9.14 Polymer base coat as used for NMR determination of the water profile showing a schematic and a TEM image.
Figure 9.15 NMR signal profile for a coating with base coat (50 µm) and top coat (50 µm) during water uptake. The vertical arrow denotes the signal increase in the base coat and the horizontal arrow denotes swelling.
Figure 9.16 Schematic stress–strain (
σ
–
ε
) relationship using natural (elongational) strain
ε
= ln(
L
/
L
0
) ≅ Δ
L
/
L
0
for
Δ
L
/
L
0
≪ 1
. Upon loading a material shows elastic behavior with modulus
E
up to the yield strength
Y
, where after plastic and/or viscoelastic deformation occurs, finally reaching the fracture strength
S
. The elastic and plastic strains are indicated by
ε
e
and
ε
p
, respectively. High hardness implies high yield strength, while high toughness implies a large area below the
σ
–
ε
curve.
Figure 9.17 Possible time‐dependent response of a material. (a) Stress–strain curve, showing increasing stress
σ
with increasing applied strain rate
at a certain strain
ε
. (b) Creep behavior, showing increasing creep rate d
ε
/d
t
with increasing applied stress level
σ
and partial or full recovery. (c) Relaxation behavior, showing increasing stress
σ
with increasing applied strain level
ε
and decay to zero stress.
Figure 9.18 Simple analogous models. (a) The Maxwell, (b) Kelvin, and (c) Burgers model.
Figure 9.19 The (reduced) dynamic response of (a) the Maxwell and (b) the Kelvin model as a function of
τω
.
Figure 9.20 The superposition process for PC using data from different temperatures and experiments.
Figure 9.21 The (idealized) change in specific volume
V
for the glass transition at cooling rate 1 > cooling rate 2, leading to glass transition temperatures
T
g1
and
T
g2
. Also shown is the normal melting behavior at melting point
T
m
.
Figure 9.22 Dynamic behavior of PCHMA. (a) The frequency dependence of the tan
δ
at various temperatures. (b) Temperature dependence of the relaxation rate of the γ‐process.
Figure 9.23 Creep compliance of PS (
M
w
= 3.85 × 10
2
kg mol
−1
). (a) Experimental data as measured at the indicated temperatures. (b) The associated master curve.
Figure 9.24 Storage shear moduli
G
′ measured for a series of PS with different molar masses in the range
M
= 8.9 kg mol
−1
to
M
= 5.8 × 10
2
kg mol
−1
.
Figure 9.25 Time dependence of the tensile modulus
E
of PIB. Measurements at the indicated temperatures (left) and master curve, constructed at the reference temperature
T
= 298 K (right). The insert displays the shift factor as a function of temperature.
Figure 9.26 The zero‐shear viscosity
η
0
of several polymers as a function of molar mass
M
. For clarity the positions are shifted.
Figure 9.27 Variation of tan
δ
with temperature for high‐ and low‐density polyethylene (HDPE and LDPE, respectively).
Figure 9.28 Schematic output of a DM(T)A measurement, showing the elastic and viscous response as well as damping.
Figure 9.29 A DMTA measurement showing fracture of the specimen at 110 °C.
Figure 9.30 A perfect DMTA measurement showing the real part (storage modulus), the imaginary part (the loss modulus), the loss tangent (tan
δ
), and the length of the specimen.
Figure 9.31 A DMTA measurement showing slippage in the clamps (note the length of the specimen).
Figure 9.32 A DMTA measurement showing a messy result.
Figure 9.33 Primary (α‐ or
T
g
‐transition) and higher transitions. (a) The effect of temperature for the α‐ and β‐transitions in the PMMA. (b) The effect of moisture for the α‐, β‐, and γ‐transitions in nylon 6‐6.
Figure 9.34 Schematic view of Brinell, Vickers, Knoop, and Berkovich indentations.
Figure 9.35 Hardness indenters. (a) Vickers. (b) Knoop.
Figure 9.36 A typical nanoindentation curve in which the unloading slope
S
is indicated.
Figure 9.37 The indentation parameter
α
as a function of
a
/
h
.
Figure 9.38 The JKR technique. (a) The configuration used. (b) Experimental relation between
a
3
and the force
F
for nonmodified PDMS. The radius of the lens used in these measurements was 1.44 mm. The open circles (o) represent the data obtained from increasing loads and the closed circles (•) represent the data obtained from decreasing loads, indicating the absence of hysteresis.
