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- Herausgeber: John Wiley & Sons
- Kategorie: Fachliteratur
- Sprache: Englisch
Valuable insights into the extraction, production, and properties of a large number of natural and synthetic oxides utilized in applications worldwide from ceramics, electronic components, and coatings This handbook describes each of the major oxides chronologically--starting from the processes of extraction of ores containing oxides, their purification and transformations into pure alloyed powders, and their appropriate characterization up to the processes of formation of 2D films by such methods as PVD, CVD, and coatings by thermal spraying or complicated 3D objects by sintering and rapid prototyping. The selection of oxides has been guided by the current context of industrial applications. An important point that is considered in the book concerns the strategic aspects of oxides. Some oxides (e.g. rare earth ones) become more expensive due to the growing demand for them, others, because of the strategic importance of countries producing raw materials and the countries that are using them. Industrial Chemistry of Oxides for Emerging Applications provides readers with everything they need to know in 7 chapters that cover: technical and economical importance of oxides in present and future; fundamentals of oxides manufacturing; extraction, properties, and applications of Al2O3; extraction, properties, and applications of ZrO2; synthesis, properties, and applications of YBaCu2O7x; extraction, properties, and applications of TiO2; and synthesis, properties, and application of hydroxyapatite. * Presents the extraction, production, and properties of a large fraction of oxides applications worldwide, both natural as well as synthetic multi-oxides * Covers a very important segment of many industrial processes, such as refractories and piezoelectric oxides--both applications constituting very large market segments * Developed from a lecture course given by the authors for over a decade Industrial Chemistry of Oxides for Emerging Applications is an excellent text for university professors and teachers, and graduate and postgraduate students with a solid background in physics and chemistry.
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Table of Contents
Cover
Title Page
Copyright
Preface
Acknowledgments
Abbreviations and Symbols
Chapter 1: Technical and Economic Importance of Oxides
1.1 Industrial Sectors in Development
1.2 Reserves, Availability and Economic Aspects of Oxides and their Ores
References
Chapter 2: Fundamentals of Oxide Manufacturing
2.1 Introduction
2.2 Fundamentals of Selected Processes Related to Oxide Manufacturing
Questions
2.3 Selected Oxide Powder Production Methods
Questions
2.4 Manufacturing Objects in 2D: Films and Coatings
Questions
2.5 Manufacturing Objects in 3D
Questions
References
Chapter 3: Extraction, Properties and Applications of Alumina
3.1 Introduction
3.2 Reserves of Bauxite and Mining
3.3 Methods of Obtaining Alumina
3.4 Properties of Alumina
3.5 Methods of Alumina Functionalizing
3.6 Applications of Alumina in Different Industries
Questions
References
Chapter 4: Extraction, Properties and Applications of Zirconia
4.1 Introduction
4.2 World Reserves of Ores and Mining Industry
4.3 Metallurgy of Zirconia
4.4 Properties of Zirconia
4.5 Physical Properties of Zirconia
4.6 Ceramic Sintering
4.7 Industrial Applications of Zirconia
4.8 Future Trends of Zirconia Materials
Questions
References
Chapter 5: Synthesis, Properties and Applications of YBa2Cu3O7−x
5.1 Introduction
5.2 Phase Diagram
5.3 Methods of YBa
2
Cu
3
O
7−
x
Powder Manufacturing
5.4 Superconductivity of YBa
2
Cu
3
O
7−
x
5.5 Properties of YBCO
5.6 Methods of YBa
2
Cu
3
O
7−
x
Functionalizing
5.7 Industrial Applications of YBa
2
Cu
3
O
7−
X
Questions
References
Chapter 6: Extraction, Properties and Applications of Titania
6.1 Introduction
6.2 World Reserves and Mining Industry
6.3 Structural Characteristics of Titania
6.4 Properties of Titanium Dioxide
6.5 Industrial Applications of Titania
6.6 Future Perspectives
Questions
References
Chapter 7: Synthesis, Properties and Applications of Hydroxyapatite
7.1 Introduction
7.2 Phase Diagram
7.3 Methods of Ca
10
(PO
4
)
6
(OH)
2
Powder Manufacturing
7.4 Properties of Ca
10
(PO
4
)
6
(OH)
2
7.5 Methods of Ca
10
(PO
4
)
6
(OH)
2
Functionalizing
7.6 Practical Applications of HA
Questions
References
Answers to Questions
Section 2.2
Section 2.3
Section 2.4
Section 2.5
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Chapter 7
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: Technical and Economic Importance of Oxides
Figure 1.1 Advanced ceramics application tree (after Y. Liang and S.P. Dutta [1.5], reproduced with permission of Elsevier).
Figure 1.2 Alumina ceramic armor for police car protection: (a) monolithic plate; (b) police car with door protection.
Figure 1.3 Ceramic knife made from blackened zirconium, heated under pressure [1.10].
Figure 1.4 Corona treater with a roll coated with electrically conducting TiO
x
(from Pawłowski [1.15], reproduced with permission John Wiley & sons).
Figure 1.5 Zirconia oxygen sensor (from Riegel
et al.
[1.18], reproduced with permission of Elsevier).
Figure 1.6 Alumina micro heat exchanger with plates 26.2 × 26 mm and channels 250 µm wide. The exchangers (a) were produced by rapid prototyping to reach an appropriate flow arrangement (b). From Sommers
et al.
[1.28], reproduced with permission of Elsevier.
Figure 1.7 Alumina foams. From Sommers
et al.
[1.28], reproduced with permission of Elsevier.
Figure 1.8 Distribution of bauxite in different continents [1.36].
Figure 1.9 World consumption evolution of zircon from 1990 to 2010
3
[1.44], reproduced with permission of Elsevier.
Figure 1.10 Price evolution of zircon from 1970 to 2010
4
[1.44, 1.45], reproduced with permission of Elsevier.
Figure 1.11 Distribution of TiO
2
production in different countries in 2003 [1.46].
Figure 1.12 Evolution of mineral rutile prices from 2000 to 2010
6
[1.45].
Figure 1.13 Rare earth oxide production from 1950 to 2000 [1.56] reproduced with permission of Rareearth production.svg.
Figure 1.14 Rare earth oxides in 2009: (a) production; (b) reserves [1.57].
Figure 1.15 World production of copper in the last century [1.66].
Figure 1.16 Price evolution of
gypsum
2001–2005: (a) FOB (mine) and (b) FOB (plant) after calcination [1.74].
Chapter 2: Fundamentals of Oxide Manufacturing
Figure 2.1 The
product triangle
, the vertices of which are the essential elements influencing the quality of a high-technology product. Inspired by Terpstra
et al
. [2.1] (reproduced with permission of Springer).
Figure 2.2 Formula of zirconium acetylacetonate [2.14] (reproduced with permission of Elsevier).
Figure 2.3 Equilibrium diagrams for formation of solid ZrO
2
(monoclinic) or solid ZrO
2
(monoclinic) with C-graphite, as a function of partial pressures of Zr(acac)
4
and O
2
at different temperatures [2.14]: (a) 300°C; (b) 400°C; (c) 500°C; (d) 600°C; 700 °C; (f) 800°C and total pressures: 0.1, 1.0, 10.0 and 100.0 Torr (1 Torr = 133 Pa), (reproduced with permission of Elsevier).
