Contents

Cover

Title page

Copyright page

Preface

Part 1: Design, Processing, and Properties

Chapter 1: Development of Epitaxial Oxide Ceramics Nanomaterials Based on Chemical Strategies on Semiconductor Platforms
1. 1.1 Introduction
2. 1.2 Integration of Epitaxial Functional Oxides Nanomaterials on Silicon Entirely Performed by Chemical Solution Strategies
3. 1.3 Integration of Functional Oxides by Combining Soft Chemistry and Physical Techniques
4. 1.4 Conclusions
5. Acknowledgments
6. References
Chapter 2: Biphasic, Triphasic, and Multiphasic Calcium Orthophosphates
1. 2.1 Introduction
2. 2.2 General Definitions and Knowledge
3. 2.3 Various Types of Biphasic, Triphasic, and Multiphasic CaPO₄
4. 2.4 Stability
5. 2.5 Preparation
6. 2.6 Properties
7. 2.7 Biomedical Applications
8. 2.8 Conclusions
9. References
Chapter 3: An Energy Efficient Processing Route for Advance Ceramic Composites Using Microwaves
1. 3.1 Introduction
2. 3.2 Historical Developments in Materials Processing by Microwaves
3. 3.3 Introduction to Microwave Heating Process
4. 3.4 Heating Methods by Microwaves
5. 3.5 Advantages/Limitations of Microwave Material Processing
6. 3.6 Application of Microwave Heating in Composite Processing
7. 3.7 Future Prospectives
8. 3.8 Conclusion
9. References

Part 2: Ceramic Composites: Fundamental and Frontiers

Chapter 4: Continuous Fiber-reinforced Ceramic Matrix Composites
1. 4.1 Introduction
2. 4.2 Parts of a CMC
3. 4.3 Modern Uses of CMCs
4. 4.4 History
5. 4.5 Ceramic Fibers
6. 4.6 Interface/Interphase
7. 4.7 Matrix Materials
8. 4.8 Matrix Fabrication Techniques
9. 4.9 Toughness of CMCs
10. 4.10 Applications
11. Acknowledgments
12. References
Chapter 5: Yytria- and Magnesia-doped Alumina Ceramic Reinforced with Multi-walled Carbon Nanotubes
1. 5.1 Introduction
2. 5.2 Dispersions and Stability of MWCNTs
3. 5.3 Influence of Yytria (Y₂O₃) Doping on MWCNT/Al₂O₃ Nanocomposites
4. 5.4 Magnesia (MgO)-Tuned MWCNT/Al₂O₃ Nanocomposites
5. 5.5 Conclusions
6. Acknowledgments
7. References
Chapter 6: Oxidation-induced Crack Healing in MAX Phase Containing Ceramic Composites
1. 6.1 History of Crack Healing in Ceramics
2. 6.2 High-temperature Crack Healing in MAX Phases
3. 6.3 Lower-temperature Crack Healing in MAX Phase-based Ceramics
4. 6.4 Conclusions
5. Acknowledgments
6. References
Chapter 7: SWCNTs versus MWCNTs as Reinforcement Agents in Zirconia-and Alumina-based Nanocomposites: Which One to Use
1. 7.1 Introduction
2. 7.2 Single-walled Carbon Nanotubes
3. 7.3 Multi-walled Carbon Nanotubes
4. 7.4 The Effects of CNTs Types on the Mechanical Properties of Al₂O₃- and ZrO₂-based Ceramics
5. 7.5 Why SWCNTs? or Why MWCNTs?
6. 7.6 Conclusions
7. Acknowledgments
8. References

Part 3: Functional and Applied Ceramics

Chapter 8: Application of Organic and Inorganic Wastes in Clay Brick Production: A Chemometric Approach
1. 8.1 Introduction
2. 8.2 Materials and Methods
3. 8.3 Results and Discussion
4. 8.4 Conclusions
5. Acknowledgments
6. References
Chapter 9: Functional Tantalum-based Oxides: From the Structure to the Applications
1. 9.1 Functional Materials: Current Needs
2. 9.2 Importance of Tantalum and Tantalum-based Oxides
3. 9.3 Properties of Alkali Tantalates
4. 9.4 Processing of Alkali Tantalate Ceramics for Electronic Applications
5. 9.5 Potential Applications of Alkali Tantalates
6. 9.6 Conclusions
7. Acknowledgements
8. References
Chapter 10: Application of Silver Tin Research on Hydroxyapatite
1. 10.1 Introduction
2. 10.2 Materials and Methods
3. 10.3 Results and Discussion
4. 10.4 Conclusion
5. References