Figure 9.39 The JKR technique. (a) The relation between
a
3
and
R
2
using PDMS lenses of various radii without external load. (b) The relation between
γ
LV
cos
θ
and
γ
SL
for mixtures of water and methanol on PDMS using independent data for
γ
SL
. Closed (•) and open (o) circles correspond to data obtained from advancing and receding contact angles, leading to
γ
SV
= 21.2 mJ m
−2
and
γ
SV
= 20.9 mJ m
−2
, respectively.
Figure 9.40 Correlation between work of adhesion and strength for adhesives. (a) The bond strength versus (1 + cos
θ
) for polyethylene using epoxy‐polyamide adhesive with
γ
LV
= 41.7 mJ m
−2
. (b) Joint strength using the butt joint geometry versus
γ
cri
of polymers using epoxy adhesive with
γ
LV
= 50 mJ m
−2
.
Figure 9.41 Correlation between work of adhesion and strength for composites and particle adhesion. (a) The shear strength for glass fiber composites. (b) The number density of adhering PE particles adhering to a silica surface immersed in water and water–alcohol mixtures.
Figure 9.42 Fracture. (a) The three modes of fracture. (b) The Griffith model for fracture consisting of a plate with a central elliptical hole of length
a
and width
b
.
Figure 9.43 The energy approach to fracture. (a) The model system consisting of a plate of width
W
, height
,
thickness
t
, and a central crack of length 2
a
. (b) The various contributions to the total Helmholtz energy
F
.
Figure 9.44 Crack tip phenomena. (a) The plastic zone ahead of a crack with length
a
. (b) Local bond breaking model as used in the description of the theoretical strength.
Figure 9.45 Bimaterial release rate as a function of the Dundurs parameter
α
. (a) Ratio
G
2
/
G
int
for a crack along the interface for
β
= 0. For any value
R
2
/
R
int
>
G
2
/
G
int
, the crack cannot deflect into material 2. (b) Ratio of
G
int
/
G
2
for a crack perpendicular to the interface for
β
= 0. For any value
R
int
/
R
2
>
G
int
/
G
2
, the crack cannot deflect along the interface.
Figure 9.46 Adhesive fracture energy
R
as a function of the reduced rate
. Actually
R
is multiplied by 223/
T
(to be conform with work of Ferry, although the physical significance is obscure).The labels refer to (a) cohesive fracture (of the crosslinked styrene–butadiene rubber adhesive), adhesive fracture on (b) fluorinated ethylene–propylene copolymer (FEP), etched 120 s, (c) modified FEP, (d) PET, and (e) nylon 11.
Figure 9.47 Adherence mechanisms. (a) Mechanical interlocking. (b) Diffusion interactions. (c) Covalent bonding.
Figure 9.48 Silane adhesion promoters. (a) Hydrolysis and condensation. (b) Hydrogen bonding and covalent bonding.
Figure 9.49 Typical silane adhesion promoters (applications in brackets). (a)
N
‐(2‐Aminoethyl)‐3‐aminopropyltrimethoxysilane (epoxies, phenolics, melamines, nylons, PVC acrylics, urethanes, nitrile rubbers). (b) 3‐Methacryloxypropyltrimethoxysilane (unsaturated polyesters, acrylics). (c) 3‐Chloropropyltrimethoxysilane (epoxies, nylons, urethanes). (d) 3‐Glycidoxypropyltrimethoxysilane (epoxies, urethanes, acrylics). (e) Vinyltriacetoxysilane (polyesters, polyolefins, EPDM). (f)
N
‐(2‐Vinylbenzylaminoethyl)‐3‐aminopropyltrimethoxysilane (unsaturated polyesters, styrenics, epoxies, PP, PE).
Figure 9.50 Flame treatment of PP‐EPDM rubber. (a) Change in
γ
with number of flame treatments. (b) Retention of
γ
with time.
Figure 9.51 Peel test. (a) Configuration. (b) Peeling force and crack tip displacement for Ni films on ABS.
Figure 9.52 Reproducibility of peel test results an 18.6 µm thick Cu coating on top of ABS, measured 24 h after the galvanic deposition using a delamination rate of 0.7 mm min
−1
. (a) For three different specimens from one sample. (b) For three different specimens from three different samples.