Figure 2.4 Maxwell-Boltzmann distribution of selected gases at a temperature of 293.15 K. The image shows the number
n
molecules per million which has determined the velocity
v
[2.17].
Figure 2.5 Schema of a boundary layer of a gas flowing over a flat plate.
Figure 2.6 Gibbs free energy vs. radius of condensed nucleus.
Figure 2.7 Function
erfc
(z) using the data shown in [2.25] (reproduced with permission of Elsevier).
Figure 2.8 Ionic concentration and two-layer structure around negatively charged solid particle immersed in a polar dispersion medium [2.31].
Figure 2.9 Potential energy of interaction between two solid charged particles immersed in a polar dispersion medium.
Figure 2.10
ζ
-potential as a function of pH for cation concentrations [H
+
]
1
> [H
+
]
2
> … > [H
+
]
7
; after [2.5] (reproduced with permission of Springer).
Figure 2.11 Principle of steric repulsion.
Figure 2.12 Sketch of layers of liquid in a laminar flow.
Figure 2.13 Variation of shear stress and strain rate for different type of fluids.
Figure 2.14 Contact between liquid droplet surrounded by its vapor and solid surface.
Figure 2.15 Zeta potential of fine hydroxyapatite particles in (a) ethanol and (b) water, as measured by dynamic light scattering [2.36] (reproduced with permission of Elsevier).
Figure 2.16 Hydroxyapatite powder: (a) SEM micrograph (secondary electrons) and particle sizes measured by dynamic light scattering in (b) ethanol (c) distilled water.
Figure 2.17 Optical micrograph in bright field of a cross-section of a powder prepared by calcination and composed of YBa
2
Cu
3
O
7
(dark fields) and CuO (white fields). The product of calcination was crushed and submitted to a number of heat treatments at 1220 K and the fraction at –56+28 µm was sieved out for plasma spraying [2.45].
Figure 2.18 SEM image using secondary electrons showing spray-dried powder of Cr
2
O
3
+SiO
2
[2.46].
Figure 2.19 XRD obtained with Cu-K
α
radiation of the calcined powder shown in Figure 2.17. This shows the two phases: YBa
2
Cu
3
O
7
(abbreviated as 1-2-3) and CuO [2.45].
Figure 2.20 Direct granulation.
Figure 2.21 Sketch of spray dryer: 1, atomizer; 2, feed pump; 3, gas cleaning filter; 4, gas heater; 5, gas distributor; 6, drying chamber; 7, duct; 8, powder separator; 9, exhaust fan; 10, outlet gas duct.
Figure 2.22 Typical industrial spray-dryer (reproduced with kind permission of SPX Flow Technology Denmark).
Figure 2.23 SEM image using back-scattered electrons showing spray-dried powder of ZnO + 3 wt.% Al
2
O
3
. Further details about process parameters are given in Table 2.9.
Figure 2.24 SEM image using back-scattered electrons showing spray-dried powder of ZnO + 3 wt.% Al
2
O
3
, as shown in Figure 2.23, submitted to hot air of temperature,
T =
1300°C for 6 h [2.57].
Figure 2.25 SEM image using secondary electrons of the hydroxyapatite powder described in Table 2.10.
Figure 2.26 SEM image (secondary electrons) of YBa
2
Cu
3
O
7-x
powder calcined at 1120°C [2.45].
Figure 2.27 SEM micrograph (secondary electrons) of a commercial Al
2
O
3
+ 3 wt.% TiO
2
powder, Metco 101 SF, obtained by fusion and crushing. The powder has particle sizes in the range 5–22 µm.
Figure 2.28 Sketch of SHS reaction moving along a rod and an instantaneous temperature distribution [2.7].
Figure 2.29 SEM image of cross-section of mechanofused stainless steel particles coated with alumina [2.66] (reproduced with permission of Elsevier).
Figure 2.30 SEM micrograph of ZrO
2
+ 8 mol.% Y
2
O
3
powder prepared by the sol–gel method [2.69] (reproduced with permission of Elsevier).
Figure 2.32 Morphologies of hydroxyapatite powder particles: after synthesis and drying; the powder after calcination is shown in Figure 2.16a [2.73] (reproduced with permission of Elsevier).
Figure 2.31 Size distribution of calcinated and balls milled hydroxyapatite in ethanol (top) and in distilled water (bottom) measured by dynamic light scattering [2.73] (reproduced with permission of Elsevier).
Figure 2.33 TEM images of TiO
2
powder prepared by CVD synthesis starting from TTIP and TiCl
4
precursors at different reactor temperatures [2.78] (reproduced with permission of Elsevier).
Figure 2.34 Flow diagram of the process steps for thin film formation by sol–gel [2.90]
Figure 2.35 SEMs of YBCO films obtained by sol–gel method with thicknesses of (a) 500 nm; (b) 100 nm. Both heat treated at 800°C under
p
O2
= 30 Pa [2.95] (reproduced with permission of Elsevier).
Figure 2.36 Anodization cell [2.98].
Figure 2.37 Top, bottom and side views of anodic TiO
2
film and the EDX spectrum of its surface [2.100] (reproduced with permission of Elsevier).
Figure 2.38 Principle of a thermal CVD deposition [2.10]
Figure 2.39 Schematic of CVD with lasers: (a) thermal LCVD; photochemical LCVD.
Figure 2.40 Sketch of a vacuum evaporation installation using electron bombardment heating.
Figure 2.41 Evaporation set up with reactive gas (RE) and with reactive plasma (ARE).
Figure 2.42 Sputtering system installation with DC diode system in which the target is the cathode and substrate is the anode.
Figure 2.43 An elastic collision between two particles: a projectile and an immobile target particle.
Figure 2.44 Sketch of a PLD system.
Figure 2.45 Phenomena of heating occurring during flight of initially solid particles in combustion flame or plasma jet.
Figure 2.46 Sketch of flame spraying of powder: 1, working gases (fuel and oxygen); 2, injection of powder; 3, torch body; 4, sprayed coating; 5, stream of particles; 6, combustion flame.
Figure 2.47 Detonation gun: 1, powder injection; 2, spark plug; 3, gun barrel; 4, oxygen input; 6, nitrogen input.
Figure 2.48 Detonation gun in operation in ARCI, Hyderabad, India (reproduced with permission of International Advanced Research centre).
Figure 2.49 Section of a plasma torch: 1, anode; 2, cathode; 3, water outlet and cathode connector; 4, water inlet and anode connector; 5, working gas inlet; 6, powder injector; 7, electrical insulator.
Figure 2.50 Modern plasma torch installed on a robot used for thermal spraying in ENSC, Lille (France).
Figure 2.51 Cross section of HA coating that was plasma sprayed using a coarse powder [2.118] (reproduced with permission of Elsevier).
Figure 2.52 Plasma-sprayed coatings: (a) SEM (secondary electrons) view of the cross section of as-sprayed coating; (b) optical microscope view of polished cross section of sprayed coating heat treated for 20 h at 950°C in air and then for 48 h at 400°C in flow of oxygen [2.45, 2.119].
Figure 2.53 Injection of suspension: (a) with an atomizer; (b) with a nozzle.
Figure 2.54 Evolution of a suspension droplet in a high-temperature plasma jet or combustion flame [2.120].
