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Contents

Cover

Title page

Copyright page

Preface

Part I: Materials and Methods: Design and Fabrication

Chapter 1: The Science of Molecular Precursor Method
1. 1.1 Metal Complex
2. 1.2 Molecular Precursor Method
3. 1.3 Counter Ion (Stability)
4. 1.4 Conversion Process from Precursor Film to Oxide Thin Film
5. 1.5 Anatase–Rutile Transformation Controlled by Ligand
6. 1.6 Homogeneity
7. 1.7 Miscibility
8. 1.8 Coatability (Thin Hydroxyapatite Coating of Ti Fiber Web Scaffolds)
9. 1.9 Oxygen-Deficient Rutile Thin Films
10. 1.10 Cu Thin Film
11. 1.11 Applications Using the Molecular Precursor Method
12. 1.12 Conclusion
13. References
Chapter 2: Cold Spray—Advanced Coating Process and 3D Modeling
1. 2.1 Introduction
2. 2.2 3D Numerical Modeling of Cold Spray Coating
3. 2.3 Experimental Methods of Cold Spray Coatings for Validation of 3D Model
4. 2.4 Results and Discussions
5. 2.5 Conclusion
6. References
Chapter 3: Effects of Laser Process Parameters on Overlapped Multipass/Multitrack Hardened Bead Parameters of Ti-6Al-4V Titanium Alloy Using Continuous-Wave Rectangular Beam
1. 3.1 Introduction
2. 3.2 Experimental Methodology
3. 3.3 Results and Discussion
4. 3.4 Conclusions
5. Acknowledgment
6. References
Chapter 4: Dimensionally Stable Lead Dioxide Anodes Electrodeposited from Methanesulfonate Electrolytes: Physicochemical Properties and Electrocatalytic Reactivity in Oxygen Transfer Reactions
1. 4.1 Introduction
2. 4.2 Chemical Composition of Coatings
3. 4.3 Electrocatalytic Properties of Materials
4. 4.4 Electrode Endurance Tests
5. 4.5 Conclusions
6. References
Chapter 5: Polycrystalline Diamond Coating Protects Zr Cladding Surface Against Corrosion in Water-Cooled Nuclear Reactors: Nuclear Fuel Durability Enhancement
1. 5.1 Introduction
2. 5.2 Zr Alloy Surface Corrosion—General Description
3. 5.3 Growth of Polycrystalline Diamond as Anticorrosion Coating on Zr Alloy Surface
4. 5.4 Properties of PCD-Coated Zr Alloy Samples Processed in Autoclave
5. 5.5 PCD Coating Increases Operation Safety and Prolongs the Zr Nuclear Fuel Cladding Lifetime—Overall Summaries
6. 5.6 Conclusion
7. Acknowledgments
8. References
Chapter 6: High-Performance WC-Based Coatings for Narrow and Complex Geometries
1. 6.1 Introduction
2. 6.2 Experimental
3. 6.3 Results and Discussion
4. 6.4 Conclusions
5. References

Part II: Coating Materials Nanotechnology

Chapter 7: Nanotechnology in Paints and Coatings
1. 7.1 Introduction
2. 7.2 Application of Nanopaints and Nanocoating in the Automotive Industry
3. 7.3 Application of Nanopaints and Nanocoating in the Energy Sector
4. 7.4 Application of Nanocoating in Catalysis
5. 7.5 Application of Nanopaints and Nanocoating in the Marine Industry
6. 7.6 Applications of Nanopaints and Nanocoating in the Aerospace Industry
7. 7.7 Domestic and Civil Engineering Applications of Nanopaints and Coating
8. 7.8 Medical and Biomedical Applications of Nanocoating
9. 7.9 Defense and Military Applications of Nanopaints and Coatings
10. 7.10 Conclusion
11. 7.11 Future Trend
12. References
Chapter 8: Anodic Oxide Nanostructures: Theories of Anodic Nanostructure Self-Organization
1. 8.1 Introduction
2. 8.2 Anodization
3. 8.3 Barrier-Type Anodic Metal Oxide Films
4. 8.4 Porous-Type Anodic Metal Oxide Films
5. 8.5 Theories or Models of Growth Kinetics of Anodic Oxide Films and Fundamental Equations for High-Field Ionic Conductivity
6. 8.6 Corrosion Characteristics and Related Phenomenon
7. 8.7 Electrochemical Impedance Spectroscopy
8. 8.8 Characterization Techniques
9. References
Chapter 9: Nanodiamond Reinforced Epoxy Composite: Prospective Material for Coatings
1. 9.1 Introduction
2. 9.2 Nanodiamond: A Leading Carbon Nanomaterial
3. 9.3 Epoxy: A Multipurpose Thermoset Polymer
4. 9.4 Nanodiamond Dispersion in Epoxy: Impediments and Challenges
5. 9.5 Epoxy/Nanodiamond Coatings
6. 9.6 Coating Formulation
7. 9.7 Industrial Relevance of Epoxy/ND Coatings
8. 9.8 Summary, Challenges, and Outlook
9. References
Chapter 10: Nanostructured Metal–Metal Oxides and Their Electrocatalytic Applications
1. 10.1 Brief History of Electrocatalysis
2. 10.2 Electrocatalytic Activity
3. 10.3 Oxygen Reduction Reaction
4. 10.4 Transition Metal Chalcogenides and Their Catalytic Applications
5. 10.5 Preparation of Nanostructured Transition Metal Oxide Surfaces
6. 10.6 Polyoxometallates (POM)
7. 10.7 Future Trends in Electrocatalysis Applications of Metal/metal oxides
8. References

