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ISBN: 978-1-119-32364-8
ISSN: 1042-1122

CONTENTS

Preface

Controlled Synthesis, Processing, and Applications of Structural and Functional Nanomaterials

Assessing the Limits of Accuracy for the TAUC Method for Optical Band Gap Determination
Investigation of Pyroaurite-Type Anionic Clay-Derived Mixed Oxides with Various Compositions
Formation and Characterization of Nano-Scale Titanium Carbides in a Titanium Trialuminide Intermetallic
Growth Kinetics of Lanthanum Phosphate Core/Shell Nanoparticles Doped with Ce-Tb and Eu
Influence of Synthesis Parameters on Morphology, Crystalline Structure and Colloidal Stability of Core and Core-Shell LaPO₄ Nanoparticles
Zinc Oxide Nanoparticles for Space Satellite Solar Panel Protection Layer

Dielectronic Materials and Electronic Devices

Synthesis and Characterization of BaTiO₃-based Ceramics Doped in B Site by BaTi_1-xNb_xO₃
Influences of the Ceramic Matrix in the Properties of Ferroelectric Composites Based on PVDF Polymers
Piezoelectric Response of SN and MN Modified Lead Titanate Piezoelectric Ceramics
Comparison of Grain Size Effects on Microstructure and Dielectric Properties of Y_2/3Cu3Ti_4-xFe_xO₁₂ (X = 0.00, 0.05 and 0.15) Ceramics Synthesized by Glycine Assisted Semi Wet Route
Calcium Copper Titanate Based High Dielectric Constant Materials for Energy Storage Applications

Sintering and Related Powder Processing

Synthesis, Characterization and Gibbs Energy of Thermoelectric Mg₂Si
Modeling Densification During Fast Firing of YTTRIA-stabilized Zirconia
Mechanistic Studies of Compacted and Sintered Rock Salt
Sintering of Nanostructured Zirconia: A Molecular Dynamics Study

Processing and Performance of Materials Using Microwaves, Electric, and Magnetic Fields

Rapid Synthesis of Nanostructured Titanium Boride (TiB) by Electric Field Activated Reaction Sintering
Verification of Effects of Alternative Electromagnetic Treatment on Control of Biofilm and Scale Formation by a New Laboratory Biofilm Reactor
Microwave Assisted Sintering of Cold Iso-Statically Pressed Titanium 6-4 Powder Compacts
Microwave Heating of Ensembles of Spherical Metal Particles Surrounded by Insulating Layers
Sintering of Oxide Ceramics Under Rapid Microwave Heating
Roles of Electromagnetically-enhanced Free Energy on Non-Thermal Microwave Effects In Materials Processing – A Review and Discussion
Thermal Stability of Electromagnetic Compressed FL-5305 PM Parts

Advances in Composites

A New Production Process for Thermal Barrier Coating Material
Simultaneous Synthesis and Sintering of Dense B₄C/CNF Composites Using a Pulsed Electric-Current Pressure Sintering and Evaluation of Their Thermal Properties

Innovative Processing

Advanced Microstructural Study of Nickel-Titanium Rotary Endodontic Instrument Tips
Synthesis of TiC-TiB₂ Composite Powders from Carbon Coated TiO₂ Precursors
Nickel Nitrate and Molybdenum Oxide as a YTTRIA-Stabilized Zirconia Synergistic Sintering Aid

Surface Protection for Enhanced Performance

Modeling and Prediction of the Effective Thermal Conductivity of Thermal Barrier Coatings Using FFT and FE Approaches
Material Design of Ceramic Coating for Jet Engine by Electron Beam PVD

Ceramic Optical Materials

Novel Glass and Glass Scintillators for Gamma-ray and Neutron Detection
Praseodymium-doped Sialon Red Phosphors Prepared by Polymer-Derived Method

Alumina Materials

Alumina Insulators for High Voltage Automotive Ignition Systems

Thermal Protection Materials and Systems

Photogrammetric Surface Recession Measurements on Ablative Samples of Various Shape