Figure 2.55 SEM (secondary electrons) of the cross-section of coating produced by plasma-spraying of an HA suspension [2.123] (reproduced with permission of Elsevier).
Figure 2.56 Phenomena occurring in a solution droplet in-flight in a high-temperature plasma or flame [2.134] (reproduced with permission of Elsevier).
Figure 2.57 SEM (secondary electron) of polished cross-section of 7YSZ coating obtained using the SPPS technique with a feedstock having (a) low and (b) high molar concentration of the precursor [2.135] (reproduced with permission of Elsevier).
Figure 2.58 Bulk coating deposition: (a) one-step; (b) two-step.
Figure 2.59 Optical micrograph of the surface of hydroxyapatite coating pre-deposited with atmospheric plasma spraying and subsequent CO
2
laser treatment [2.147].
Figure 2.60 SEM micrograph (backscattered electrons) of the polished cross section of a thermal barrier coating consisting of a MoCrAlY bond coating and ZrO
2
+ 8 wt% Y
2
O
3
ceramic top coating. The top coating was remelted with a CO
2
laser [2.149].
Figure 2.61 3 SEM image using secondary electrons of (a) surface and (b) fractured section of TiO
2
coatings that have been plasma sprayed and laser engraved [2.152] (reproduced with permission of Elsevier).
Figure 2.62 Different stages of pressing occurring with increasing pressure [2.5].
Figure 2.63 Co-extruder used to obtain a SOFC with cylindrical geometry [2.154] (reproduced with permission of Elsevier).
Figure 2.64 The tape casting process, in which micrometric screws control the gap between the doctor blade and the support [2.155] (reproduced with permission of Elsevier).
Figure 2.65 SEM (secondary electrons) image of PZT pillar array produced by ink-jet printing [2.159] (reproduced with permission of Elsevier).
Figure 2.66 Sketch of two particles sintering.
Figure 2.67 Sintering time necessary to reach neck ratio
X
/
d
= 0.1 for particles of an initial diameter of
d
= 0.3 µm for (a) TiO
2
; (b) HA; (c) 8YSZ as a function of temperature for three mechanisms of mass transport: volume, grain boundary and surface diffusion [2.161, 2.162]. Pawłowski et al. http://www.mdpi.com/1996-1944/3/7/3845/htm-CC BY 3.0.
Figure 2.68 SEM micrographs (secondary electrons) of alumina prepared initially by CIP under a pressure p = 50 MPa then (a) pressure-less sintering at 1350°C or (b) HIP sintered at the same temperature but under pressure p = 150 MPa [2.163] (reproduced with permission of Elsevier).
Figure 2.69 Model of densification in the presence of liquid phase, indicating the stages of sintering [2.4] (reproduced with permission of John Wiley & Sons).
Figure 2.70
(a), (b)
TEM showing intergranular liquid in liquid-phase sintered 8YSZ + 0.5 mol.% Al
2
O
3
+ 0.5 mol.% SiO
2
at 1450°C with zero sintering time (that is, cooling started after reaching the sintering temperature} and heating and cooling rates of 200°C/h [2.164] (reproduced with permission of Elsevier).
Figure 2.71 Sketch of spark plasma sintering [2.165] (reproduced with permission of Elsevier).
Figure 2.72 Sketch of continuous microwave sintering of alumina grit: (1) preheating zone; (2) sintering zone; (3) cooling zone [2.166] (reproduced with permission of Elsevier).
Figure 2.73 Laser rapid prototyping process with injection of powder [2.138].
Figure 2.74 Installation of rapid prototyping with the help of laser cladding with injection of powder [2.138].
Figure 2.75 Calcium phosphate sample produced by rapid prototyping based on Nd:YAG laser cladding (complete sample height 60 mm, laser power 160 W, scanning speed 3.0 mm/s, mass flow 10 mg/s, 320 stacked layers) [2.168] (reproduced with permission of Elsevier).
Chapter 3: Extraction, Properties and Applications of Alumina
Figure 3.1 Annual production of
bauxite
from 1900 to 2001 and projected production from 2002 to 2005 [3.5] (reproduced with permission of Springer).
Figure 3.2
(a), (b)
The depth profiles of
bauxite
deposit in India [3.7] (reproduced with permission of Elsevier).
Figure 3.3 The Bayer process [3.7] (reproduced with permission of Elsevier).
Figure 3.4
Red mud
lake at the refinery Nalco in India [3.7] (reproduced with permission of Elsevier).
Figure 3.5 Hydrothermal Al
2
O
3
–H
2
O system [3.14] (reproduced with permission of Elsevier).
Figure 3.6 Nano-alumina synthesized by sol–gel method [3.15] (reproduced with permission of Elsevier).
Figure 3.7
Lime
sintering process of alumina recovery from coal ash [3.20] (reproduced with permission of Elsevier).
Figure 3.8 Leaching process of alumina recovery from coal ash [3.21] (reproduced with permission of Elsevier).
Figure 3.9 FE SEM (secondary electrons) images of anodized alumina films obtained using (a) phosphoric acid and (b) oxalic acid [3.59] (reproduced with permission of Elsevier).
Figure 3.10 Optical micrograph of a plasma-sprayed alumina coating cross-section [3.66].
Figure 3.11 Schema of vacuum infiltration process of spheres prepared by 3D ink-jet printing [3.68] (reproduced with permission of Elsevier).
Figure 3.12 SEM microstructure (secondary electrons) of polished cross-section of a sample sintered at 2123 K for 30 min, showing desirable transparency and about 0.14% porosity [3.69] (reproduced with permission of Elsevier).
Figure 3.13 Parts produced by selective laser sintering followed by various post-treatments [3.71] (reproduced with permission of Elsevier).
Figure 3.14 Holes drilled in dense alumina with a YAG laser [3.74] (reproduced with permission of Elsevier).
Figure 3.15 Alumina thread guide [3.76] (reproduced with permission).
Figure 3.16 Armor systems with using alumina: (a) ceramic spheres attached to a backing material; (b) monolithic alumina with nodes on backing material; (c) monolithic ceramic with alumina spheres on backing material and spall protection [3.77] (reproduced with permission of Elsevier).
Figure 3.17 Commercial cutting tools made of alumina [3.79] (reproduced with permission).
Figure 3.18 Corona treater with a roll coated with electrically insulating alumina [3.66].
Figure 3.19 Principal elements of hip prosthesis (inspired by [3.84] and reproduced after https://en.wikipedia.org/wiki/Hip_replacement checked on 31 July 2017).
Figure 3.20 Evaporative cooler made using ceramic pipes made of alumina-based ceramics [3.99] (reproduced with permission of Elsevier).
Chapter 4: Extraction, Properties and Applications of Zirconia
Figure 4.1 Transition of zirconia phases in the temperature range for monoclinic-to-tetragonal structure changes.
Figure 4.2 Phase diagram of the system ZrO
2
–MgO. Cubic ss, tetragonal ss and monoclinic ss refer to cubic, tetragonal, and monoclinic solid solutions based on ZrO
2
. A and B indicate eutectoid positions [4.5] (reproduced with permission of Springer).
Figure 4.3 System ZrO
2
–CaZrO
3
. Cub, cubic; Mon, monoclinic; Tet, tetragonal [4.6] (reproduced with permission of John Wiley and Sons).