Index

End User License Agreement

List of Illustrations

Chapter 1

Figure 1.1 General schematic diagram representing all the processes, oxide nanomaterials integrated on silicon, and applications discussed in this book chapter.
Figure 1.2 Thermally activated devitrification-crystallization of amorphous silica monoliths assisted by different doping levels of Sr²⁺ catalyst and monitored by neutron thermodiffractometry. (a) 1 atomic percent (1%) of Sr²⁺, (b) 2 atomic percent (2%) of Sr²⁺, and (c) 6 atomic percent (6%) of Sr²⁺. Notice that under this amount of Sr²⁺, amorphous silica monoliths crystallize into pure quartz polymorph at relative low temperature. (d) 12 atomic percent (12%) of Sr²⁺. Notice that under this doping level within the silica, the crystallization of silica results in a competition between cristobalite and quartz polymorphs.
Figure 1.3 Schematics of the growth mechanism of epitaxial quartz thin films on (100) Si substrate. (1) Cross-sectional cartoon of the initial amorphous mesoporous silica film where the 6% of Sr²⁺ catalyst is homogeneously distributed along the silica matrix and silicon interface. (2) Devitrification and melting of the original amorphous mesoporous film and first crystallization above 925 °C of epitaxial α-quartz film. (3) Epitaxial quartz film formation on (100) Si substrate. After crystallization process all Sr²⁺ sinters and forms spherical amorphous nanoparticles of SrCO₃ that are finally fixed at the surface within quartz grain boundaries.
Figure 1.4 (a) Graphic that exhibits the starting crystallization temperature of epitaxial α-quartz thin films on silicon. Inset figure shows the evolution of rocking curves for samples grown at different temperatures. Notice that 1000 °C is the optimal temperature that achieves the lower FWHM value (3°), indicating low out-of-plane misorientation of nanostructured α-quartz films. (b) Devitrification–crystallization of amorphous silica films at 1000 °C assisted by different doping levels of Sr²⁺ catalyst and analyzed by XRD: 1 atomic percent (1%) of Sr²⁺ (green), 2 atomic percent (2%) of Sr²⁺ (blue), 6 atomic percent (6%) of Sr²⁺ (red), and 12 atomic percent (12%) of Sr²⁺ (pink). Notice that as shown in Figure 1.2c only samples with 6% of Sr²⁺ can achieve the crystallization of quartz polymorph and consequently the direct epitaxy on (100) silicon. (c) Pole figure of quartz films that confirms the epitaxial relationship between quartz thin film and (100) silicon substrate which is [210]Q//[100]Si. (d) HRTEM image of the α-quartz along [001] crystallographic direction that shows a high-quality crystallinity without structural and chemical defects.
Figure 1.5 Epitaxial growth of α-quartz thin films on Si(100) with tunable textures by using sol-gel chemistry. Two different approaches can be used in order to obtain amorphous silica films with different pore sizes: one-pot synthesis which allows to prepare macropores quartz films (a and b) and two-step synthesis that can produce mesopores with an average pore of 28 nm and dense quartz films (c, d, e, and f).
Figure 1.6 Piezoelectric measurements by PFM technique. Notice that quartz films on silicon vivrates under the applied AC voltage and this feature is detected through the deflection of the tip at a particular resonance frequency (a). The tip displacement is linear with the amplitude of the applied AC field, and the piezoelectric coefficient obtained is in the order of 2 picometers per volt, which is of comparable to the one measured in quartz bulk material.
Figure 1.7 Growth mechanism and synthesis methods of both, thin-film and vertical epitaxial oxide nanowires on Si (100) substrate. (1a) Nanoporous polymer template deposited on a SiO₂/Si substrate filled with the chemical precursor solution containing Sr²⁺ melting agents. (1b) 1D-confined nucleation in high-aspect-ratio nanopores of oxide nanowires seeds and first devitrification and nucleation of disoriented quartz crystals at the silicon interface. (1c) α-Quartz film formation at higher temperatures (800 °C), allowing the epitaxial stabilization of oxide nanowires. (2a) Chemical precursor solution containing Sr²⁺ melting agents deposited on a SiO₂/Si substrate by using spin-coating technique. (2b) 2D-confined nucleation in thin film form of oxide nanowires seeds and first devitrification and nucleation of disoriented quartz crystals at the silicon interface. (2c) α-Quartz film formation at higher temperatures (800 °C), allowing the epitaxial stabilization of thin-film oxide nanowires.
Figure 1.8 Low-magnification FEG–SEM images of both, vertical and thin film of epitaxial SrMn₈O₁₆ nanowires grown at 800 °C during 2 h on an α-quartz/Si substrate (a and b), respectively. Inset images and 3D schematics show an enlarged view of the SrMn₈O₁₆ nanowires on silicon substrate. Low-magnification HAADF image of epitaxial ferromagnetic LaSr-2 × 4 nanowires stabilized on α-quartz/Si substrate (800 °C during 5 h) (c). HRTEM image showing, the interface between quartz film and epitaxial LaSr-2 × 4 nanowires, viewed along [010]. The inset image represents the Fast Fourier Transform (FFT) of both crystallographic phases that confirm the epitaxial relation between the LaSr-2 × 4 nanowires and the α-quartz and which is given by [20-2] LaSr-2 × 4 // [-101] α-quartz. (d). Lebail fitting refinement of the XRD pattern of single-crystalline LaSr-2 × 4 nanowires on silicon substrate. Experimental records: red points; calculated: continuous black line; Bragg reflections: vertical green marks. The difference between the observed and calculated profiles is presented as a blue line. The inset image represents the proposed LaSr-2 × 4 nanowires cell model, where yellow spheres represent the Sr columns position, blue spheres the La columns position, and red and green spheres the O and Mn positions, respectively (e). Normalized magnetization versus temperature curve of LaSr-2 × 4 nanowires and La_0.7Sr_0.3MnO₃ powder blank samples measured at H = 1.5 T in an orthogonal configuration to the substrate. (f) Dichroism measurement performed by using TEM and Mn L_2,3 edges, along the two polarized configurations (+) and (−) (g).
Figure 1.9 3D Schematics exhibiting the chemical deposition and growth of highly textured ZnO thin film on Si (100) substrate (a). XRD pattern of textured ZnO thin film on silicon substrate. The inset image shows the 2D XRD pattern confirming the textured growth of polycrystalline ZnO thin film (b). Low magnification HAADF image of textured polycrystalline ZnO thin films stabilized on α-quartz/Si substrate (c). Cross-sectional HRTEM image of the quartz/ZnO interface viewed along the [001] crystallographic direction of quartz phase. The inset image represents the Fast Fourier Transform (FFT) of both crystallographic phases and confirms the orientation of ZnO nanoparticles induced by the α-quartz film which is given by the following crystallographic relation [010] ZnO //[001] α-quartz (d).
Figure 1.10 Schematic diagram that shows a new approach that combines MBE and PAD methods allowing the epitaxial growth of high-quality functional perovskite complex oxides multilayers on silicon substrate. First stage consists on the epitaxial growth of STO film on silicon by MBE. Inset shows 3D diagram and a cross-sectional HAADF–STEM image of a STO thin film epitaxially grown on silicon substrate by MBE (1). Second stage involves the use of STO/Si(100) as a large-scale pseudo-substrate which is combined with PAD chemical methodology for the integration of a new perovskite layer by spin-coating deposition technique (2). Finally, the resulting heterostructure produced by mixing MBE and PAD is combined again with MBE in order to produce the desired perovskite complex oxides multilayers on silicon substrate.
Figure 1.11 Low-magnification FEG–SEM image of a porous epitaxial BTO/LSMO/STO/Si(100) thin film grown by the combination of MBE and PAD methods. (a) Low-magnification HAADF image of a porous epitaxial BTO/LSMO/STO/Si(100) thin film (b) and (c), respectively. HRTEM image showing the interface between BTO layer grown by MBE and LSMO layer grown by PAD, viewed along the crystallographic direction [110]. Inset image shows the elemental mapping for Ti (yellow spheres), Ba (blue spheres), Mn (green spheres), and La/Sr (red spheres) indicating a high-quality and abrupt chemical interfaces between both perovskite layers (d). Reciprocal space map of a porous epitaxial BTO/LSMO/STO/Si(100) thin film (e). Rocking curve of BTO layer grown by MBE on LSMO/STO/Si(100) with a FWHM value of 1.15°. The inset shows the RHEED pattern exhibiting the epitaxial growth and high-quality surface of the BTO layer grown by MBE on the chemically synthesized LSMO film (f).
Figure 1.12 PFM analysis illustrating the electromechanical behavior of the porous columnar thick epitaxial BTO/LSMO/STO/Si(100) films. PFM phase and amplitude images of the 50-nm-thick BTO film after electrical poling (a and b), respectively. Local PFM amplitude and phase hysteresis loops measured in the same BaTiO₃ film, respectively (c).