Figure 9.53 Work of adhesion between Cu and ABS as calculated using MD simulations depending on the amount of oxidation of the Cu surface and the coupling agent SMAh (poly(styrene‐
alt
‐maleic anhydride)) with the constituents of ABS (pBd, polybutadiene and SAN, (poly(styrene‐
co
‐acrylonitrile).
Figure 9.54 Pull‐off test. (a) Configuration during gluing. (b) Configuration during testing.
Figure 9.55 Ball‐drop test. (a) Configuration used. (b) Example of a pattern obtained on the coating.
Figure 9.56 Schematic of cross‐hatch test results showing typical patterns and their assessment. The labels 1, 2, etc. and 5B, 4B, etc. refer to the ISO and ASTM labeling, respectively.
Chapter 10
Figure 10.1 Schematics of the various types of flow behavior. (a) Newtonian. (b) Shear thinning. (c) Shear thickening. (d) Bingham plastic.
Figure 10.2 Thixotropy. (a) Shear stress
τ
as a function of shear rate
showing reversible (—) and partly reversible (‐ ‐) behavior for (positive) thixotropy. (b) Viscosity
η
as a function of time
t
showing reversible (—) and partly reversible (‐ ‐) behavior. (c) Casson plot showing
η
n
as a function of
.
Figure 10.3 Consistency for a drying paint. (a) Schematic of a plate–plate geometry using the rotation mode. (b)
G
and tan
δ
as a function of time
t
, as measured in oscillatory mode.
Figure 10.4 Viscosity of fluids. (a) Relative viscosity
η
r
= η
/
η
s
of suspensions as a function of volume fraction
φ
according to various models. For the Batchelor and Green expression,
B
2
= 6.0, and for the Krieger–Dougherty expression
φ
m
= 0.64 was taken. (b) The dependence of viscosity
η
of a polymer melt or concentrated solution on molar mass
M
, showing
η
∼
M
ν
. Below the critical molar mass
M
cri
, the fluid is nonentangled, and
ν
≅ 1.0 for polymer melts, while for polymers solutions
ν
≅ 0.5–0.8. Above the critical molar mass
M
cri
,
the fluid is entangled with
ν
≅ 3.4.
Figure 10.5 Intrinsic viscosity [
η
] for spheroids with aspect ratio
w
=
a
/
b
, where
a
and
b
are the major and minor semiaxes. The broken lines represent expressions for oblate spheroids or disk‐shaped particles (
w
≪ 1) and prolate spheroids or rodlike particle (
w
≫ 1).
Figure 10.6 Intrinsic viscosity [
η
] as a function of
for ellipsoids with varying aspect ratio
w
=
a
/
b
, where
a
and
b
are the major and minor semiaxes, as indicated. (a) Oblate spheroids or disk‐shaped particles (
w
≪ 1). (b) Prolate spheroids or rodlike particles (
w
≫ 1).
Figure 10.7 Rheological behavior for polymers. (a) End‐to‐end distance
r
2
as a function of concentration
c
. (b) Schematic of the
M
–
c
diagram for polymers with molar mass
M
as a function of concentration
c
showing the various regimes. D, dilute; S, semidilute; C, concentrated; −, not entangled; +, entangled. Numbers approximately valid for polybutadiene.
Figure 10.8 Viscosity behavior of powder coatings. (a) Dynamic viscosity of a polyester powder coating material. (b) The viscosity
η
as a function of time
t
during the baking process.
Figure 10.9 Examples of conventional thickeners for waterborne coatings. (a) Polyethylene glycol. (b) Cellulose derivative thickener.
Figure 10.10 Viscosity
η
as a function of shear rate
. (a) Viscosity
η
of conventional (solid symbols) and associative thickeners (open symbols) in water and in combination with latex. (b) Viscosity
η
of a waterborne (WB) acrylic paint and that of a traditional alkyd paint.
Figure 10.11 Example of (a) an associative thickener and (b) its associative character in aqueous solution.
Figure 10.12 (a) Viscosity
η
as a function of temperature
T
of an oligomer solution for 93%, 89%, and 79% solid contents. (b) The temperature–time–transformation (TTT) diagram.