Figure 4.4 Binary diagram ZrO
2
–YO
1.5
. Thick lines are stable boundaries; thin lines are metastable boundaries, solid lines are evaluated data, dashed lines are probable, dotted lines are uncertain [4.7] (reproduced with permission of Elsevier).
Figure 4.5 Binary system ZrO
2
–CeO
2
[4.9] (reproduced with permission of John Wiley and Sons).
Figure 4.6 Transformation zone change when crack length increases.
Figure 4.7 Typical R-curve behavior of sintered zirconia.
Figure 4.8 Strength-toughness variations for zirconia stabilized with different additives. Solid lines are fits to experimental data. Dashed line represents the critical stress for the tetragonal-to-monoclinic transformation [4.12] (reproduced with permission of John Wiley and Sons).
Figure 4.9 Schematic representation between water and a constrained Zr–O–Zr bond at a crack tip [4.13] (reproduced with permission of Elsevier).
Figure 4.10 Crack velocity as a function of the maximum stress intensity factor obtained under cyclic loading in air and in water [4.14] (reproduced with permission of Elsevier).
Figure 4.11 Sintering curves of nanopowder compacts having monoclinic (m), tetragonal (t) or cubic (c) structures [4.23] (reproduced with permission of John Wiley and Sons).
Figure 4.12 Size evolution of the most frequent pore in zirconia nanopowder compacts as a function of sintering temperature [4.23] (reproduced with permission of John Wiley and Sons).
Figure 4.13 Thermal expansion of 8YSZ doped with 1, 3 and 5 mol% of sintering additive [4.29] (reproduced with permission of Elsevier).
Figure 4.14 SEM images of 3YSZ pellets sintered at 1500°C [4.34] (reproduced with permission of Elsevier).
Figure 4.15 Scanning electron micrograph of polished surface of: (a) 3 mol% Ca-8YSZ; (b) 5 mol% Co-8YSZ, sintered at 1525°C [4.29] (reproduced with permission of Elsevier).
Figure 4.16 SEM photo at grain boundaries and triple junctions in 10 mol% Bi
2
O
3
-doped YSZ specimens sintered in a controlled-atmosphere kiln [4.31] (reproduced with permission of Elsevier).
Figure 4.17 SEM images showing the microstructure of 10 vol.% ZrO
2
in Al
2
O
3
; brighter ZrO
2
grains are distributed in a fine-grained and darker Al
2
O
3
matrix: (a, b) images from a mixing–milling process; (c, d) images from a colloidal process [4.13] (reproduced with permission of Elsevier).
Figure 4.18 Alumina–zirconia (5 vol.%) obtained by two-step sintering at T
1
= 1450°C and T
2
= 1350°C/12 h. The bright grains are the second phase zirconia [4.36] (reproduced with permission of Elsevier).
Figure 4.19 Joint prostheses used in therapeutic practice.
Figure 4.20 Accelerated transformation of tetragonal-to-monoclinic zirconia in an autoclave and domains of the experimental techniques as a function of the transformation stage [4.41].
Figure 4.21 Averaged wear data for zirconia on PE and Co/Cr metal on cross-linked polyethylene [4.42]. Kenneth_http://www.mdpi.com/2075-4442/3/2/459-Attribution 4.0 International (CC BY 4.0).
Figure 4.22 Zirconia tooth crown [4.45].
Figure 4.23 Weibull plots of fracture data for two zirconia materials [4.46] (reproduced with permission of Elsevier).
Figure 4.24 XRD pattern of zirconia crown material (A) and after ageing in acetic acid (B) [4.47] (reproduced with permission of Elsevier).
Figure 4.25 Activation enthalpy Δ
H
of ZrO
2
with 3–25 mol% of Y
2
O
3
as a function of reciprocal temperature [4.49] (reproduced with permission of Elsevier).
Figure 4.26 Assembly of solid electrolyte fuel cell (SOFC).
Figure 4.27 SEM images of the fracture surface of a cathode–electrolyte (LSCF La
0.58
Sr
0.4
Co
0.2
Fe
0.8
O
3
) assembly after sintering for 6 h at 1050°C [4.51] (reproduced with permission of Elsevier).
Figure 4.28 SEM observations of the cross-section of the anode (A) and electrolyte (E) assembly [4.53] (reproduced with permission of Elsevier).
Figure 4.29 Cross section of a zirconia electrochemical sensor.
Figure 4.30 Resistivity-temperature variations of yttrium stabilized zirconia, a platinum electrode and manganite electrode [4.54]. Courtesy of Shuk.
Figure 4.31 SEM photos of 15–22 mol% CaO-stabilized zirconia sintered at 1650°C for 2 h [4.55]. The 22 mol% CaO has calcium zirconate phases segregated at the grain boundaries. B, close pore entrapped at grain boundary; C, calcium zirconate; D, CaO stabilized zirconia (Reproduced with permission of John Wiley and Sons).
Figure 4.32 Electrical response of sensor with zirconia stabilized with 15 or 22 mol% CaO and Pt electrodes [4.55] (reproduced with permission of John Wiley and Sons).
Figure 4.33 Relative quantities of low-yttria tetragonal and high-yttria tetragonal cubic phases after 100 h annealing of zirconia 8 wt.% yttria [4.59] (reproduced with permission of Elsevier).
Figure 4.34 Typical multilayer thermal barrier coating [4.60] (reproduced with permission of Elsevier).
Figure 4.35 Microstructure of (a) plasma sprayed and (b) EB-PVD coatings [4.61, 4.60] (reproduced with permission of Elsevier).
Figure 4.36 Thermal conductivity versus temperature for several refractory compounds [4.62] (reproduced with permission of John Wiley and Sons).
Chapter 5: Synthesis, Properties and Applications of YBa2Cu3O7−x
Figure 5.1 Elementary unit of YBa
2
Cu
3
O
7−
x
.
Figure 5.2 The phase ternary diagram of CuO–BaO-YO
1.5
at 1223 K [5.6]. The superconducting phase YBa
2
Cu
3
O
7−
x
is denoted 123 and the phases YBa
3
Cu
2
O
x
and Y
2
BaCuO
x
are denoted 132 and 211 respectively.
Figure 5.3 The limit between tetragonal and orthorhombic phases and the area of superconducting effect appearance in the space of temperature and number of oxygen atoms per YBCO molecule [5.2].
Figure 5.4 Powder YBCO prepared by
freeze-drying
[5.22].
Figure 5.5 Exclusion of magnetic field from a bulk superconducting sample.
Figure 5.6 Temperature dependence of critical magnetic field in superconductors of Type I.
Figure 5.7 Interface between superconducting and normal zones in the intermediate state, showing the penetration and coherence lengths in Type-I superconductors [5.25].
Figure 5.8 Typical temperature dependence of upper and lower critical magnetic fields on temperature in superconductors of Type II.
Figure 5.9 Partial oxygen pressure vs deposition temperature, showing the area of formation of crystal phases for deposition with different thin films methods [5.27] (reproduced with permission of Elsevier).
Figure 5.10 SEM images (secondary electrons) of PLD films with thicknesses of: (a) 0.4 µm, (b) 0.72 µm, (c) 1.17 µm, (d) 1.79 µm, (e) 2.33 µm [5.34] (reproduced with permission of Elsevier).