Part III: Advanced Coating Technology and Applications

Chapter 11: Solid-Phase Microextraction Coatings Based on Tailored Materials: Metal–Organic Frameworks and Molecularly Imprinted Polymers
1. 11.1 Solid-Phase Microextraction
2. 11.2 HS-SPME-GC Applications Using MOF-Based Coatings
3. 11.3 DI-SPME-LC Applications Using MIP-Based Coatings
4. 11.4 Conclusions and Trends
5. Acknowledgements
6. References
Chapter 12: Investigations on Laser Surface Modification of Commercially Pure Titanium Using Continuous-Wave Nd:YAG Laser
1. 12.1 Introduction
2. 12.2 Experimental Design
3. 12.3 Experimental Methodology
4. 12.4 Results and Discussions
5. 12.5 Conclusions
6. Acknowledgements
7. References
Chapter 13: Multiscale Engineering and Scalable Fabrication of Super(de)wetting Coatings
1. 13.1 Introduction
2. 13.2 Fundamentals of Wettability and Superwettability
3. 13.3 Nature to Artificial: Bioinspired Engineering
4. 13.4 Top-Down and Bottom-Up Nanotexturing Approaches
5. 13.5 Superhydrophilicity
6. 13.6 Superhydrophobicity
7. 13.7 Superoleophobicity and Superamphiphobicity
8. 13.8 Superomniphobicity
9. 13.9 Conclusions
10. References
Chapter 14: Polymeric Materials in Coatings for Biomedical Applications
1. 14.1 Introduction
2. 14.2 Polymeric Coating Materials
3. 14.3 Conclusion
4. References

Index

End User License Agreement

List of Illustrations

Chapter 1

Figure 1.1 An ORTEP view of the precursor complex having the EDTA and peroxo ligands linked to the central Ti⁴⁺ ion.
Figure 1.2 Schematic for shrinkage models of metal complex film (left: Ti–EDTA complex; right: Ti–NTA complex).
Figure 1.3 The relation of the concentration of the complex and the thickness of the resulting anatase thin film.
Figure 1.4 The TG–DTA curves of the LTO precursor gel obtained by evaporating the precursor solution. The measurement temperature was increased from 25 °C to 1000 °C at a rate of 10 °C/min using an air flow rate of 0.1 dm³/min.
Figure 1.5 Cross-sectional FE-SEM images of the single- and double-layer films on the Si substrate with trenches of (a) 1.0, (b) 0.5, and (c) 0.2 µm widths and 5 µm depth.
Figure 1.6 The colorless battery before charge and after discharge (left) and blue-gray battery after charge (right).
Figure 1.7 The charge/discharge cyclic test of the assembled battery. The lines indicate the following: —; a constant current of 0.2 mA, —; 1-sun irradiation.

Chapter 2

Figure 2.1 CGT KINETIKS 3000 System [19].
Figure 2.2 Plasma Giken PCS 1000 CS system [19].
Figure 2.3 Impact innovations GmbH inside diameter spray head and adapter [19].
Figure 2.4 Axial power-feed adapter with water cooling by Impact Innovations GmbH [19].
Figure 2.5 Use of cold spray to repair aeronautic gearbox made of A357 aluminium alloy. (Courtesy of Avio and Veneto Nanotech) [9].
Figure 2.6 (a) The computational domain showing boundary condition, nozzle, and substrate used in 3D CS numerical model and (b) specifications of CS nozzle [32].
Figure 2.7 Developed mesh for solid and fluid domains: (a) complete CFD three-dimensional computational grid; (b) cold spray convergent–divergent nozzle throat; (c)cold spray nozzle exit and substrate surface at 35 mm standoff distance; (d) high pressure gas inlet plane [32].
Figure 2.8 Distribution of particle size for a commercial purity (CP) titanium powder used for the 3D modelcold spray [47, 48].
Figure 2.9 Cross section of titanium substrate showing exact placement of diagonally oriented five k-type thermocouples from rear side [32].
Figure 2.10 Schematic diagram of cold spray system with particle image velocimetry (PIV) set-up to quantify titanium particles velocity in the cold spray whole flow field (cold spray plume) [61].
Figure 2.11 Comparison of experimental results with calibrated 3D multicomponent model thermal outcome for all five thermocouples at 550 °C and 1.4 MPa cold spray conditions [32].
Figure 2.12 Holistic estimation of temperature from gas injection point to the titanium substrate surface for cold spray conditions 550 °C and 1.4 MPa, using the calibrated 3D multicomponent model [32].
Figure 2.13 PIV measured velocity [48, 61] for cold spray CP titanium supersonic jet with (a) helium at 550 °C, 1.4 MPa, (b) nitrogen at 550 °C, 1.4 MPa, (c) nitrogen at 550 °C, 2.5 MPa, (d) nitrogen at 750 °C, 2.5 MPa, and 3D model estimated velocity for spherical titanium particles with (e) helium at 550 °C, 1.4 MPa, (f) nitrogen at 550 °C, 1.4 MPa, (g) nitrogen at 550 °C, 2.5 MPa, and (h) nitrogen at 750 °C, 2.5 MPa.
Figure 2.14 3D model particle velocity estimations for spherical CP titanium particles in cold spray supersonic jet with nitrogen [48] at (a) 600 °C, 3 MPa (b) 750 °C, 3 MPa (c) 750 °C, 4 MPa (d) 800 °C, 4 MPa and helium at (e) 70 °C, 0.75 MPa.
Figure 2.15 Comparison of PIV-measured CP titanium spherical particle velocity with 3D multicomponent model outcome at 40 mm away from the nozzle exit for five cold spray experiment conditions [48].
Figure 2.16 Estimated particle velocity as a function of distance normal to the nozzle centerline for two particle size groups, (a) D1 (15–27) µm and (b) D2 (40–55) µm, for all cold spray conditions presented in Table 2.2 where maximum velocity in the cold spray plume was achieved [48].
Figure 2.17 3D model estimated temperature of CP titanium particles with respect to the nozzle centerline axis as a function of distance from nozzle exit for four nitrogen jet conditions [48].
Figure 2.18 3D model estimated titanium particles thermal profile normal to cold spray nozzle centerline for four experimental conditions at 40 mm distance outside of the nozzle [48].