Chapter 11
Figure 11.1 OM images of dewetting of PS films of thickness
h
= 64 ± 2 nm with different molar mass
M
w
and aging time
t
A
under saturated acetone vapor at room temperature. (a)–(c)
M
w
= 4.1 kg mol
−1
,
t
A
= 12 h;
t
A
= 60 h;
t
A
= 108 h, respectively; (d)–(f)
M
w
= 48.1 kg mol
−1
,
t
A
= 12 h;
t
A
= 60 h;
t
A
= 108 h, respectively. The bar scale is 100 µm in (a)–(e) and 200 µm in (f).
Figure 11.2 Segregation defects. (a) Flooding and floating. (b) Agglomerated, dispersed, and flocculated particles.
Figure 11.3 Schematic of the change in viscosity
η
with temperature
T
for a conventional and high solids (HS) coating, indicating the approximate transition between the flow dominated regime (solvent evaporation) and the diffusion dominated regime (crosslinking).
Figure 11.4 The stimulus for color depends on factors related to the light source, the colored object, and the sensitivity of the eye.
Figure 11.5 Intensity distribution of radiation of black body as function of its temperature.
Figure 11.6 The sensitivity and the angular distribution of the different receptor types.
Figure 11.7 The contrast effect: the central part in a left frame is erroneously seen as darker than the central part in the right frame.
Figure 11.8 Color matching functions (the sensitivities of the color receptors for spectral light) for the color receptors with 2° (•) and 10° (o) foveal angle.
Figure 11.9 The 1931 CIE
x
,
y
chromaticity diagram.
Figure 11.10 Reflection and transmission. (a) Specular and diffuse reflection and transmission. (b) Schematic of multiple reflection on particles dispersed in a coating. The angles of incidence and reflection are not necessarily the same as the particles may be rough. The dotted line indicates the maximum penetration depth from below which light no longer escapes.
Figure 11.11 The additive and the subtractive trichromatic systems.
Figure 11.12 The CIELAB system. (a) The CIELAB color chart, where A indicates a typical yellow color and B a typical red color in this black‐and‐white image. (b) The total system where the
L
*
value is represented on the center axis and the
a
*
and
b
*
axes appear on the horizontal plane.
Figure 11.13 CIE recommended geometries for reflectance measurement with white light. (a) Single angle using the 0°/45° geometry. (b) Multiangle geometry. (c) Integrating sphere.
Figure 11.14 Tolerance ellipsoid inside the tolerance box (Δ
a
*
,Δ
b
*
) of the CIELAB system and within the tolerance wedge (Δ
C
*
,Δ
h
°) of CIELCH system.
Figure 11.15 Quantitative descriptive analysis. (a) Correlation matrix for the nine attributes chosen, showing strong positive correlation for A3–A4 and A8–A9 and a strong negative correlation for A3–A6. (b) Plot of the samples used, including benchmark materials, in the cross section with axes
velvety–silky
and
roughness
of the 3D principal components space having
stickiness
as the third axis.
Chapter 12
Figure 12.1 Electrical conductivity measurement configurations. (a) In‐plane two‐point. (b) In‐plane four‐point. (c) Through‐the‐thickness two‐point. (d) Through‐the‐thickness with guard electrode.
Figure 12.2 Carbon‐black coating containing 1.25 vol% CB on an AA2024 aluminum alloy substrate. (a) TEM micrograph, scale bar = 0.2 µm. (b) Bode plot showing the absolute value of the impedance |
Z
| and phase angle
φ
as function frequency
ν
.
Figure 12.3 The molecular structure of
trans
‐polyacetylene. (a) Regular or equal bond length structure. (b) Distorted or alternating bond length structure for which the displacement from the average bond length is given by
u
n
= (−1)
n
u
.
Figure 12.4 Intrinsically conductive polymers. (a)
trans
‐Polyacetylene (t‐PAc). (b)
cis
‐Polyacetylene (c‐PAc). (c) Poly(
para
‐phenylene) (p‐PP). (d) Polypyrrole (PPy). (e) Polythiophene (PTh).
Figure 12.5 Band scheme where
E
F
indicates the Fermi level. (a) A single band when using one atomic wave function per atom (full line in the scheme). (b) Two bands when using two atomic wave functions per atom (dotted lines in the scheme).