Figure 5.11 Epitaxial growth of YBCO on a monocrystalline substrate with different crystal planes at the interface [5.37].
Figure 5.12 Sketch of spray pyrolysis process [5.47].
Figure 5.13 Chemical composition of initial powder and of thermally sprayed coatings [5.63].
Figure 5.14 X-ray diffraction diagrams (a) of powder prepared by calcination having composition YBa
2
Cu
4
O
X
(6.5 =<x =< 7), (b) as-sprayed coating, (c) of coating heat treated at 1233 K in air for 3 h, (d) for 19 h, (e) for 115 h [5.63].
Figure 5.15 Optical micrograph in bright field of polished cross-section of coatings as-sprayed on steel substrates to a thickness of 700–1000 µm from powder obtained by calcination and having composition YBa
2
Cu
4
O
x
(6.5 =<x =< 7) [5.63].
Figure 5.16 Scanning electron micrograph (secondary electrons) of a fractured cross-section of sample shown in Figure 5.15 submitted to heat treatment in air at 1223 K for 95 h followed by treatment in flowing oxygen at 773 K for 24 h and at 673 K for 48 h [5.63].
Figure 5.17 Calculation of theoretical density of YBCO powder of 50 µm size at 1113 K vs HIP pressure for different times of processing [5.74] (reproduced with permission).
Figure 5.18 Typical microstructure of melt processed YBCO sample exhibiting the layered
ab
-planes [5.75] (reproduced with permission).
Figure 5.19 Critical current density vs. applied magnetic field intensity for YBCO samples produced using different methods [5.75] (reproduced with permission of Elsevier).
Figure 5.20 Sketch of a crystal grown from a melt with top seeding [5.79] (reproduced with permission of Elsevier).
Figure 5.21 Typical layered structure of YBCO tape.
Figure 5.22 Cross-section of YBCO conducting tape [5.82] (reproduced with permission of Elsevier).
Figure 5.23 Structure of a cable including superconducting tapes [5.84] (reproduced with permission of Elsevier).
Figure 5.24 Sketch of an FCL with closed cooling cycle [5.83] (reproduced with permission of Elsevier).
Figure 5.25 Levitation force vs. distance from magnet and YBCO samples produced by top-seeded melting growth at 77 K and at magnetic field of 0.5 T [5.78] (reproduced with permission of Elsevier).
Figure 5.26 Arrays tested for achieving the greatest levitation force [5.92] (reproduced with permission of Elsevier).
Figure 5.27 The first
maglev
vehicle used to transport humans [5.93] (reproduced with permission of Elsevier).
Figure 5.28 Synchronous superconducting generator [5.94] (reproduced with permission of Elsevier).
Figure 5.29 Critical current for a commercial 12 mm wide YBCO tape (including 50 µm thick nickel base substrate, 0.2 µm thick buffer layer, 1 µm thick YBCO layer and 2 µm thick silver layer as in Figure 5.21) vs. magnetic field perpendicular to tape, at different temperatures [5.99] (reproduced with permission of Elsevier).
Chapter 6: Extraction, Properties and Applications of Titania
Figure 6.1 Titanium dioxide demand by industry sector.
Figure 6.2 Titanium dioxide demand by end market.
Figure 6.3 Anatase structure.
Figure 6.4 Rutile structure.
Figure 6.5 Brookite structure.
Figure 6.6 System Ti–O: calculated solid solution limits. α
ss
= α-Ti solid solution; β = β-Ti solid solution [6.9] (reproduced with permission of Elsevier).
Figure 6.7 Anatase–rutile transition temperature as a function of crystallite size [6.12] (reproduced with permission of Nature Publishing Group).
Figure 6.8 Projection of the (112) plane of anatase and the rearrangement of atoms necessary to form the rutile structure, and the mutual orientations of anatase and rutile structures [6.13]. Reproduced with permission of Elsevier.
Figure 6.9 Flow chart of the sol–gel process for the preparation of nano-TiO
2
powders.
Figure 6.10 Band model of TiO
2
showing the energy levels of intrinsic lattice defects [6.30]. Reproduced with permission of American Chemical Society.
Figure 6.11 Electronic structure of TiO
2
showing the energy levels of different cations [6.32]. Reproduced with permission of The Physical Society of Japan.
Figure 6.12 Equilibrium defect concentrations in bulk, undoped TiO
2
as a function of inverse temperature at p
O2
= 1 atm and p
H2O
= 0.025 atm [6.36]. Reproduced with permission of American Chemical Society.
Figure 6.13 Dielectric constants and fitting curve for multiphase TiO
2
films of 400 nm [6.41]. Reproduced with permission of Springer.
Figure 6.14 Frequency dependence of dielectric constant measured at different temperatures for rutile [6.45]. Aleksandra Wypych et al_https://www.hindawi.com/journals/jnm/2014/124814/abs/-Attribution 3.0 Unported (CC BY 3.0).
Figure 6.15 Frequency dependence of loss tangent measured at different temperatures for rutile [6.45]. Aleksandra Wypych et al_https://www.hindawi.com/journals/jnm/2014/124814/abs/-Attribution 3.0 Unported (CC BY 3.0).
Figure 6.16 Frequency dependence of dielectric constant measured at 20°C for TiO
2
pellets in Table 6.5 [6.45]. Reproduced with permission of Springer.
Figure 6.18 Frequency dependence of loss tangent measured at 20°C for TiO
2
pellets of Table 6.5 [6.46]. Reproduced with permission of Springer.
Figure 6.17 Frequency dependence of dielectric constant measured at 20°C for TiO
2
pellets sintered in the 700–1000°C temperature range [6.46]. Reproduced with permission of Springer.
Figure 6.19 Experimental dielectric constant of TiO
2
films (0.6 µm) as a function of thickness [6.47]. Reproduced with permission of Elsevier.
Figure 6.20 The polarization effects on capacitance and dielectric loss for TiO
2
film within aluminum electrodes [6.48]. Reproduced with permission of Elsevier.
Figure 6.21 The temperature dependence of electric capacitance for a TiO
2
thin film (0.6 µm) [6.48]. Reproduced with permission of Elsevier.
Figure 6.22 Dilatometric shrinkage curves and differential curves against temperature of two powder compacts of different densities: MC, 59% and GC, 87% theoretical density respectively, where MC is a pellet compacted at 65 MPa and GC at 4.5 GPa. Heating rate is 10°C/min [6.50]. Reproduced with permission of Elsevier.
Figure 6.23 Relative density and grain size of TiO
2
ceramics against sintering temperature.
Figure 6.24 Microstructural aspects of TiO
2
nanopowder sintered in oxidizing atmosphere at 800°C [6.46]. Reproduced with permission of Springer.
Figure 6.25 Microstructural aspects of TiO
2
nanopowder sintered in oxidizing atmosphere at 1000°C [6.46]. Reproduced with permission of Springer.
Figure 6.26 Microstructure of TiO
2
ceramic sintered at 1350°C [6.51]. Courtesy of Rubenis 2013.
Figure 6.27 SEM image of rutile crystal grown on Si substrate. Insert: magnified image of the TiO
2
[6.60]. Reproduced with permission of Cambridge University Press.
Figure 6.28 AFM micrographs of 2 × 2 µm thin film crystallized at 800°C for 1 h [6.61]. Reproduced with permission of Elsevier.