Chapter 3

Figure 3.1 Schematic representation of laser transformation hardening by rectangular or line beam.
Figure 3.2 Diode-Pumped Solid-State (DPSS) Nd:YAG Laser source [18].
Figure 3.3 Experimental setup connections showing the laser beam head with shielding arrangements [18].
Figure 3.4 The overlapped multipass laser hardened bead on trial profiles for rectangular/line beam for the selected laser process parameters as received after the bead on trial [18].
Figure 3.5 The schematic diagram of top and side view of assembly of fixture plates to be fabricated for laser hardening.
Figure 3.6 Photographic view of bottom fixture plate provided with a slot fitted with the hollow cylindrical copper tube to circulate the shielding gas [18].
Figure 3.7 Photographic view of top fixture plate provided with a slot of 20 mm wide and 95 mm length for hardening window and two side holes inserted with a pair of hollow cylindrical copper tubes with small pores, throughout the hardening window length to circulate the shielding gas [18].
Figure 3.8 The overall assembly of fixture plates fabricated for laser transformation hardening [18].
Figure 3.9 Maximum, minimum, and average values of HD for the two selected laser process parameters using rectangular beam.
Figure 3.10 Microstructures of overlapped multipass laser hardened surfaces of Ti-6Al-4V alloy using rectangular beam for the two selected process parameters: 1. high laser process parameter (HLPP), LP = 800 Watts, SS = 800 mm/min and 2. low laser process parameter (LLPP), LP = 600 Watts, SS = 600 mm/min, at 200 × magnification.
Figure 3.11 Showing the SEM image of as-received 2-mm-thick Ti-6Al-4V titanium alloy base material.

Chapter 4

Figure 4.1 SEM micrographs of coatings, obtained from next solutions: (a) 0.1 M Pb(NO₃)₂ + 0.1 MHNO₃; (b) 0.1M Pb(CH₃SO₃)₂ + 0.1 M CH₃SO₃ H.
Figure 4.2 PbO₂ (a) PbO₂-1.81wt% Bi; (b) O 1s core level structures.
Figure 4.3 Steady-state polarization curves of oxygen evolution on PbO₂-based electrodes in solutions: 0.1 M Pb(CH₃SO₃)₂ + 0.1 M CH₃SO₃H + X g dm^–3 TrO_2(colloidal), where 1—1.0; 2—2.0; 3—5.0; 4—0. j_a = 5 mA cm^–2. Supporting electrolyte 1 M HClO₄.
Figure 4.4 Electrolysis of 2-hydroxyterephthalate on PbO₂ (1) and PbO₂-Bi (2).
Figure 4.5 Natural logarithm of the concentration of the initial compound versus electrolysis duration on PbO₂ (1) and PbO₂-Bi (2) anodes.
Figure 4.6 Electrolysis of p-nitrophenol (1) and benzoquinone (2) solutions in carbonate buffer (a) and acidic medium (b).
Figure 4.7 The absorption spectra of salicylic acid solution (initial concentration 2 × 10^–4 M) obtained at different time of electrolysis in a phosphate buffer on lead dioxide anode, pH = 6.55.
Figure 4.8 The absorption spectra of salicylic acid solution (initial concentration 2 × 10^–4 M) obtained at different time of electrolysis in a phosphate buffer on PbO₂-Bi anode, pH = 6.55.
Figure 4.9 The absorption spectra of sulfosalicylic acid solution (initial concentration 10^–4 M) obtained at different time of electrolysis in a phosphate buffer on lead dioxide anode, pH = 6.55.
Figure 4.10 The absorption spectra of 5-aminosalicylic acid solution (initial concentration 2 × 10^–4 M) obtained at different time of electrolysis in a phosphate buffer on PbO₂-Bi anode, pH = 6.55.
Figure 4.11 Photographs of lead dioxide coating on a platinized titanium substrate before accelerated tests (a) and after their completion due to the mechanical destruction of the active layer (b).
Figure 4.12 The dependence of the potential versus time of polarization at 500 mA cm^–2 in 1 M H₂SO₄ for electrodes obtained from electrolytes: 1 – 0.1 M Pb(CH₃SO₃)₂ + 0.1 CH₃SO₃H, 2 – 0.1 M Pb(CH₃SO₃)₂ + 0.1 CH₃SO₃ H + 2 g dm^–3 TiO₂.
Figure 4.13 SEM photographs of Ti/Pt: (a) as prepared; (b) after 60 h of anodic polarization at 100 mA cm^–2.
Figure 4.14 SEM photographs of Ti/Pt after 1 h heat treatment in air at 410 °C.
Figure 4.15 Potential versus polarization time at 500 mA cm^–2 in 1M H₂SO₄ for electrodes, obtained from: 0.1 M Pb(CH₃SO₃)₂ + 0.1M CH₃SO₃H, on different substrates: (1) Ti-Pt (230° C); (2) Ti-Pt (310° C); (3) Ti-Pt (410° C).
Figure 4.16 Potential versus polarization time at 500 mA cm^–2 in 1M H₂SO₄ for electrodes, obtained from: (1) 0.1 M Pb(CH₃SO₃)₂ + 0.1M CH₃SO₃H; (2) 0.1 M Pb(CH₃SO₃)₂ + 0.1M CH₃SO₃H + 2 g dm^–3 TiO₂ deposited on Ti/Pt substrate, after heat treatment at 410°C.