Chapter 2

Figure 2.1 XRD patterns: bottom, the patterns of pure HA and β-TCP printed together; middle, mathematical summation of HA and β-TCP patterns; upper, biphasic calcium phosphate (BCP) consisting of 50% HA and 50% β-TCP. Reprinted from Refs [8, 9] with permission.
Figure 2.2 Phase diagram of the system CaO–P₂O₅ (C = CaO, P = P₂O₅) at elevated temperatures. Each line represents a phase boundary. Here, C₇P₅ means 7CaO·5P₂O₅; other abbreviations should be written out in the same manner. Reprinted from Refs [171, 172] with permission.
Figure 2.3 SEM images of β-TCP, HA, and BCPs with different β-TCP/HA ratios after sintering at 1130 °C. One can see that HA amount increasing results in gradual decreasing of the grain sizes. Reprinted from Ref. [133] with permission.
Figure 2.4 XRD patterns of the freeze-dried ACP precipitates and the calcined powders. One can see formation of biphasic formulations with variable α-TCP/β-TCP ratios at temperatures within 830–850 °C. Reprinted from Ref. [71] with permission.
Figure 2.5 Yield of HA, α-TCP, and β-TCP depending on the pH of the starting solution. Reprinted from Ref. [77] with permission.
Figure 2.6 A schematic picture of uniaxially pressed CaPO₄ samples consisting of symmetric layers with different compositions. Sintering of such formulations will result in functionally graded multiphasic bioceramics. Reprinted from Ref. [119] with permission.
Figure 2.7 Reconstruction of a femoral bone defect with BCP. X-ray images of a femur before (a) and after (b) reconstruction with the BCP and stabilized with internal fixation system, after trauma. Reprinted from Ref. [409] with permission.