Figure 6.29 Relative density and grain size versus sintering time for a 140 nm film at different sintering temperatures [6.63]. Reproduced with permission of John Wiley and Sons.
Figure 6.30 SEM photo of a TiO
2
film on mica after sintering at 850°C [6.62]. Reproduced with permission of Elsevier.
Figure 6.31 SEM micrograph (secondary electrons) of cross-section of multilayer TiO
2
and hydroxyapatite coating with gradient of chemical composition [6.65]. Reproduced with permission of Elsevier.
Figure 6.32 TiO
2
and Al
2
O
3
dual-layer thin films as antireflection coatings on silicon [6.66]. Reproduced with permission of Elsevier.
Figure 6.33 UV–visible transmittance spectra: solid line, experimental; dotted line, calculated. The glass substrate transmittance is also shown, as a dashed line [6.67]. Reproduced with permission of Elsevier.
Figure 6.34 Refractive index n versus the wavelength in the transparent region: A, anatase–rutile; B, amorphous; C, anatase; D, rutile [6.68]. Reproduced with permission of Elsevier.
Figure 6.35 Extinction coefficient k versus the wavelength in the transparent region: A, anatase–rutile; B, amorphous; C, anatase; D, rutile [6.68]. Reproduced with permission of Elsevier.
Figure 6.36 Schematic representation of the photocatalytic process on TiO
2
[6.70]. Ed. M. NageebRashed CC BY 3.0 license.
Figure 6.37 Absorbance of SiO
2
/VO
2
and SiO
2
/VO
2
/TiO
2
samples [6.73]. Reproduced with permission of Elsevier.
Figure 6.38 Electrons from the valence band are excited to the conduction band by UV irradiation. Electrons migrate to gold particles and induce hydrogen production, while holes left behind in the valence band promote the evolution of oxygen [6.75]. Credit courtesy Chi-Sheng Wu.
Figure 6.39 Scattering of light by rutile for blue, green and red light as a function of particle size [6.81].
Figure 6.40 Scattering coefficient for two different rutile particles having different morphologies, as a function of interparticle separation. The horizontal line shows the results for two non-interacting morphological rutile particles [6.80]. Reproduced with permission of John Wiley and Sons.
Figure 6.41 Pigment-use in industry [6.82].
Figure 6.42 Concentrations of anatase and rutile in enamel fired at 780°C. Points are experimental data and fitted curves are calculated from simulations [6.84]. Reproduced with permission of John Wiley and Sons.
Figure 6.43 Coefficient of diffusive reflectivity of two different enamel coatings having a thickness of 0.15 mm on sheet steel, in relation to the enamel's content of TiO
2
. The two enamel recipes have different chemical compositions [6.86]. Reproduced with permission of Springer.
Figure 6.44 TiO
2
Effect of particle size and distribution on properties [6.81].
Figure 6.45 SEM micrographs of a clay-rutile coated paper at 50 wt.% addition [6.92]. Reproduced with permission of Springer.
Figure 6.46 Transmittance spectra for untreated and treated plain white cotton.
Figure 6.47 High resolution field emission SEM images of titania coated on the surface of a cellulose fiber [6.94]. Reproduced with permission of Elsevier.
Figure 6.48 Cross section of an anatase TiO
2
coating seen by scanning electron microscopy. The coating thickness is about 1 µm [6.97]. Reproduced with permission of Elsevier.
Figure 6.49 Schematic representation of a UV-LED-based photocatalytic reactor equipped with a real time in-stream sensor unit [6.99]. Reproduced with permission of Elsevier.
Figure 6.50 Typical carbon dioxide formation profiles during photocatalytic decomposition of gaseous acetaldehyde (CH
3
CHO) on un-doped TiO
2
and doped with Mn samples under UV and visible light irradiation [6.100]. Reproduced with permission of Elsevier.
Figure 6.51 Schematic representation of SEM images of thin TiO
2
films annealed at: (a) 800°C (b) 900°C; (c) 1000°C. The initial grain size is below 1 µm and becomes larger with temperature, simultaneous with anisotropic growth.
Figure 6.52 Self-cleaning effect of 0.2–0.5 µm film of TiO
2
glass surface.
Figure 6.53 Removal of atmospheric air pollution at the surface of TiO
2
concrete [6.103]. N. Bengtsson_http://materconstrucc.revistas.csic.es/index.php/materconstrucc/article/view/1461-Attribution 3.0 Spain (CC BY 3.0 ES).
Chapter 7: Synthesis, Properties and Applications of Hydroxyapatite
Figure 7.1 Elementary unit of Ca
10
(PO
4
)
6
(OH)
2
[7.4] (reproduced with permission of Elsevier).
Figure 7.2 Phase diagram of CaO and P
2
O
5
at high temperatures under partial pressure of steam equal to
p
H2O
= 66.5 kPa. AP, Ca
10
(PO
4
)
6
(OH)
2
, HA; C
4
P, Ca
4
P
2
O
9
, TTCP; αC
3
P, β-Ca
3
(PO
4
)
2
, β-TCP; α′C
3
P: α-Ca
3
(PO
4
)
2
, α-TCP [7.6] (reproduced with permission of John Wiley and Sons).
Figure 7.3 Part of the CaO and P
2
O
5
phase diagram showing (a) temperature
T
1
of transformation of HA into
α
-TCP and TTCP; (b) evolution of this temperature with partial steam pressure
p
H20
. HA
p
, Ca
10
(PO
4
)
6
(OH)
2
, HA; C
4
P, Ca
4
P
2
O
9
, TTCP; αC
3
P, β-Ca
3
(PO
4
)
2
, β-TCP; α′C
3
P: α-Ca
3
(PO
4
)
2
, α-TCP [7.6] (reproduced with permission of John Wiley and Sons).
Figure 7.4 Phase diagram of Ca and P
2
O
5
at high temperatures under partial pressure of steam equal to
p
H2O
= 0. C
4
P, Ca
4
P
2
O
9
, TTCP; αC
3
P, β-Ca
3
(PO
4
)
2
, β-TCP; α′C
3
P: α-Ca
3
(PO
4
)
2
, α-TCP [7.6]
2
(reproduced with permission of John Wiley and Sons).
Figure 7.5 Production of HA (abbreviated as HAP) by solid-state reaction at room temperature [7.11] (reproduced with permission of Elsevier).
Figure 7.6 Sol–gel procedure for HA powder synthesis [7.17] (reproduced with permission of Elsevier).
Figure 7.7 Fluidized bed installation used to synthesize HA powder [7.8] (reproduced with permission of Elsevier).
Figure 7.8 Abandoned abalone shells [7.22] (reproduced with permission of Elsevier).
Figure 7.9 Rotating packed bed [7.26] (reproduced with permission of Elsevier).
Figure 7.10 Representation of solution combustion process for HA synthesis in which DAP abbreviates (NH
4
)
2
HPO
4
[7.27] (reproduced with permission of Elsevier).
Figure 7.11 Morphology of composite powder HA+Ti6Al4V obtained from the slurry [7.28] (reproduced with permission of Springer).
Figure 7.12 Specific heat of HA vs temperature, according to references cp1 [7.36] and cp2 [7.37], averaged and extrapolated following a regression equation
c
p
= 269.55 ln (T)–748.22, with a regression coefficient
R
2
= 0.99 [7.35] (reproduced with permission of Elsevier).