Chapter 5

Figure 5.1 New strategy of zirconium nuclear fuel cladding surface protection: nanosize (300–700 nm) thick polycrystalline diamond layer deposition.
Figure 5.2 PCD layer on a section of Zr-alloy nuclear fuel rod, 488 nm Raman spectroscopy confirms the presence of diamond (1332 cm^–1) and amorphous carbon at all parts of the Zr sample (ZIRLO).
Figure 5.3 SEM image of the PCD layer deposited onto Zircaloy2 sample.
Figure 5.4 Band structure of a metal (Zr alloy) and n-type semiconductor (ZrO₂) interface before (left, A) and after metal and semiconductor connection (right). If there is no contact, electrochemical potentials of the metal and semiconductor are different than at the first moment after contact, where diffusion electrical current will flow through the boundary. Flowing will continue until a difference of charges between metal and semiconductor is set up, and an electric field is created so that further current flowing is ceased. Charge is injected through the ZrO₂/Zr interface. E_c denotes conductive band edge, E_v valence band edge, and E_f Fermi level. In this work we showed that the oxide layer on Zr samples formed during hot steam/water exposure exhibited n-type character. Oxygen anions with an excess of electrons coming from dissociated water molecules increase the concentration of possible electron donors in the n-type semiconductor. Then at the ZrO₂/Zr interface, oxygen anions donate electron(s) through the n-type semiconductor/metal interface, and oxygen finally interacts with Zr to create an oxide [21].
Figure 5.5 Schematic showing the transport of H and O from the surface and into the bulk of Zr alloy during hot water/steam exposure for (a) uncoated ZIRLO, which is mainly chemically composed of ZrO₂, implying a large uptake of oxygen forming an n-type semiconductor. (b) PCD-coated Zr alloy, where carbides formed by C penetration from the PCD layer are present in the ZrO₂ layer and the bulk Zr alloy forming a mixture of p-type and n-type semiconductor. The presence of electrical fields and gradients of chemical potentials affects transport mechanisms through the surface layer reducing O and H uptake [21].
Figure 5.6 A photo of the Microwave Plasma-Enhanced Linear Antennas Chemical Vapor Deposition apparatus for the growth of polycrystalline diamond layers. The growth chamber potentially allows the deposition on substrates up to the size of 500 mm × 300 mm. [19].
Figure 5.7 A photo of MW-LA-PECVD apparatus chamber interior. Microwave plasma sources (antennas) arranged parallel to one another [19].
Figure 5.8 Schematic of linear antenna microwave plasma-enhanced chemical vapor deposition (MW-LA-PECVD) apparatus. A large and diffuse plasma is formed along the quartz envelopes beneath which large 3D objects can be coated [21].
Figure 5.9 (a) Weight gains (mg/dm^–2) measured after 6, 15, 30, 90, 120, 150, 170, and 195 days of exposure to hot water (360 °C) for uncoated and 300-nm PCD-coated ZIRLO plate samples. (b) Weight gains (mg/dm^–2) measured after 6, 15, 20, 30, 40, and 90 days of exposure to hot water (360 °C) for uncoated, 300-nm PCD-coated, 500-nm PCD-coated, and 700-nm PCD-coated ZIRLO plate samples. Thicker PCD layers provide ZIRLO plates with stronger protection against oxidation than thinner layers [21].
Figure 5.10 Lines C1s of Zr alloy (ZIRLO™) covered by PCD after calibration on Zr3d5/2. Analysed area is at the PCD surface and at the PCD/ZrO₂ interface after autoclave exposure (400 °C, 4 days). Different states of carbon: graphite with a binding energy of 285.4 eV, a diamond with a binding energy of 284.2 eV, carbon in a single bond with oxygen having binding energy 286.1 eV, and carbide at 282 eV are identified (left). Carbides were present under the PCD layer (right) [21].
Figure 5.11 Average hydrogen concentration measured after hot steam processing at 1100 and 1200 °C hot steam for 60 min and 20 min, respectively, of uncoated (reference) Zr tubes (ZIRLO) and PCD-coated (500 nm) Zr samples [21].
Figure 5.12 488-nm Raman spectra of PCD-covered ZIRLO™ and PCD-coated ZIRLO™ after 4 days, 15 days, and 30 days autoclave exposure at 400 °C. A 1332 cm^–1 peak is vibration typical for diamond. A broad peak 1400–1550 cm^–1 is a vibration of amorphous carbon, vibration at 1600 cm^–1 is coming from disorder carbon [21].
Figure 5.13 (a)SEM images of the PCD-covered ZIRLO™ sample before (left) and after (right) ion beam irradiation. (b) SEM images of the PCD-covered ZIRLO™ sample before (left) and after 6 days 400 °C autoclave (middle) and 900 °C autoclave testing (right) [33].
Figure 5.14 SIMS data show that after 4 days at 400 °C hot steam 300-nm PCD-covered ZIRLO™ (left) contained C smeared in the ZrO₂. Autoclaved PCD-protected ZIRLO™ contained more C in deeper parts of approximately 1.7-µm-thick ZrO₂ layer [21].
Figure 5.15 Scratch test depth profiles for uncoated and PCD-coated ZIRLO™ /Zr alloy before and after hot steam test (autoclave, 4 days at 400 °C and 16 MPa); dash line represents scratch load. The sudden drop in scratch depth in the case of autoclaved ZIRLO™ (scan distance of ~330 µm; critical load of ~370 mN) reflects the potential vulnerability of the bare ZIRLO™ under conditions of mechanical loading. Although ZrO₂ improves surface hardness, its abrupt failure manifests its unreliable performance under extreme conditions. On the other hand, deposition of PCD layers provides an extra level of surface mechanical durability during and after hot steam exposition. The underlying ZIRLO™ r remains protected even under severe scratch loading. The scratch resistivity of PCD-protected ZIRLO™ remains unchanged following 4 days at 400 °C in an autoclave [21].
Figure 5.16 SRIM calculated distribution of target displacements as a function of depth into the surface of the sample. Doubly charged Fe ions were accelerated up to the energy of 3 MeV [23].
Figure 5.17 Raman characterization of PCD layer after ion beam irradiation test—satisfactory structural integrity with both sp³ and sp² carbon phases [33].

Chapter 6

Figure 6.1 Powder morphology of as-received WC-10Co-4Cr powder.
Figure 6.2 X-ray diffraction pattern of as-received WC-10Co-4Cr powder.
Figure 6.3 (a) Internal diameter (ID) coating, (b) coating inside rectangular box, (c) coating on the complex geometry of Francis runner, and (d) schematic presentation of coating deposition in complex curved geometry.
Figure 6.4 Schematic of spray angles.
Figure 6.5 Coating morphologies; cross sections and their corresponding top surfaces of (a) A45°, (b) B70°, and (c) C70°.
Figure 6.6 X-ray diffraction patterns of (a) A45°, (b) B70°, and (c) C70°.
Figure 6.7 Phase diagram of the WC system.
Figure 6.8 SprayWatch results of as-sprayed WC-Co-Cr coatings.
Figure 6.9 Stress analysis of as-sprayed WC-Co-Cr coatings.
Figure 6.10 The variation of d-spacing versus the ψ measurement.