Figure 12.6 Band structure for
trans
‐polyacetylene showing (
ε
k
−
α
)/
β
=
f
(
k
;
γ
) where
k
is the wave vector and
γ
the coupling constant. The upper curve represents the conduction band, while the lower curve represents the valence band. Conventionally band diagrams, for example, as given in Figure 12.7, typically show only the part as indicated by the box in (c). (a)
γ
= 0.0
β
; (b)
γ
= 0.1
β
; (c)
γ
= 0.3
β
.
Figure 12.7 Band structure for t‐PAc using five atomic wave functions per atom so that five valence and five conduction bands result. The dotted line indicates the Fermi level. The symbols at the
x
‐axis indicate the direction in the unit cell in
k
‐space, the so‐called Brillouin zone. (a) For identical bond lengths (1.4 Å) showing the absence of a band gap. (b) For alternating bond lengths with experimental bond length values (1.36 and 1.43 Å) showing the presence of a band gap. (c) For alternating bond lengths with exaggerated bond length difference (1.34 and 1.54 Å) showing an increased band gap.
Figure 12.8 (a) Total energy for
trans
‐polyacetylene as a function of
u
showing a double well, favoring the alternating bond length structure. (b) Schematic of a soliton.
Figure 12.9 Energy levels in t‐PAc for solitons and polarons. (a) Soliton. (b) Antisoliton. (c) Negative soliton. (d) Positive soliton. (e) Negative polaron. (f) Positive polaron.
Figure 12.10 The effect of doping on the conductivity of t‐PAc.
Figure 12.11 Disordered semiconductor conductivity. (a) Charge transfer via hopping and tunneling. (b) Band structure and the associated mobility gap.
Figure 12.12 P3HT characteristics. (a) Isosurface generated from tomographic reconstruction of a P3HT nanowire. (b) Isosurface from the middle of the nanowire showing increased order. (c) Model of the lamellar order in the middle of the nanowire. (d) Model showing crystalline order in the bulk and disorder on the side of the nanowire. (e) Slice from the tomographic reconstruction showing a cross section of the wire. (f) The same slice overlaid with the corresponding segment of the segmented structure. (g) Cartoon depicting the ordered bulk and the disordered edges.
Figure 12.13 P3HT–PCBM characteristics. (a–c) TEM images of photoactive layers obtained from the initial solution, an intermediate state, and the final dispersion, respectively. The P3HT is light and PCBM dark. The insets are the LDED patterns corresponding to the images. (d) Radially integrated LDED patterns. (e) WAX diffraction patterns of the photoactive layers. (f) UV–vis absorption spectra of the photoactive layers. Note that the final PCBM has a higher density than P3HT, so that the contrast is inverted and P3HT will show up as lighter areas. In contrast, the cryo‐TEM images show P3HT as dark areas against a background of vitrified solution of PCBM in toluene.
Figure 12.14 Some regular lattices. (a) Bethe lattice,
z
= 3. (b) Honeycomb lattice,
z
= 3. (c) Square lattice,
z
= 4. (d) Kagomé lattice,
z
= 4. (e) Triangular lattice,
z
= 6.
Figure 12.15 Percolation and renormalization by taking three spheres together applying the majority rule. (a) A schematic of the original packing. (b) Four possible renormalized sites.
Figure 12.16 Generalized EMT models. (a) Building blocks for the microstructure of the symmetric Bruggeman (BS), Maxwell–Wagner (MW), and asymmetric Bruggeman model (BA). (b) DC conductivity behavior of a matrix (
σ
f
= 3.3 × 10
9
Ω m) as a function of filler volume fraction
φ
(
σ
f
= 3.3 × 10
6
Ω m) showing the Hashin–Shtrikman bounds or Maxwell–Wagner results (curves a and e), the asymmetric Bruggeman result (curves b and d), and the symmetric Bruggeman result (curve c).
Figure 12.17 The experimentally determined
σ
‐values for various volume fractions of ATO particles and different MPS/ATO ratios (dots), fitted to the modified EMT model (curves).
Figure 12.18 Percolation behavior for carbon–fiber/PMMA composites with well‐defined fiber aspect ratios. (a) Normalized conductivity
σ/σ
m
as a function of volume fraction
φ
. The dotted line represent the fit to Eq. 12.40. (b) Experimental and Monte Carlo simulation results for
φ
cri
as a function of inverse aspect ratio
A
with either soft‐core (overlapping) or hard‐core/soft‐shell (nonoverlapping) fibers.
Figure 12.19 The relation between a graphene sheet and buckyballs, carbon nanotubes, and graphite.