Figure 7.13 Thermal conductivity of dense and porous (
P
= 12%) HA vs temperature [7.35] (reproduced with permission of Elsevier).
Figure 7.14 Modulus of elasticity of sintered HA samples vs sintering temperature (using data presented in [7.48] and manufacturing technology described in Table 7.4) (reproduced with permission of Elsevier).
Figure 7.15 Temperature fields inside a HA powder particle in flight in plasma jet/combustion flame and associated crystal phases [7.35] (reproduced with permission of Elsevier).
Figure 7.16 SEM image (secondary electrons) of surface of commercial HA coating: (a) small powder particles resulting from disintegration upon impact; (b) partly molten powder particle.
Figure 7.17 Profile of atomic ratio Ca/P obtained using EMPA through the thickness of a commercial HA coating.
Figure 7.18 TEM micrograph of the sintered zone inside an HA coating formed by plasma spraying of a suspension.
Figure 7.19 SEM micrograph (secondary electrons) of cross-section of a suspension precursor plasma-sprayed HA coating.
Figure 7.20 Sintering time for HA particles of initial diameter
d
= 0.1, 0.3 or 1 µm to reach a neck size of
X
/
d
= 0.1 vs temperature for surface diffusion mechanism.
Figure 7.21 Titanium alloy stem of a hip prosthesis: (a) before; (b) after deposition of HA coating by plasma spraying.
Figure 7.22 The main parts of a knee prosthesis [7.91] (reproduced with permission of Medial Multimedia Group, LLC).
Figure 7.23 Tibial component of a prosthesis with HA coating on the undersurface [7.92] (reproduced with permission of Elsevier).
Figure 7.24 Dental implant for individual tooth replacement [7.95].
Figure 7.25 Dental implants coated with plasma-sprayed HA coating: (a) screw; (b) cylinder [7.96] (reproduced with permission).
List of Tables
Chapter 1: Technical and Economic Importance of Oxides
Table 1.1 Applications of advanced ceramics related to their mechanical properties
Table 1.2 Applications of oxides in electrical and electronic engineering
Table 1.3 Dielectric properties of oxides having different modes of conduction
Table 1.4 Applications of coatings with different modes of conduction
Table 1.5 High-temperature applications of selected oxides and their thermophysical properties [1.27, 1.28]
Table 1.6 Application of oxides in medical devices
Table 1.7 Prices of bauxite and alumina
Chapter 2: Fundamentals of Oxide Manufacturing
Table 2.1 The fundamental steps in manufacturing objects with modern oxides and associated processes [2.1, 2.2]
Table 2.2 Possible combinations of dispersed and continuous phases [2.29]
Table 2.3 Viscosity of some Newtonian liquids at different temperatures
Table 2.4 Examples of surface tension of a few common liquids in air [2.34]
Table 2.5 Stability of suspension vs
ζ
- potential [2.5]
Table 2.6 Isoelectric points of some oxides [2.4, 2.5]
Table 2.7 Conversion of equivalent diameters
Table 2.8 Examples of external and internal morphologies of metal oxide powders
Table 2.9 Parameters used in development of a new powder using a spray drying technique
Table 2.10 Commercial hydroxyapatite powder produced by spray-drying
Table 2.11 Examples of operational parameters used in mechanofusion of cermet powders
Table 2.12 Examples of preparation procedures of different oxides with the use of sol–gel technique
Table 2.13 Examples of preparation procedures of different oxides using the wet-precipitation method
Table 2.14 Methods of oxide films and coatings manufacture [2.83, 2.84].
a
Table 2.15 Examples of oxide films synthesized by sol–gel process
Table 2.16 Reactions in photochemical LCVD processes [2.104]
Table 2.17 Parameters of PEPVD for oxide films processes [2.106]
Table 2.18 Sputtering yield of Ar
+
ion having initial energy of
E
p
i
= 500 eV (8.01 × 10
−17
J) [2.109]
Table 2.19 Examples of solutions used as feedstocks in SPPS processes to obtain oxide coatings
Table 2.20 Examples of wetting angles between liquid metals and some oxides [2.139]
Table 2.21 Industrial lasers used in surface treatments
Table 2.22 Typical composition of ceramics inks [2.158]
Table 2.23 Coefficients for the initial stage of sintering [2.58]
Table 2.24 Examples of binary oxide systems used commercially and produced by liquid-phase sintering [2.58]
Chapter 3: Extraction, Properties and Applications of Alumina
Table 3.1 Synthesis of
α
-Al
2
O
3
powders using different methods
Table 3.2 Chemical properties of alumina monocrystals.
a
Table 3.3 Thermal expansion coefficient and thermal conductivity of
α
-Al
2
O
3
at different temperatures
Table 3.4 The self-diffusion data of of
α
–Al
2
O
3
Table 3.5 Dielectric properties of alumina at room temperature
Table 3.6 Elastic constants of alumina at room temperature
Chapter 4: Extraction, Properties and Applications of Zirconia
Table 4.1 Chemical analyses of zircon and zirconia products from Australia and South Africa
Table 4.2 World zirconium reserves
Table 4.3 World zirconium mine production
Table 4.4 Physical properties of sintered partially stabilized zirconia with 8 mol% of yttria
Table 4.5 Wear rate and friction coefficient of different joint prosthesis materials
Table 4.6 Experimental and calculated mechanical parameters of materials used in crown fabrication [4.48]
Table 4.7 Effective diffusion coefficient of oxygen in zirconia with 6–25 mol% Y
2
0
3
[4.50]
Table 4.8 Physical properties of oxide materials for thermal barrier coatings
Chapter 5: Synthesis, Properties and Applications of YBa2Cu3O7−x
Table 5.1 Electrical and superconducting properties of YBCO monocrystals and polycrystal at critical temperature of
T
= 92 K [5.26].
a
Table 5.2 Influence of major PLD process parameters on film microstructures [5.29]
Table 5.3 Description of recent studies on YBCO films obtained by PLD
Table 5.4 Spray pyrolysis deposition studies and the obtained YBCO films
Table 5.5 Description of sol–gel deposition processes and of obtained YBCO films
Table 5.6 Technology and superconducting properties of YBCO 3D samples obtained using melt-texturing growth
Chapter 6: Extraction, Properties and Applications of Titania
Table 6.1 Identified reserves of ilmenite and rutile in 2014
Table 6.2 Physical properties of anatase, rutile and brookite phases
Table 6.3 Synthesis methods of TiO
2
and resultant phases
Table 6.4 Dielectric properties of anatase, rutile and brookite
Table 6.5 Processing method of TiO
2
discs for dielectric characterizations. TIP is titanium isopropoxide and TMAOH is tetramethyl ammonium hydroxyde solution [6.45]
Table 6.6 Refractive indices of pigment dispersions and media
Table 6.7 Typical chemical composition of a vitreous enamel for sheet steel, fired at 800°C
Chapter 7: Synthesis, Properties and Applications of Hydroxyapatite
Table 7.1 Calcium phosphates having atomic ratio Ca/P ≥ 1 [7.2, 7.3]
Table 7.2 Mechanical properties of HA single cystals
Table 7.3 Mechanical properties of HA coatings
Table 7.4 Mechanical properties of 3D objects of hydroxyapatite
Table 7.5 Ion concentrations of simulated body fluid and human blood plasma [7.56]
Table 7.6 Relative solubility of calcium phosphates for buffer solutions of different pH values [7.5]
Table 7.7 Atomistic methods of HA films deposition
Table 7.8 Experimental observations of different phases in coatings plasma sprayed using HA powder and different working gas compositions and carrier gas flow rates [7.67]
Table 7.9 Evolution of crystal phase content in suspension plasma-sprayed HA coating, when soaked in SBF during
in-vitro
tests [7.43]
Table 7.10 Features of chemical methods of HA film and coating deposition [7.80]
Table 7.11 Typical conventional sintering processes applied to obtain 3D objects
Table 7.12 Some applications of HA in oral, head and neck surgery [7.5]
Table 7.13 Requirement for HA coatings to be applied in bioimplants
Industrial Chemistry of Oxides for Emerging Applications
Lech PawłowskiPhilippe Blanchart
Laboratory SPCTS, University of Limoges, France
This edition first published 2018
© 2018 John Wiley and Sons Ltd
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Library of Congress Cataloging-in-Publication Data
Names: Pawłowski, Lech, author. | Blanchart, Philippe, author.