Chapter 7

Figure 7.1 ZnO nanopaint can create new insights into the maritime industry. Source: Nightman1965/Fotolia [26]. Source: http://www.european-coatings.com/Raw-materials-technologies/Raw-materials/Coatings-fillers/Preparing-ZnO-nanopaint-for-marine-antifouling-applications, accessed on January 08, 2018.
Figure 7.2 Waterproof rock wool [30],
Figure 7.3 Nanoceramic titles [32].
Figure 7.4 Low-E (low emissivity) glasses heat transfer controller glass made of nanolayers of ceramic and metal [34].

Chapter 8

Figure 8.1 The shift of the oxide taken from [42, 43].
Figure 8.2 Polarization behavior of a metal (M) in deaerated acid solution.
Figure 8.3 Shape and size of the Nyquist plots give different indication about the characteristics of the film and surface.
Figure 8.4 Bode plot.

Chapter 9

Figure 9.1 Nanodiamond structure.
Figure 9.2 Nanodiamond surface with various functional groups.
Figure 9.3 Formation of epoxy resin and hardening reaction.
Figure 9.4 Coating formulation by dipping method.
Figure 9.5 Doctor blade coating.
Figure 9.6 Epoxy/nanodiamond coating formation by spin coating method.
Figure 9.7 Effects of nanodiamond content on tensile strength of epoxy/nanodiamond nanocomposite [42]. NDP = nanodiamond powder.
Figure 9.8 Thermal stability of neat epoxy (EP) and its nanocomposite [45]. GN = Graphene oxide–nanodiamond hybrid.
Figure 9.9 DSC curves for epoxy/ND composites. Negative slope of thermograms is related to increased thermal conductivity [51].
Figure 9.10 (a) TEM photograph of epoxy/ND sample with 50 wt% ND and (b) plot showing interparticle distance as a function of nanofiller volume fraction [52].

Chapter 10

Figure 10.1a and b The volcano curve showing the catalytic activity as a function of binding energies and the volcano curve of Trassati regarding the HER in acidic environment [13].
Figure 10.2 Applied potential pattern of (a) constant potential, (b) cyclic voltammetry, (c) pulsed potential deposition.

Chapter 11

Figure 11.1 Typical SPME device, with details of the coating and the handling.
Figure 11.2 SPME coatings with advanced materials for target applications: (a) fiber coatings based on MOFs to be used in HS-SPME applications in combination with gas chromatography, and (b) fiber coatings based on MIPs to be used in DI-SPME applications in combination with liquid chromatography.
Figure 11.3 (a–e) Main methods to prepare MOFs.
Figure 11.4 Coatings strategies most commonly used for MOFs-based SPME fibers. (a) In situ growth by solvothermal/hydrothermal procedure; (b) physical adhesion support—MOF; and (c) immersion of the pretreated support into a MOF colloidal suspension. Examples of coatings obtained by each procedure are shown in the SEM images: (a) [33], (b) [48], and (c) [51]. Figures obtained with permissions. Copyright 2013 Elsevier and 2017 Elsevier and Copyright 2013 Royal Society of Chemistry.
Figure 11.5 Most common synthetic routes for MIPs: (a) covalent and (b) noncovalent bonding.
Figure 11.6 MIPs-based coatings strategies. (a) Bulk polymerization assisted by heating or photoirradiation and (b) electrochemical polymerization. Examples of coatings obtained by each procedure are shown in the SEM images (a) [68] and (b) [77]. Figures obtained with permissions. Copyright 2018 Elsevier and 2014 Elsevier.

Chapter 12

Figure 12.1 Solid-state Nd:YAG laser source at WRI used for experimental work.
Figure 12.2 Experimental set-up showing the laser beam head and shielding arrangements in the working chamber.
Figure 12.3 The schematic diagram of laser hardened bead profile geometry with experimental measurable responses.
Figure 12.4 Scatter diagram of heat input (HI).
Figure 12.5 Scatter diagram of hardened bead width (HBW).
Figure 12.6 Scatter diagram of hardened depth (HD).
Figure 12.7 Scatter diagram of angle of entry of hardened bead profile (AEHB).
Figure 12.8 Scatter diagram of power density (PD).
Figure 12.9 3D graph shows the effect of LP and SS on the heat input.
Figure 12.10 Contours graph shows the effect of LP and SS on the heat input.
Figure 12.11 3D graph shows the effect of LP and SS on the hardened bead width.
Figure 12.12 Contour graph shows the effect of LP and SS on the hardened bead width.
Figure 12.13 3D graph shows the effect of LP and FP on the hardened bead width.
Figure 12.14 Contours graph shows the effect of LP and FP on the hardened bead width.
Figure 12.15 3D graph shows the effect of SS and FP on the hardened bead width.
Figure 12.16 Contours graph shows the effect of SS and FP on the hardened bead width.
Figure 12.17 3D graph shows the effect of LP and SS on the hardened depth.
Figure 12.18 Contour graph shows the effect of LP and SS on the hardened depth.
Figure 12.19 3D graph shows the effect of LP and FP on the hardened depth.
Figure 12.20 Contour graph shows the effect of LP and FP on the hardened depth.
Figure 12.21 3D graph shows the effect of SS and FP on the hardened depth.
Figure 12.22 Contour graph shows the effect of SS and FP on the hardened depth.
Figure 12.23 3D graph shows the effect of LP and SS on AEHB.
Figure 12.24 Contour graph shows the effect of LP and SS on AEHB.
Figure 12.25 3D graph shows the effect of LP and FP on AEHB.
Figure 12.26 Contour graph shows the effect of LP and FP on AEHB.
Figure 12.27 3D graph shows the effect of SS and FP on AEHB.
Figure 12.28 Contour graph shows the effect of SS and FP on AEHB.
Figure 12.29 3D graph shows the effect of LP and SS on power density
Figure 12.30 Contour graph shows the effect of LP and SS on power density.
Figure 12.31 3D graph shows the effect of LP and FP on power density.
Figure 12.32 Contours graph shows the effect of LP and FP on power density.
Figure 12.33 3D graph shows the effect of SS and FP on power density.
Figure 12.34 Contour graph shows the effect of SS and FP on power density.
Figure 12.35 Microstructure of commercially pure titanium base material.
Figure 12.36 Microstructures of laser hardened surface of commercially pure titanium run order from 1 to 8.
Figure 12.37 Microstructures of laser hardened surface of commercially pure titanium run order from 9 to 16.
Figure 12.38 Microstructures of laser hardened surface of commercially pure titanium run order from 17 to 24.
Figure 12.39 Microstructures of laser hardened surface of commercially pure titanium run order from 25 to 27.