Chapter 3

Figure 3.1 Developments in microwave material processing.
Figure 3.2 Effect of critical temperature on temperature rise (microwave effect).
Figure 3.3 Microwave–material interactions for various materials [119] © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.4 Effect of skin depth on microwave absorption for materials having (a) high skin depths, (b) skin depth comparable to material size, and (c) low skin depths.
Figure 3.5 (a) Direct microwave heating, (b) MHH, (c) effect of MHH on temperature profile, and (d) selective microwave heating.
Figure 3.6 Favorable characteristics of microwave material processing.
Figure 3.7 Comparison of sintering time for microwave and conventional heating of titanium [101].
Figure 3.8 Processing time curve for conventional and microwave heating of stainless steels [102]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.9 Temperature and power curves for microwave and conventional heating of W–Fe–Ni alloy [103]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.10 Comparison of microwave and conventional heating on melting of aluminum [104]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.11 Effect of heating modes on sintered density of W-Cu alloys [105].
Figure 3.12 Fields of microwave material processing [119] © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.13 Schematic principle for developments of joints through microwave [131]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.14 Copper joint produced by microwave heating [129]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.15 (a and b) SEM images of dissimilar joints of SS-316 and mild steel produced by MHH [128]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.16 Development of stainless steel (SS) joints by MHH [130]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.17 Schematic principle of MHH for development of claddings on bulk substrate [138]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.18 (a) XRD spectrum of composite clad, (b) typical SEM image showing microstructure of composite clad, and (c) microhardness profile along the cross section of clad [134]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.19 Schematic of LMH and (b) part produced by LMH [145]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.20 FGM developed by microwave heating [148]. © [Elsevier]. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the rights holder.
Figure 3.21 Various metallic parts sintered by microwaves [157].
Figure 3.22 (a) Schematic setup for development of composites via MHH and (b) actual processing of composites.
Figure 3.23 Metal–ceramic composites developed by MHH.
Figure 3.24 Typical back electron scattered images showing microstructures of (a) EWAC+10%SiC, (b) EWAC+10% Al₂O₃, (c) EWAC+10%WC10Co2Ni metal ceramic composites, and (d) magnified image showing the equiaxed grains.

Chapter 4

Figure 4.1 Cross-sectional micrograph of CMC.
Figure 4.2 Photograph of a bicycle composed of carbon fiber composite.
Figure 4.3 (a) Toray^® T-300 Carbon tow. (b) 3MNextel™ 610 woven fabric.
Figure 4.4 (a) A fiber (black) coated in an interphase (dark grey) surrounded by a matrix (grey). White lines indicate where the weak debonding interface lies. (b) A crack (white) traveling through the matrix (grey) into the interface material (dark grey) and deflecting around the fiber (black). (c) Duplex interphase system composed of a fiber (black), interphase 1 (dark grey), interphase 2 (light grey), and a matrix (grey). Interphase 1 bonds strong to the fiber and weak to interphase 2. Interphase 2 bonds weak to interphase 1 and strong to the matrix. The weak interface is where debonding will occur.
Figure 4.5 PIP process.
Figure 4.6 (a) Monolithic ceramic showing full crack propagation. (b) Ceramic matrix composite showing the disruption of crack propagation at the fiber–matrix interface.
Figure 4.7 (a) Axial tensile failure, (b) transverse tensile failure, and (c) shear failure.
Figure 4.8 Schematic representation of (a) fiber-matrix debonding and (b) fiber pullout.
Figure 4.9 SEM micrograph of a composite cross section showing energy absorbing mechanisms such as debonding and fiber pullout.
Figure 4.10 Diagram of cold and hot sections of an aircraft engine. Adapted from The Federal Aviation Administration, Tikalon, LLC [96].