Title: Industrial chemistry of oxides for emerging applications / Lech Pawłowski, Philippe Blanchart.
Description: First edition. | Hoboken, NJ : John Wiley & Sons, 2018. | Includes bibliographical references and index. |
Identifiers: LCCN 2017056376 (print) | LCCN 2018004507 (ebook) | ISBN 9781119423676 (pdf) | ISBN 9781119424055 (epub) | ISBN 9781119423621 (cloth)
Subjects: LCSH: Oxides-Industrial applications.
Classification: LCC TP245.O9 (ebook) | LCC TP245.O9 P43 2018 (print) | DDC 549/.5-dc23
LC record available at https://lccn.loc.gov/2017056376
Cover Design: Wiley
Cover Images: Courtesy of Lech Pawłowski and Philippe Blanchart
Preface
The idea of this book matured during the cycle of lectures on industrial chemistry given by one of the authors of this book, Lech Pawłowski, to the students of Ecole Nationale Supérieure de Chimie de Lille (ENSCL) in the years 1999 to 2010. The lectures were supported by his research activity, which has been focused, since the end of his PhD at the Technical University of Wrocław in Poland, on plasma spraying of oxides. He initially developed alumina coatings on metal substrates for hybrid microelectronics. Alumina coatings were also an important feature of anilox rolls used in the printing industry, which he developed at the W. Haldenwanger business in Berlin. Finally, after coming back to the academic world, he researched YBCO high-temperature superconductors at Monash University in Melbourne in Australia, and suspension and solution plasma sprayed titania, hydroxyapatite and zirconia at ENSCL and the University of Limoges in France.
After having worked for more than four decades on the science and engineering of metal oxide films and coatings, he decided to enlarge the area of his scientific interest to the problems of the oxide ore mining and refining industries. The problems of oxide powder manufacturing are important since they are intermediate products in the manufacturing of final 2D and 3D objects. The 2D manufacturing methods include principally the preparation of thin films and thick coatings, while the 3D methods are the well-known sintering process and also the emerging methods of laser and arc prototyping, more recently referred to as “additive manufacturing”.
The students listening to the lectures were particularly interested in the industrial aspects of each stage of the oxides' transformation, including industrial methods, the location of the industry, and the availability and prices of the raw materials. Also of interest were the many new applications of oxides in the energy, biomedical, chemical, and electronics sectors as well as elsewhere.
The coverage of each oxide adopted in this book is chronological, starting from an insight into the extraction processes of the oxide ores, their purification and transformation into pure or alloyed powders, their appropriate characterization, and the subsequent processes of formation: 2D films by PVD and CVD, coatings by thermal spraying, and complicated 3D objects by sintering and rapid prototyping.
The selection of oxides for inclusion in the book was guided mainly by the current context of industrial applications. Consequently, the discussion concerns the natural metal oxides such as:
alumina, which is used in electronics as an insulator, and in the chemical industry as a support for catalysts
zirconia, used in the transportation industry as a thermal barrier coating, and in energy generation as a solid electrolyte in solid oxide fuel cells
titania, used in water treatment as a photo-catalyst, and in electronics as a hydrogen sensor.
The synthetic multi-oxides selected and discussed in detail are:
hydroxyapatite, used in the biomedical industry as a bioactive material
YBa
2
Cu
3
O
7−
x
, which is about to be used in the energy transport industry as a superconductor; its critical temperature of about 90 K enables it to be cooled down by cheap liquid nitrogen.
An important point that is considered in the book is the strategic aspect of oxides. Some oxides, such as the rare earth oxides, are becoming more and more expensive because of growing demand and because of their strategic importance for the countries producing them as raw materials and the countries using them. This aspect cannot be neglected any longer because the price of final products will depend heavily on the price of the raw materials. This perspective is, however, more often included in only the industrial research and development sector.
Philippe Blanchart is associated with the writing of this book due to his experience in the field. His experience was gained during many years of research in different areas of ceramic science and technology, including development of new industrial applications in collaboration with many European and overseas laboratories and companies. He teaches and researches at the Ecole Nationale Supérieure de Céramique Industrielle at Limoges University. In particular, his extensive teaching experience in the School of Engineering helped him collate the essential information and structure the chapters in a pedagogic way.
Oxide ceramics may be crystalline or amorphous. They have been used by humans since early history and have contributed considerably to improving the quality of our lives. High-temperature processes are often associated with the manufacturing of ceramics. Manufacturing also encompasses many economic and environmental issues and there is a growing need to develop ceramic processing methods that are adapted to environmental requirements and norms.
Many improvements in the quality of ceramic objects are being achieved through use of nanosized powders. These powders have given new potential for innovation and brought about new and effective applications of ceramics.
The science of metal oxides is multidisciplinary and combines powder processing, morphological and structural characterization, and the science and technology of engineering processes. It also involves knowledge of physical processes and inorganic–organic physical chemistry. There is a clear need to review the abundant and diverse literature from many significantly different disciplines.
The literature devoted to oxides amounts to thousands of new contributions every year. Recent years have been particularly rich, and the coverage in the present book tries to take in all of the most important contributions since 2013.
The book deals with the chemistry and technology of oxides used in industrial applications by engineers. It requires a fundamental knowledge of physical chemistry, materials science and related disciplines. Special emphasis is given to both the underlying science and to industrial applications.
The authors hope that this book will be useful to active researchers and engineers, the managers who take decisions related to new technologies, and to university professors and their students. All the chapters of the book are up-to-date and show that metal oxides are the source of numerous emerging applications, with properties that will have a considerable impact on the development of continuously evolving production methods.
The authors hope that this book will encourage the reader to enter and understand these challenging fields.
Lech PawłowskiPhilippe Blanchart
Limoges 26 June 2017
Acknowledgments
The authors would like to thank the team from Wiley – Emma Strickland, Jennifer Cossham, Elsie Merlin, and Shyamala Venkateswaran – for their professional, rapid and friendly help. Colleagues from our common laboratory, SPCTS, Thierry Chartier and Bernard Pateyron helped the authors with their friendly support.