Chapter 13

Figure 13.1 Burgeoning momentum in the field of super(de)wettability. Publication records extracted from the Web of Knowledge ISI, publication numbers highlighting the superhydrophilic, superhydrophobic, superoleophobic, superamphiphobic and superomniphobic materials.
Figure 13.2 Fundamentals of Wettability. (a) Contact angle interpreted as an equilibrium force balance between interfacial surface tension forces (γ) for Young’s equation. States of (super)wettability: (b) superhydrophilicity–hemiwicking superhydrophilicity, (c) hydrophilicity, (d) hydrophobicity, (e) adhesive superhydrophobicity. (f) Moderate states of hydrophobicity are described by the Wenzel regime, where 90° < θ < θ_c, where θ is the observed CA and θ_c is CA enhanced by surface texturing. When θ > θ_c, air gaps are trapped between the interface, forming the triple-phase state of wetting, also known as the Cassie regime, with Φ_s representing the fraction of wetted solid. The Cassie regime can also occur at times with θ < θ_c, and these metastable states are indicated by the broken line [32]. (g) Schematic description of the Gibbs free energy when transiting along the Cassie–Baxter and Wenzel states through partial “impalement” via energy input [134]. States of superdewettability: (h) slippery superhydrophobicity which is (i) oleophilic, (j) superoleophobicity–superamphiphobicity, and (k) superomniphobicity. Impact of reentrant profiles on the range of superdewettability, highlighted by (l) reentrant profiles (inverse trapezoids) inhibiting fluid penetration by virtue of the ratio between reentrancy (α) and Young’s CA (θ) [105]. (m) A secondary reentrant profile can be created orthogonal to the first, inducing double reentrancy. Contact line advancement thus becomes thermodynamically unfavorable even for fluids that are completely wetting, with characteristic CA or Young’s CA (θ) of 0° [105]. Copyright 2003, 2009, 2016. Reprinted with permission from the Nature Publishing Group, American Chemical Society and AIP Publishing.
Figure 13.3 Modes of wettability analysis. Static contact angle analysis: (a) Gravity-induced sagging of droplet profiles can amplify measurement variations in goniometric systems. Superphobic CAs (> 150°) are particularly affected, as demonstrated by potentially erroneous analytical profiles. (b) Schematics describing the measurement of CAH through the drop-in, drop-out (DIDO) method. (c) Sliding angle schematics of a superphobic droplet that slides off upon a certain tilt angle. (d) Droplet impact on a patterned superhydrophobic surface by varying droplet impact parameters, such as an increased Weber number (We) [122]. (e) Immersion experiments showcasing the pressure- or time-dependent collapse of plastron layers on superphobic membrane cavities [11]. Copyright 2014. Reprinted with permission from the Nature Publishing Group and Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
Figure 13.4 Bioinspired nanomorphological features. (a) The multicellular epidermal layers of the Brazilian petunia (Ruellia devosiana) [144]. (b) A lotus leaf (Nelumbo nucifera), where epidermal cells form a papilla-like structure made up of dense layers of epticuticular waxes with hierarchical (micro- and nanoroughness) textures [132]. (c) PS positives using actual rose petals as templating molds [70]. The (d) Morpho butterfly’s wings exhibiting low-adhesion superhydrophobicity when approaching the scales from inside to out (with respect to the body), and pinning superhydrophobicity when approaching the scales from outside to in (with respect to the body). Models for the mechanism suggest that the motion of the droplet down the scale “terrace” takes place through a discontinuous three-phase contact line (TCL), with air gaps that enable the smooth sliding motion. When droplets are made to slide up against the scale “terrace,” a continuous TCL exists with minimal air gaps, resulting in droplet pinning [156]. (e) The springtail (Folsomia candida) skin’s surface textures resemble mushroom-like reentrant profiles. This enables the preservation of a plastron layer in both water and oil, thus achieving superoleophobicity [104]. (f) SEM micrograph of a single mosquito eye. (g) Hexagonal ncp nanonipples covering an ommatidial surface [362]. Copyright 2002, 2007, 2008, 2009, 2013. Reprinted with permission from the Royal Society, Royal Society of Chemistry, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
Figure 13.5 Soft-, Nano-, Optical Lithography. Precision of lithography-developed microfeatures: (a) Soft PDMS pillars on flexible films [164, 174], (b) square, trianglular, round, and cross-shaped PDMS pillars [164], (c) cone-shaped PDMS pillars for fog-havesting [175], (d) silicon pillars with multiple reentrant texturing [107], (e) inverse trapezoidal PDMS pillars with reentrant profiles [103], (f) reverse imprint lithography-based T-shaped hoodoo-like reentrant profiles (PFPEdma) [104], (g) doubly reentrant profiles (mushroom-like) from silicon texturing. Copyright 2010, 2011, 2013. Reprinted with permission from the Nature Publishing Group, IOP Publishing, Royal Society of Chemistry, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
Figure 13.6 Superhydrophilicity. (a,b) Hydrophobic–hydrophilic properties of TiO₂ coatings upon sequential exposure to UV irradiation and darkness [3]. Multilayer PAH/SiO₂-induced superhydrophilicity. Dynamic CAs (time-dependent) with respect to the spread of the (c,e) first and (d,f) second deposited droplet with respect to deposited bilayers [51]. Liquid flame spray pyrolysis-derived (g) nanowires [363], with potential for silica nanofibrous-enhanced (h,i) superhydrophilicity [52]. Organothiol functionalization. (j) Trialkoxy silanization of SiO₂ surfaces [364]. (k) Sequential addition and hydrogen abstraction during thiol-ene polymerization [365]. Copyright 1990, 1997, 2006, 2009, 2010. Reprinted with permission from the Nature Publishing Group, IOP Publishing, American Chemical Society and Springer Publishing Group.