Chapter 5

Figure 5.1 (a) TEM image of a MWCNT; (b) MWCNTs in an aqueous suspension, (i) agglomerated MWCNTs, (ii) partially suspended MWCNTs, and (iii) homogenously suspended MWCNTs; and (c and d) TEM images of SDS around MWCNTs.
Figure 5.2 Fractured surface SEM images of MWCNT/Al₂O₃ nanocomposites. (a) MWCNT gluts (black arrows), (b) partially dispersed MWCNTs and well-dispersed MWCNTs at (c) low and (d) high magnifications.
Figure 5.3 SEM fractured surface images of the nanocomposites showing well-dispersed MWCNTs (white arrows) within Al₂O₃ grains at (a) low and (b) high magnifications; and (c) TEM image of a MWCNT (white arrow) retrieved from the sintered nanocomposites, exhibiting its structural and morphological stability.
Figure 5.4 Densities and grain size of monolithic Al₂O₃ and MWCNT/Al₂O₃ nanocomposite samples with/without Y₂O₃ doping.
Figure 5.5 SEM images of polished and thermally etched (a) monolithic Al₂O₃-coarse Al₂O₃ grains; (b) Y₂O₃-free nanocomposites, showing heterogeneous fine and coarse (black circle) grained microstructure with residual flaws/pores (black arrows) in inset; (c) Y₂O₃-doped Al₂O₃ showing equiaxed grains; (d) Y₂O₃-doped nanocomposites exhibit flaw-free, fine-grained, and dense microstructure; (e) Y₂O₃-doped Al₂O₃ showing submicron Y₃Al₅O₁₂ precipitates (white arrow) at grain junctions with EDS analysis of the same precipitates in the inset; and (f) Y₂O₃-doped nanocomposite showing Y₃Al₅O₁₂ precipitates (white arrow) within matrix grains, at high magnification with EDS analysis of precipitate particle in the inset.
Figure 5.6 XRD patterns of powdered MWCNT and sintered samples of Al₂O₃ and Al₂O₃–CNT nanocomposites containing 0 ppm (A0, A2C) and 300 ppm (A3Y, A2C3Y) Y₂O₃, respectively.
Figure 5.7 SEM images. (a) The fractured surface of MWCNT/Al₂O₃ nanocomposites, exhibiting MWCNT across the flaws (black circles), MWCNT pull-out (white arrows) and (b) MWCNT bridging the crack surfaces (black arrow).
Figure 5.8 SEM images of fractured surface: (a) monolithic Al₂O₃-large grains with intergranular fracture; (b) Y₂O₃-free nanocomposites showing residual porosity (white square), sharp flaws at matrix grain junctions (white circle), MWCNTs within flaw cavity (short white arrow), transgranular fracture (double-headed long white arrows); (c) mixed mode fracture in doped MWCNT/Al₂O₃ nanocomposites transgranular (double-headed long white arrows), intergranular (short black arrows); and (d) high-magnification SEM image of doped nanocomposites showing MWCNT (short white arrows) at individual matrix grains.
Figure 5.9 SEM images of (a) Vickers’ hardness indent at 9.8 N used for fracture toughness assessment and indent crack profile of (b) monolithic Al₂O₃, (c) dopant-free nanocomposites and (d) Y₂O₃-doped MWCNT/Al₂O₃ nanocomposites.
Figure 5.10 (a) Densities of the monolithic Al₂O₃ and nanocomposites samples as the function of MgO concentrations, sintered under pressures and pressure-free conditions, and (b) comparison of the density of MgO-doped nanocomposites with previous reports.
Figure 5.11 Low-magnification images SEM fractured surfaces details the samples sintered without external pressures, 600 ppm MgO-doped (a) monolithic Al₂O₃, (b) nanocomposite, microcracks clearly visible (white arrows) and HP-sintered MgO-free (c) monolithic Al₂O₃, (d) nanocomposite, exhibiting well-integrated flaws-free homogenous microstructure.
Figure 5.12 Influence of the MgO contents on the grain size of the monolithic Al₂O₃ and nanocomposites consolidated by PL sintering and HP sintering.
Figure 5.13 Fractured surfaces SEM images of the samples underwent PL sintering, (a) untuned Al₂O₃, (b) 300 ppm MgO-tuned Al₂O₃, (c) 600 ppm MgO-tuned Al₂O₃, (d) untuned nanocomposite, (e) 300 ppm MgO-tuned nanocomposite, and (f) 600 ppm MgO-tuned nanocomposite.
Figure 5.14 (a) XRD patterns of (i) pristine MWCNT, (ii) monolithic Al₂O₃, (iii) 300 ppm MgO-tuned Al₂O₃, (iv) 600 ppm MgO-tuned nanocomposite, (b) SEM micrograph of thermally etched 600 ppm MgO-tuned Al₂O₃ showing precipitates of MgAl₂O₄ at Al₂O₃ grain boundaries (white arrows), and (c) chemical composition of the same precipitates confirming the elements of sample constituents.
Figure 5.15 Fractured surfaces SEM images of the HP-sintered monolithic Al₂O₃ tuned with MgO contents (a) 0 ppm, (b) 300 ppm, and (c) 600 ppm and nanocomposites tuned with MgO (d) 0 ppm, (e) 300 ppm, and (f) 600 ppm contents.
Figure 5.16 Hardness Vickers’ profile of the monolithic Al₂O₃ and nanocomposites tuned with various (300 and 600 ppm) MgO contents and sintered with and without external pressures.
Figure 5.17 Comparison of the (a) K_IC and (b) σ_f values obtained in the present study with previous reports.