Figure 12.20 The molecular and crystal structure of Phthalcon 11/12.
Figure 12.21 Temperature dependence of the conductivity of CB–polymer composites, plotted in the form of ln[
σ
cri
/
σ
(
T
)] versus
T
−
α
for different values of
α
. (a)
α
= 1.0, (b)
α
= 0.70, (c)
α
= 0.65, (d)
α
= 0.60, and (e)
α
= 0.50, showing that the best fit by a straight line is given by
α
= 0.65 (c).
Figure 12.22 Latex‐based carbon composite coatings. (a) UV–vis monitoring of the exfoliation process in water over time following the height of the peak located at about 268 nm for aqueous 0.1 wt% filler solutions (diluted 150 times). (b) Electrical conductivity versus filler mass concentration. To obtain conductivity as function of volume concentration, values must be multiplied by ≅2, which corresponds to the average density of the carbon fillers in g cm
−3
. Values represent an average of three measurements with standard deviations below 10%.
Chapter 13
Figure 13.1 Different phases of marine biofouling: timeline evolution and respective roughness increase.
Figure 13.2 Schematic of marine AF coatings approaches. (a) and (c) Biocide‐release‐based strategies; (b) and (d) Non‐biocide‐release‐based strategies.
Figure 13.3 The Baier curve demonstrating the relative amount of biofouling versus the critical surface tension of various chemical substrates. Source: Baier (2006) [17]. Adapted with permission of Springer.
Figure 13.4 The relationship between relative adhesion
R
and the square root of the product of critical surface energy
γ
cri
and
E
modulus for polymers to be used in AF surfaces. The inset numbers correspond to the polymers listed in Table 13.1. Source: Redrawn from data in Ref. [43].
Figure 13.5 Schematic of the formation of self‐stratifying coatings.
Figure 13.6 Examples of typical chemical segments (chemical structures) introduced into PDMS‐based formulations or prepolymers to improve its mechanical and adhesion properties. (a) Poly(urethane) [58]. (b) Poly(urea) [61]. (c) Epoxy [62]. (d) Oxetane [63]. Source: Chen et al. (2008) [63]. Reproduced with permission of John Wiley & Sons.
Figure 13.7 Examples of perfluoropolymers used for AF surfaces with improved immobilization of the perfluoroalkyl groups, that is, decreased chances of surface reorganization. (a) Perfluoro(methacrylate)‐acrylic acid copolymer crosslinked with (2‐isopropenyl‐2‐oxazoline)‐methacrylate copolymer. Source: Schmidt et al. (2004) [73]. Reproduced with permission of the American Chemical Society. (b) Poly(
n
‐alkyl methacrylates) end capped with 2‐perfluorooctyl methacrylates. Source: Gao et al. (2013) [74]. Reproduced with permission of Elsevier. (c) and (d) fluorinated block copolymers with semifluorinated liquid crystalline side chains connected by an ester or ether bond, respectively. Source: (c) and (d) Wang et al. (1997) [75]. Reproduced with permission of the American Chemical Society and Youngblood et al. (2003) [76]. Reproduced with permission of Taylor & Francis.
Figure 13.8 Examples of silicone–fluorine components for AF coatings. (a) Trifluoromethyl‐branched fluorine end‐capped PFPE (Fomblin Y). (b) Linear diorgano end‐capped PFPE (Fomblin Z). (c) (Heptadecafluoro‐1,1,2,2‐tetrahydrodecil)triethoxysilane (fluorinated‐TEOS). (d) Copolymer of perfluorinated‐ and polysiloxane‐modified acrylates [81]. Source: Mielczarski et al. (2010) [81]. Reproduced with permission of the American Chemical Society.
Figure 13.9 Schematic representation of preventing the attachment of proteins via hydration layer derived on PEG chains.
Figure 13.10 Chemical structures of (a) poly(sulfobetainmethacrylate) (PSBMA), (b) hyaluronic acid (HA), (c) alginic acid (AA), (d) pectic acid (PA), (e) triethylamine N‐oxide (TMAO), (f) arginine, and (g) polyglycerol dendroid.
Figure 13.11 (a) Chemical structure of comblike block copolymer with amphiphilic side chains; (b) Proposed mechanism for surface reorganization of the ethoxylated fluoroalkyl side chains upon immersion of the surface in water. Source: Krishnan et al. (2006) [121]. Reproduced with permission of the American Chemical Society.