Figure 13.8 Superhydrophobicity from spontaneously formed regularized structures. Electrospun (a) bead-on-string PS film [315] and (b) Rag-wort leaf-like textured PS fibers [316]. (c) Carbon nanotube (CNT) forests [228]. (d) Evaporation deposited waxes of n-hexatriacontane platelet-like surface [368]. (e) Wrinkled Teflon films [369]. (f) Petal-like etched Fe₂O₃ structures [302]. Copyright 2003, 2006, 2010, 2012, 2016. Reprinted with permission from the Elsevier Publishing Group, IOP Publishing and American Chemical Society.
Figure 13.7 Superhydrophobicity from spontaneous structures. (a) Textured beeswax resulting in superhydrophobicity [366]. (b) Low-density PE through a xylene (solvent)—cyclohexanone (nonsolvent) demixing process demonstrating the formation of floral textures [367]. Sol–gel superhydrophobic SnO₂ nanorod films from the (c) top and (d) side profiles [287]. (e) 10-nm-thick gold half shells formed by colloidal lithography, subsequently made superhydrophobic by a C₁₆S coating [261]. (f) Superhydrophobic PS-SiO₂ raspberry hybrid particles [320]. (g) Superhydrophobic spray-deposited poly(SiMA-co-MMA) [234]. Liquid flame spray-deposited in situ superhydrophobic (h and i) M₃O₄ [247]. Copyright 2002, 2004, 2006, 2011, 2012, 2014, 2016. Reprinted with permission from the Elsevier Publishing Group, Royal Society of Chemistry, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
Figure 13.9 Petal-like superhydrophobicity. (a) Aqueous TMPSi-synthesized films from sol–gel processes [370]. (b) Stereocomplex bottom surfaces of phase-separated PLLA/PDLA films [371]. (c) Structured bead-on-string coatings prepared by spray-coating [372]. (d) Electrospun part-bead, part-fiber PS with petal-like wetting properties [79]. (e) Micro- and nanotextured Zn substrates after electrodeposition [84]. (f) Wrinkled GO nanoshells with different rotational speeds during Pickering emulsions (RPM: 20k) [82]. Copyright 2012, 2015, 2016. Reprinted with permission from the Elsevier Publishing Group, Royal Society of Chemistry, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
Figure 13.10 Superoleo(amphi)phobicity from fiber- or cylindrical based reentrant profiles. (a) Silicone-coated polyester textiles [328]. (b) Polyester fibers coated with (c) SiO₂ NPs-HFA-TiO₂ [87]. (d) Sprayed CNTs-SiO₂ coatings. TiO₂ / single-wall nanotube (SWNT) porous coating. (e) Cross-sectional view of the coating shows overhanging structures formed by the TiO₂/SWNT clusters. (f) High-magnification view of the coating surface shows that the surface of TiO₂ particles is covered by nanocrystals, forming hierarchical surface structures [344]. (g) Stochastically spray-deposited SNTs-perfluorodecyltrichlorosilane (PFDTCS) [373]. Anodically oxidized aluminum plate (h) after anodic oxidation for nanoroughness on micropillars, at (i) higher magnifications [348]. Copyright 2011, 2015, 2016. Reprinted with permission from the Royal Society of Chemistry, American Chemical Society and Wiley-VCH Verlag GmbH & Co. KGaA Weinheim.
Figure 13.11 Superoleo(amphi)phobicity from fractal based textures. Electrodeposited (a) fluorinated PEDOP, in contrast, possesses very porous features down to the nanometer length scale [350]. (b) Electrodeposited fluorinated derivatives of EDOP monomers (polyEDOPC₃F₈), with enhanced nanoroughness [351]. Electrochemically etched Al surfaces with (c) multiscale texturing of aluminum plates by HCl etching and boiling water nanotexturing [352]. Micropillars with hierarchical, triple-scale roughness produced by the combination of colloidal lithography of 1-µm particles followed by plasma etching. Dual-scale nanoroughness on top of the pillars formed during plasma etching (d) with and (e) without colloidal particles [374]. Super(oleo) amphiphobicity from (f) candle soot templating. (g) After CVD coating with a SiO₂ shell and calcination at 600 °C. (h) Transmission electron micrograph revealing the thin templated SiO₂ shells [85]. Cross-sectional SEM analyses of the inherent reentrant nanotextures with a liquid flame spray pyrolysis (LFSP)-SiO₂ deposition time of (i) 15 s. (j) SA of water (72.8 mN/m), sunflower oil (32.9 mN/m), hexadecane (27.47 mN/m), tetradecane (26.56 mN/m), and dodecene (25.6 mN/m) as a function of the aerosol deposition time [253]. Copyright 2009, 2011, 2012, 2013, 2016. Reprinted with permission from the American Association for the Advancement of Science, Royal Society of Chemistry and American Chemical Society.
Figure 13.12 Superomniphobicity from scalable texturing. (a) Electrospun PMMA/F-POSS composite with superomniphobic properties down to a fluid surface tension of 20 mN/m [101]. Electrospun superomniphobic multiscale fractal features on (b) wire meshes. Superomniphobic surface composed of electrospinning (c) cross-linked PDMS and 50 wt% F-POSS on a stainless steel wire mesh 70. Scanning electron micrographs of the electrospun texture [95]. Hyperbranched structures with three levels of hierarchy. (d) Branched ZnO NWs on Si microposts, (e) branched NWs grown with higher density of “trunks” and (f) branched NWs grown with lower density of “trunks” [102]. (g) Three-electrode electrodeposition set-up consisting of a track-etched template, metal electrode, and Ni deposition which is localized on one side of the template. (h) SEM micrograph of a cluster of electrodeposited Ni micronails [361]. Copyright 2008, 2012, 2013, 2017. Reprinted with permission from the National Academy of Sciences, U.S.A. and American Chemical Society.