Chapter 6

Figure 6.1 Schematic image of oxidation-induced crack-healing mechanism [3].
Figure 6.2 Location of the elements of M_n+₁AX_n in the periodic table [31].
Figure 6.3 Unit cells of MAX phase (http://en.wikipedia.org/wiki/MXenes).
Figure 6.4 Low- and high-magnification images showing the completely filled crack in the Ti₂AlC sample after eigth fracture and then annealing at 1200 °C for 100 h. (a) Optical overview image of the healed crack. (b) An enlarged optical image taken from (a). (c) Detailed micrograph of the healed-damage zone obtained with scanning electron microscopy using EBSD [46].
Figure 6.5 Strength recovery of Ti₂AlC specimens after crack healing at 1200 °C for 2 h in air. (a) Optical image of the 3 Knoop indents at the center of long sample to create crack damage. (b) Optical image of the healed sample after flexural strength testing. (c) Flexural strength of the virginal Ti₂AlC, after creating crack damage and after crack healing, respectively [46].
Figure 6.6 Black-scattered scanning electron micrographs of fracture and crack healing of Ti₂AlC samples. (a) Crack path after one cycle of healing and subsequent fracture. The yellow arrows indicate the crack completely filled, and the white arrows indicate the new introduced crack. Note that the subsequent crack almost deflects around the healed zone of the first crack. (b) After two cycles of healing, the second crack was completely filled again. (c) Crack path after four cycles of healing, and subsequent fracture. (d) Crack path after seven cycles of healing, and subsequent fracture. The red arrows indicate the location of remnant crack parts [46].
Figure 6.7 Fracture toughness of Ti₂AlC as a function of the number of fracture and healing cycles [46].
Figure 6.8 Back-scattered electron images of the polished Cr₂AlC samples after healing at 1100 °C for (a–b) 4 h and (c) 100 h. (a) Low-magnification image of the healed zones around indentation on the polished surface. The inset is an enlarged image taken from the marked area in (a). (b) An enlarged image taken from the marked area in the inset in (a). (c) An enlarged image showing a 100 h healed crack [40].
Figure 6.9 Oxidation behavior of Ti₂AlC and Cr₂AlC ceramic at 900–1200 °C in synthetic air [40].
Figure 6.10 Strength recovery of Cr₂AlC after healing at 1100 °C for 4 h in air, (a) residual flexural strength and recovered flexural strength as a function of crack length. Data marked with asterisks mean that samples fractured outside the crack-healed zones. (b) Recovered flexural strength as a function of crack length and for different healing time [40].
Figure 6.11 (a) Lattice parameters ratio c₀/a₀ and (b) mean Ti–A and Ti–C atomic distances as a function of Sn content in Ti₂Al_(1−x)Sn_xC solid solution [51].
Figure 6.12 (a) DTA spectra of Ti₂Al_(1−x)Sn_xC solid-solution powder heated in air atmosphere with a constant heating rate of 5 °C/min. (b) Characteristic temperatures of oxide reaction product formation derived from DTA, TG, and XRD measurements [51].
Figure 6.13 Cross-sectional BSE-SEM images of healed zones after 4 cycles of healing at 800 °C. (a) Larger crack opening filled by the mixture of TiO₂ and SnO₂, (b) thinner cracks filled with Sn, and (c) EBSD micrograph of metallic Sn distribution in a small crack area [53].
Figure 6.14 TEM analysis of the healed T_i2SnC sample. (a) Representative HAADF-STEM image showing the healed zone in a major crack. The dotted line in (a) indicates the boundary between the Ti₂SnC and the healed crack zone; (b) is an EDX spectrum of the area marked with the blue square in (a). (c–f) are SAED patterns of the regions marked with the dotted circles and letters (c–f) in (a). (c) The [0 1 2 1] ZA of hexagonal Ti₂SnC, (d) the [1 2 0] ZA of tetragonal Sn and the [1 3 1 0] ZA of tetragonal SnO₂, (e) the [0 0 1] ZA of cubic TiC, and (f) the [1 0 0] of tetragonal TiO₂ [53].
Figure 6.15 Strength recovery and electrical conductivity recovery after healing process. (a) Flexural strengths of quenched samples before and after healing at 800 °C for 1 h. (b) Recovered electrical conductivity as a function of quenching and healing temperature. (c) Electrical conductivity as a function of quenching and healing cycle. In each cycle, samples were quenched at 700 °C in water and then healed at 800 °C for 1 h in air [53].
Figure 6.16 The morphologies of cracks generated on Al₂O₃ composite mixed with 10 vol.% Ti₂Al_0.5Sn_0.5C repair filler before and after healing. (a) Cracks generation by Vickers’ indentation with a load of 100 N, (b) enlarged SEM image of cracks in the black rectangle in (a), and (c) a crack healed at 900 °C for 3 h. (d) a polished surface of (c), (e) EBSD analysis of crack filling near to the surface and at large distance from the surface [65].
Figure 6.17 The virgin strength, residual strength, and sintered density of Ti₂Al_0.5Sn_0.5C–Al₂O₃ composite as a function of repair filler content [65].
Figure 6.18 Strength recovery (σ_heal/σ_virgin) as function of the repair filler content and annealing time at (a) 700 °C, (b) 900 °C, and (c) 1100 °C, respectively [65].
Figure 6.19 Summary of crack-healing dependence on temperature and time measured on the MAX phase alumina composites [65].