Figure 13.12 Schematic model representing the spore adhesion to different surface features. Source: Callow et al. (2002) [127]. Adapted with permission of Taylor & Francis.
Chapter 14
Figure 14.1 Performance of a material along its service lifetime, showing the performance of the original material, the traditionally improved material, and the ideal and the real self‐healing material.
Figure 14.2 Damage from the microscopic to the macroscopic level. (a) Escalation and associated phenomena and (b) recovery and associated mechanisms.
Figure 14.3 Extrinsic healing approaches in polymeric coatings: (a) 2K capsules with a liquid healing agent [21], (b) 1K capsules with a surface active agent [22], (c) expansive phases [23], and (d) release of corrosion inhibitors from inorganic carriers [24].
Figure 14.4 Scratch formation and recovery in thermoplastic (a) and thermoset (b) films.
Figure 14.5 Schemes of (a) molecular interdiffusion and (b) chain end segregation models showing the stages of healing occurring at polymer–polymer interfaces: (1) surface rearrangement, (2) surface approach, (3) wetting of surfaces, (4) low level of diffusion across interfaces, and (5) high level of diffusion, equilibration, and randomization.
Figure 14.6 Reversible covalent networks based on azlactone and phenol.
Figure 14.7 Reversible covalent networks based on imidazole and isocyanate.
Figure 14.8 (a) Furfuryl methacrylate‐
block
‐butyl methacrylate (FMA‐
b
‐BA) (co)polymer; (b) Schematic representation of the crosslinked network made by reacting with a bismaleimide according to DA (reversible acrylic‐based polymer networks for powder coatings); (c) Furan‐modified, (d) maleimide‐modified epoxies; (e) Jeffamine as components for reversible epoxy–amine networks containing Diels–Alder (DA) adducts.
Figure 14.9 Reversible covalent networks based on thiol–ene combination.
Figure 14.10 (a) Idealized structure of a hybrid sol–gel intrinsic self‐healing polymer network. Insets show some of the key chemical structures used on the hybrid systems, (b) reversible tetrasulfide (S─S─S─S) bonds, (c) inorganic crosslinks, and (d) organic epoxy–amine crosslinks. Source: Adapted from Ref. [99].
Figure 14.11 Bayer Materials Science's representation of scratch‐healing polyurethane coatings, showing (a) virgin coating; (b) inflicted damage, for example, by car washing; (c) recovery by thermal treatment above
T
g
(2 h, 60 °C); (d) recovered coating by reflow.
Figure 14.12 Delamination (white irregular lines) and pitting (white‐gray dots) around a scribe (vertical line) of a coated AA7050 panel exposed to 0.05 M NaCl in distilled water, showing a significant time delay in the appearance of both delamination and pitting using a silyl ester as healing agent (from 3 days to more than 12 days). Source: Adapted from Garcia et al. 2014 [141].
Figure 14.13 Schematic of the dual experimental–simulation approach used to investigate self‐replenishing functional polymeric coatings in a loop‐feeding process.
Figure 14.14 (a) Low surface energy films components (
EXP
= experimental and
SIM
= simulation): (1) polyester precursor (TMP–PCL
x
,
x
= 3
n
, where
n
is the number of caprolactone (CL) units per arm), (2) perfluorinated dangling chains (F
17
C
8
–PCL
y
,
y
= total number of CL units), and (3) tri‐isocyanate crosslinker and (b)
simulation
box snapshots: complete system (A) and details of the air–film interface (B) and bulk (C). Sources: Esteves et al. 2014 [70]. Adapted with permission of AIP Publishing and Esteves et al. 2014 [150]. Adapted with permission of the Royal Society of Chemistry.
Figure 14.15 F/C ratios at a probe depth of 5 and 10 nm after cutting slices of 30 μm from a 200 μm thick polyurethane coating containing perfluorooctyl–PCL with 1 wt% of fluorine in bulk.
Figure 14.16 Simulation of fluorine‐beads profile as function of
z‐
coordinate. (a) Top layer: Damage and multiple self‐replenishing of films prepared from TMP–PCL
24
and 2 wt% of fluorine (via F
17
C
8
–PCL
16
dangling chains)
. Spheres
: Before the damage.
Open stars
and
triangles