Author Index

EULA

List of Tables

Chapter 2

Table I
Table II
Table III

Chapter 5

Table I
Table II

Chapter 6

Table I

Chapter 7

Table I

Chapter 9

Table 1
Table 2

Chapter 10

Table 1
Table 2

Chapter 12

Table I
Table II

Chapter 13

Table I
Table II

Chapter 14

Table 1
Table 2

Chapter 15

Table 1
Table 2

Chapter 16

Table 1
Table 2

Chapter 17

Table 1

Chapter 18

Table I
Table II

Chapter 22

Table 1
Table 2
Table 3
Table 4

Chapter 23

Table 1

Chapter 24

Table I

Chapter 26

Table I

Chapter 27

Table I
Table II

Chapter 28

Table 1
Table 2

Chapter 32

Table I
Table II
Table I

Chapter 33

Table 2

List of Illustrations

Chapter 1

Figure 1: Example Tauc Plot from UV-Vis analysis of a ZnO thin film, illustrating the method of fitting the linear region to extrapolate the band-gap at the X-axis intercept, here about 3.28 eV. Data replotted from ref.[18].
Figure 2: Band diagram for ZnO showing direct transitions at the central Γ point. One direct transition at slightly higher energy is illustrated.
Figure 3: Linear regression fitting quality for different portions of the data as a method of choosing the best region for extrapolating the “Tauc gap”: using (•) 5, (▪) 11, or (▴) 15 sequential points.
Figure 4: Fitted Tauc gap obtained from linear regression fits covered in Figure 1 and 3. The region where the best R² values resulted is also the region where the fitting slope is steepest and the largest Tauc gap intercept is found: (•) 5, (▪) 11, and (▴) 15 sequential points used.
Figure 5: Band structure for silicon showing the indirect transition that is responsible for the onset of absorption and a direct transition (blue arrow) that occurs at certain higher energy values (figure adapted from helikowsky [21]).
Figure 6: Dispersion of absorption coefficient at 300°K for intrinsic silicon. Open symbols are data from spnes and Studna[24]; filled symbols are from Green and Keevers[25]. The rapid rise above 3 V (indicated by the arrow) comes from the onset of direct transitions.
Figure 7: Overview Tauc plot examination of the single crystal silicon absorption data of Green and Keevers[25]. Data are plotted up to 3 eV showing the long region of good linearity (from the band edge up to about 2.2 eV) and including the higher energy range where there is strong upward deviation from the ideal ½-power indirect correspondence.
Figure 8: Close-up of the near-edge region of the indirect Tauc plot for silicon [25]. Two different indirect regions are found: the solid line includes phonon absorption and the dashed line is for phonon emission.
Figure 9: Absorption coefficient values for silicon in the region from 1.05 through 2.20 eV [25]. The parabolic shape associated with an indirect transition is clear.
Figure 10: Fitted indirect band-gap values for each 10-point linear regression window (small circles) including their mathematical confidence interval based on the variability within each 10-point window. The specific values of mathematical confidence interval are referenced to the right side scale (open diamonds).

Chapter 2

Figure 1. X-Ray diffraction patterns of pyroaurite samples: a. Mg/Fe 1:3 (Insert), b. Mg/Fe 2:1, c. Mg/Fe 5:2;
Figure 2. X-Ray diffraction patterns for the oxides obtained at 550°CC: a. Mg/Fe 1:3, b. Mg/Fe 2:1, c. Mg/Fe 5:2.
Figure 3. X-Ray diffraction patterns for the oxides obtained at 900°C: a. Mg/Fe 1:3, b. Mg/Fe 2:1, c. Mg/Fe 5:2.
Figure 4. Thermal analysis of the pyroaurite samples.
Figure 5. FTIR spectra of pyroaurite samples. a. Mg/Fe 1:3, b. Mg/Fe 2:1, c. Mg/Fe 5:2.
Figure 6. FTIR spectra of a. oxides at 550°C, b. oxides at 900°C a. Mg/Fe 1:3, b. Mg/Fe 2:1, c. Mg/Fe 5:2.
Figure 7. Adsorption isotherms for all pyroaurite samples
Figure 8. Adsorption isotherms for Mg/Fe 1:3 at all studied temperatures.
Figure 9. Adsorption isotherms for Mg/Fe 2:1 at all temperatures
Figure 10. Adsorption isotherms for Mg/Fe 5:2 at all temperatures.
Figure 11. Particle size distribution for all samples: a. pyroaurite, b. oxides at 550°C, c.oxides at 900°C.
Figure 12. TEM micrographs for pyroaurite samples: a. Mg/Fe=1:3, b. Mg/Fe= 2:1, c. Mg/Fe 5:2.
Figure 13. TEM micrographs for oxides at 550°C: a. Mg/Fe=1:3, b. Mg/Fe= 2:1, c. Mg/Fe 5:2.
Figure 14. TEM micrographs for oxides at 900°C: a. Mg/Fe=1:3, b. Mg/Fe= 2:1, c. Mg/Fe 5:2.

Chapter 3

Figure 1 XRD Pattern after 90 h of mechanical alloying with identified reaction product phase Ti(C,N) with TiC identified by the * symbol and TiN identified by the + symbol with the representative stick patterns for each with the admixed TiB₂ identified by the ^ symbol.
Figure 2 Dependence of carbon uptake on MNS processing time with elemental titanium amounts increased by the same factor for each test increment.
Figure 3 XRD patterns for the alloys MNS processed for 5, 10, 15, 20, 25, 30, and 40 h times all with similar starting chemistries.
Figure 4 Profile fit example for phases identified in the XRD pattern for the 20 h MNS processing time.
Figure 5 Comparison of as-milled powder to annealed powder with the same intensity scale.
Figure 6 Phase volume fractions for the various MNS processing times all with the same starting composition.
Figure 7 Warren-Averbach results of synthesized diffraction peaks for <111 > and <200> directions in the L1₂ intermetallic phase.
Figure 8 XRD patterns of as-milled powder for longer MNS processing times and similarly larger amounts of elemental titanium.
Figure 9 Field emission electron microscope micrograph of powder particle surface from MNS processing for 10 h.
Figure 10 Microstructural model of nano-scale MNS processed as-milled material considering mean sizes of the L1₂ intermetallic and TiC phases and data developed in this analysis with the area representing the volume fraction calculated for these regions.