Chapter 7

Figure 7.1 (a) SWCNT and (b) MWCNT. (From Ben Cornwell-Mott, Effect of perfectly aligned CNTs under cohesive crack bridging in adhesive joints. A project submitted in conformity with the requirements for the degree of Master of Engineering Graduate Department of Mechanical and Industrial Engineering University of Toronto, 2010 [13]).
Figure 7.2 HRTEM micrographs of SWCNTs (a), SDWCNTs (b), and MWCNTs (c). Note in each inset the distribution of the number of walls.
Figure 7.3 SEM image of fracture surface of a ZTA composite [94] sintered at 1520 °C, 1 h showing SWCNT bundles (a) and MWCNT tangles (b) after sonication in aqueous solution.
Figure 7.4 ZTA composites sintered by means of SPS at 1475 °C with additions of 0.01 wt% MWCNTs (a) and 0.01 wt% SWCNTs.
Figure 7.5 SEM fracture surfaces of Al₂O₃ ceramics with additions of 0.1 wt% SWCNTs (a) and MWCNTs (b) pressureless sintered at 1520 °C during 1 h. Arrow marks explained in text [96].
Figure 7.6 SEM fracture surfaces of pure Al₂O₃ reinforced with MWCNTs: MW1 (a), MW2 (b), MW3 (c), MW CIMAV (d), SDWCNT (SD) (e), and SWCNTs (SW) (f). Characteristics of these CNTs can be shown in Table S1 in Supplementary information Ref. [21].

Chapter 8

Figure 8.1 Changes in shaping and drying with waste material addition. ^aSM – shaping moist, ^bΔSk – shrinkage in Bigot’s curve critical point, ^cΔGk – weight loss in Bigot’s curve critical point, ^d PC – plasticity coefficient by Pfefferkorn
Figure 8.2 Changes of observed parameters during firing of products with waste materials addition.
Figure 8.3 Target and predicted CSB, CSC, WAT, WAB, WAC, WLFT, WLFB, and WLFC (MLP 12–6–10).
Figure 8.4 PCA graphic, showing the behavior in shaping and drying in the air.
Figure 8.5 PCA of fired products ceramic-technological characteristics.
Figure 8.6 FSE analysis for ceramic-technological characteristics for different waste materials additions, when firing at 850, 900, 950 and 1000 °C.

Chapter 9

Figure 9.1 Spectrum of functional materials applications. Adapted from Ref. [6].
Figure 9.2 The variation of enthalpies of formation of alkali tantalates, LiTaO₃, NaTaO₃, and KTaO₃, as a function of tolerance factor, t, and stability index, s. With the increase in the tolerance factors and stability index of alkali tantalate perovskites, the formation enthalpies become more negative. Adapted from Ref. [61] with permission from The Royal Society of Chemistry.
Figure 9.3 Temperature dependence of the real part of the dielectric permittivity ε′ (a) and of the dielectric loss tanδ (b) of NaTaO₃, KTaO₃, and SrTiO₃ ceramics at 10 kHz together with the fit of the ε′(T) experimental data to the Barrett’s relation, indicating them as incipient FEs.
Figure 9.4 Diffuse reflectance spectra versus wavelength of perovskite-like alkali tantalates [154]. The spectra were acquired in the UV–Vis range, with 0.02 nm in step-size and using BaSO₄ as reference, and the Kubelka–Munk function was applied with the aim to convert the diffuse reflectance into the absorption coefficient that is proportional to F(R_∞).
Figure 9.5 Photocatalytic efficiency of alkali tantalates after 7 h of UVA irradiation [154]. The rate constant, k_app, was also calculated for the assessed powders, and results are included.
Figure 9.6 (a) SEM micrograph of calcium phosphate precipitates with cauliflower-like morphology in LTO powder incubated for 21 days in SBF. (b) FTIR spectra of LTO powders incubated for 0, 7, and 21 days in SBF; inset shows phosphate bands. Reprinted from Ref. [185], with permission from Elsevier.
Figure 10.1 Scheme of antibacterial action of nanosilver/bacteria (about 100 nm size) encircled with silver nanomolecules (1 nm nanomolecules outnumber).
Figure 10.2 Diffractogram of the HAP sample with the adsorbed silver.
Figure 10.3 Diffractogram of the HAP sample with adsorbed silver.
Figure 10.4 The diagram of dependence of the zeta potential of HAP prepared by co-precipitation of the Ca(NO₃)₂·4H₂O and (NH₄)HPO₄ solutions on pH in the sodium nitrate solutions of the concentrations 10⁻³, 10⁻², and 10⁻¹ M.
Figure 10.5 The dependence of the zeta potential of HAP obtained by the wet method on pH in the 10⁻³ M solution of NaNO₃ electrolyte containing Ag+ ions at appropriate concentration.
Figure 10.6 The dependence of the zeta potential of AgHAp (x_Ag = 0.4) on pH in the NaNO₃ solutions of the concentrations 10⁻³, 10⁻², and 10⁻¹ M.
Figure 10.7 The dependence of the zeta potential of AgHAp (x_Ag = 0.8) on pH in the NaNO₃ solutions of the concentrations 10⁻³, 10⁻², and 10⁻¹ M.
Figure 10.8 The dependence of pH on V_(NaOH) for the HAP/electrolyte system.
Figure 10.9 The dependence of pH on V_(NaOH) for the HAP 0.4 Ag/electrolyte system.
Figure 10.10 The dependence of pH on V(_NaOH) for the HAP 0.8 Ag/electrolyte system.
Figure 10.11 The dependence of surface charge density on pH for the HAP/electrolyte/Ag system.
Figure 10.12 Dependence of density of Ag⁺ adsorption on pH for the HAP/0.001 mol/dm³ NaNO₃ + 0.001 mol/dm³ Ag⁺.
Figure 10.13 Dependence of density of Ag⁺ adsorption on pH for the HAP/0.001 mol/dm³ NaNO₃ + 0.0001 mol/dm³ Ag⁺.
Figure 10.14 Dependence of density of Ag⁺ adsorption on pH for the HAP/0.001 mol/dm³ NaNO₃ + 0.00001 mol/dm³ Ag⁺.
Figure 10.15 Dependence of density of Ag⁺ adsorption on pH for the HAP/0.001 mol/dm³ NaNO₃ + 0.000001 mol/dm³ Ag⁺.
Figure 10.16 Kinetics of Ag⁺ ions adsorption on the HAP from the 0.001 mol/dm³ NaNO₃ solution with Ag⁺ ions initial concentration of 0.000001 mol/dm³.
Figure 10.17 Kinetics of Ag⁺ ions adsorption on the HAP from the 0.001 mol/dm³ NaNO₃ solution with Ag⁺ ions initial concentration of 0.001 mol/dm³.