List of Tables

Chapter 1

Table 1.1 HSAB classification of metal and ligand.
Table 1.2 Relationship between the structure of complexes in the precursor solutions and the anatase–rutile transition temperatures.
Table 1.3 The reaction rate v of the decoloration reaction in an aqueous solution containing 0.01 mol/dm³ of methylene blue under visible- and UV-light irradiation and under dark conditions. Calculated standard deviations are presented in parentheses.

Chapter 2

Table 2.1 CFD analysis flow and boundary conditions.
Table 2.2 Cold Spray conditions for calibration and validation of the developed multicomponent model.
Table 2.3 Experimentally recorded average temperature for each thermocouple with respect to CS condition 1 [37].
Table 2.4 Experimental conditions for PIV measurement of titanium cold spray-free jet [61].
Table 2.5 CS experiment parameters and PIV measured particle velocity by Wong et al. [10, 62].
Table 2.6 Calibrated parameters for k-ε model [32, 37].

Chapter 3

Table 3.1 Chemical Composition of Ti-6Al-4V alloy.
Table 3.2 Laser source technical data [19].
Table 3.3 Experimental measured overlapped multipass hardened bead profile responses.

Chapter 4

Table 4.1 The phase composition of PbO₂-TiO₂ composites.
Table 4.2 Kinetic parameters of the electrochemical oxidation of p-nitroaniline (2 × 10^-⁴ M) on modified PbO₂ anodes.

Chapter 5

Table 5.1 Weight gains (mg/dm²) measured after autoclave tests of uncoated ZIRLO samples (fuel cladding and plates) and samples coated with 300 or 500 nm of PCD. The samples were processed in 360 °C hot water for 6, 15, 30, 90, 120, 150, 170, and 195 days under primary circuit conditions in a PWR in accordance with ASTM standard procedures [21]. The greater relative weight gain of the uncoated ZIRLO plates and fuel cladding indicated stronger oxidation of the unprotected surfaces [21].
Table 5.2 Acceptor and donor densities obtained from Mott-Schottky plots for uncoated Zr pre- and post-hot steam exposure and PCD-coated Zr samples post-hot steam exposure. Uncoated Zr exhibits an n-type semiconductive character, and PCD-protected Zr post-hot steam exposure exhibits a mixed p- and n-type semiconductive character [33].
Table 5.3 Results of the neutron transmission experiments. I₀ and I are the incident and transmitted beam intensity, respectively; t is the tested specimen thickness and is the observed linear absorption coefficient [22].
Table 5.4 Average hydrogen concentration measured after hot steam processing at 1100 and 1200 °C hot steam for 60 min and 20 min, respectively, of uncoated (reference) Zr tubes (ZIRLO) and PCD-coated (500 nm) Zr tubes (ZIRLO). Compared to PCD-protected Zr, a much larger hydrogen concentration was found in unprotected samples confirming PCD layer’s protection of Zr alloy against H penetration [21].

Chapter 6

Table 6.1 Chemical composition of the CA6NM steel.
Table 6.2 Optimized spray parameters for the HVOLF coatings.
Table 6.3 Microhardness, porosity, and surface roughness of the WC-Co-Cr coatings.

Chapter 7

Table 7.1 Nanomaterials in paints and their possible benefits.
Table 7.2 Characteristics of nanostructured γ-alumina-based catalyst [24].
Table 7.3 Typical characteristics of mesoporous aluminum-based desulfurization catalyst [24].
Table 7.4 Typical characteristics of mesoporous γ-based oxchlorination catalyst [25].
Table 7.5 Properties of structural lightweight concrete with/without nanoparticles [33].
Table 7.6 Properties of low-E glass with nanoparticles inclusion [34].
Table 7.7 Types of stent coatings and overview/functions [42].

Chapter 9

Table 9.1 Epoxy resins.
Table 9.2 Mechanical properties of pure epoxy and the nanocomposites [44].
Table 9.3 Thermal stability of GO/GN-filled epoxy composites obtained from TGA thermograms [45].

Chapter 10

Table 10.1 Common applications of metal oxide in fuel cell technologies.
Table 10.2 Application of metal chalcogenides in solar cells, Li-ion batteries, and supercapacitor technologies.

Chapter 11

Table 11.1 MOFs most employed for the generation of MOFs-based SPME coating fibers.
Table 11.2 MOF-based SPME coatings for HS-SPME-GC analytical applications.
Table 11.3 MIP-based SPME coatings for DI-SPME-LC analytical applications.
Table 11.4 Comparison of several parameters of MOFs and MIPs as SPME coatings.

Chapter 12

Table 12.1 Chemical composition of commercially pure titanium.
Table 12.2 Process variables and experimental design levels used.
Table 12.3 3³ = 27 experimental full factorial design (FFD) layout matrix with coded independent variables.
Table 12.4 Experimental measured laser hardened bead profile responses.
Table 12.5 ANOVA table for heat input (Reduced Quadratic Model).
Table 12.6 ANOVA table for hardened bead width (Reduced Quadratic Model).
Table 12.7 ANOVA table for hardened depth (Reduced Quadratic Model).
Table 12.8 ANOVA table for angle of entry of hardened bead profile (Reduced Linear Model).
Table 12.9 ANOVA table for power density (Reduced Quadratic Model).
Table 12.10 Confirmation of experiments.

Chapter 14

Table 14.1 The different properties of the common types of parylene.

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Library of Congress Cataloging-in-Publication Data

ISBN 978-1-119-40756-0