List of Tables

Chapter 2

Table 2.1 Existing calcium orthophosphates and their major properties [3–5].
Table 2.2 Trademarks of the commercially produced biphasic, triphasic, and multiphasic calcium orthophosphates [3].

Chapter 6

Table 6.1 Crack-healing kinetic parameters of Ti₂Al_0.₅Sn_0.₅C–Al₂O₃ composites [65].

Chapter 7

Table 7.1 Some characteristics of SWCNTs (from Ref. [47]).
Table 7.2 Comparison of mechanical properties (from Ref. [48]).
Table 7.3 Processing details of different CNTs-reinforced Al₂O₃ and ZrO₂ ceramics nano composites.
Table 7.4 Some general characteristics of MWCNTs (from Ref. 47).
Table 7.5 Properties of different CNTs-reinforced ceramics.

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ISBN 978-1-119-24244-4

Preface

Ceramic materials are inorganic and nonmetallic porcelains, tiles, enamels, cements, glasses and refractory bricks. Today, the term “ceramics” has gained a wider meaning as a new generation of materials which influence our lives; electronics, computers, communications, aerospace and other industries rely on them for a number of uses. In general, advanced ceramic materials include electroceramics, optoelectronic ceramics, superconductive ceramics and the more recently developed piezoelectric and dielectric ceramics. Due to their features, including their mechanical properties and decorative textures, they can be considered for environmental uses and energy applications, as well as for use in bioceramics, composites, functionally graded materials, intelligent ceramics and so on. This book has a transdisciplinary readership that spans students, engineers, scholars, scientists, physicists, chemists, life scientists and beyond. The volume brings together innovative methodologies and strategies adopted in the research and development of advanced ceramic materials and offers a comprehensive view of cutting-edge research on ceramic materials and technologies.

A wide range of processing methods used to generate ceramic materials for a variety of functional, structural and biomedical applications are described in this book. The book starts with an excellent review of solution-based methods that can be used to deposit epitaxial films of oxide nanomaterials for microelectronics applications and is followed by a detailed description of tantalum oxides and related phases and their potential use in solar cells and other applications. In the next chapter there is a discussion of the basics of microwave processing which contains a brief summary of its history in various materials and a description of the recent work on hybrid microwave sintering of metal matrix composites containing absorbing ceramic materials.

The next chapters focus on structural applications, starting with a description of continuous fiber ceramic matrix composites, where typical matrix and filler materials are discussed along with the interfacial layers needed to induce crack deflection and improved fracture toughness. The following two chapters deal with the addition of carbon nanotubes (single-wall and multiwall) into bulk alumina and zirconia and how the characteristics of the nanotubes as well as the processing methods used can affect the resultant properties. Next the detection of crack healing in MAX phase ceramics and their enhanced properties as a result of the incorporation of these unique materials are discussed.

Additional chapters investigate the effect of the additives on manufacturability and biocompatibility. In the first chapter of this section, waste materials from a variety of industries are incorporated into ceramic brick for sustainable manufacturing. The authors propose the use of an artificial neural network optimization program for identifying the conditions that work best for each additive. The next chapter focuses on the importance of different additives to improve the bioactivity of calcium orthophosphates used in medical implants, followed by a chapter investigating the effect of silver additions to hydroxyapatite for improved antifungal and antibacterial responses using a variety of surface controlled schemes.

This book is written for readers from diverse backgrounds across the fields of chemistry, physics, materials science and engineering, medical science, pharmacy, environmental technology, biotechnology, and biomedical engineering.

Editors
Ashutosh Tiwari, PhD, DSc
Rosario Gerhardt, PhD
Magdalena Szutkowska, PhD
July, 2016

Advanced Ceramic Materials

Preface

Part 1
DESIGN, PROCESSING, AND PROPERTIES

Part 1DESIGN, PROCESSING, AND PROPERTIES

Part 1
DESIGN, PROCESSING, AND PROPERTIES