Chapter 4

Figure 1. a) And b) are the UV-Vis absorption spectra at different time of synthesis from the La_40%Ce_45%Tb_15%PO₄ and La_75%Eu_25%PO₄ nanoparticles, respectively. c) And d) Time evolution of the absorption bands at 273 nm and 230 nm for the La_40%Ce_45%Tb_15%PO₄ and La_75%Eu_25%PO₄ nanoparticles respectively.
Figure 2. TEM Micrographs and their respective size distribution of a). Core La_40%Ce_45%Tb_15%PO₄ b). Core-4 shells La_40%Ce_45%Tb_15%PO₄ c). Core La_75%Eu_25%PO₄ d). Core-4 shells La_75%Eu_25%PO₄.
Figure 3. XRD Pattern of a). Core shell Structures La_40%Ce_45%Tb_15%PO₄ and b) Core shell structures La_75%Eu_25%PO₄
Figure 4. a). HRTEM of Core-4 shell La_75%Eu_25%PO₄ nanoparticles and b) SAED Core-4 shells La_40%Ce_45%Tb_15%PO₄ nanoparticles

Chapter 5

Figure 1. Absorption spectra for a) 75, 80, 85, and 90 °C synthesis temperatures and b) 80 and 90 °C at 3 synthesis times.
Figure 2. XRD spectra for LaPO₄ core NPs at the 4 combinations of synthesis temperature and time.
Figure 3. XRD spectra for LaPO₄ core + 2 shells NPs at the 4 combinations of synthesis temperature and time.
Figure 4. XRD spectra for LaPO₄ core + 4 shells NPs at the 4 combinations of synthesis temperature and time.
Figure 5. Crystallite size for core, core + 2 shells, and core + 4 shells NPs for different synthesis parameters.
Figure 6. TEM micrograph and particle size distribution for core LaPO₄ synthesized at 90 °C for 2 hours.
Figure 7. TEM micrograph and particle size distribution for core + 4 shells LaPO₄ synthesized at 80 °C for 2 hours.
Figure 8. TEM micrograph and particle size distribution for core + 4 shells LaPO₄ synthesized at 90 °C for 3 hours.

Chapter 6

Figure 1. Conceptual design of flexible solar array with PMG coverglass and PMG substrate for hybrid configuration.
Figure 2. Schematic of tube furnace and synthesis apparatus.
Figure 3. (a) SEM images of ZnO-A and (b) ZnO-T.
Figures 4. (a) SEM images of 2wt% ZnO-A with fused silica beads, and (b) 2wt% ZnO-T with fused silica beads.
Figure 5. UV/Vis spectra of composite with various loadings of ZnO nanocrystals.
Figure 6. Conductivity plot of ZnO composite materials. ITO and AZO composite data is from Wilt et al. ¹, these composites were tested with and without an induced voltage applied to the sample. The ZnO-A and ZnO-T composites were only tested without an applied voltage.

Chapter 7

Figure 1. Distribution of particle sizes of raw materials.
Figure 2. SEM images of raw materials a) BaCO₃, b) TiO₂ c) Nb₂O₅.
Figure 3. XRD patterns of BaTi_1-xNb_xO₃ (0 ≤ x ≤ 0.25).
Figure 4. Unit cell volume as a function of x.
Fig. 5. Raman spectra of samples with 0 ≤ x ≤ 0.25.
Fig. 6. Permittivity against temperature plots of samples, at 1 kHz.
Fig. 7. Hysteresis loops of BaTi_1-xNbxO₃ in a range of 0-0.005.
Fig. 8. Hysteresis loops of BaTi_1-xNb_xO₃ in a range of 0.04-0.25.
Fig. 9. SEM images of BaTi_1-xNbxO₃, a) 0.001, b) 0.005, c) 0.08, d) 0.25

Chapter 8

Figure 1: XRD patterns of PVDF/PLZT composites crystallized at 90° C, for 25% PVDF/75% PLZT. The inset is a zoom of the PVDF pattern identifying the diffraction peaks of α and β phases.
Figure 2: FTIR spectra of PVDF/PLZT composites crystallized at 90° C, for 25% PVDF/75% PLZT.
Figure 3: Real and Imaginary parts of the electrical of PVDF/PLZT composites crystallized at 90° C, for 25% PVDF/75% PLZT.
Figura 4: Hysteresis loop of the electrical of PVDF/PLZT composites crystallized at 90° C, for 25% PVDF/75% PLZT.

Chapter 9

Figure-1 The XRD spectra recorded at room temperature (RT) for Pb_1-xSn_xTiO₃ ceramics (a) Calcined at 800°C (2h) and (b) sintered at 1150°C (2h). The XRD spectra recorded at RT for Pb_1-_xSn_xTi_1-yMn_yO₃ (x =0.10, 0.15, 0.20, y = 0.05) ceramics (a) Calcined at 800°C (2h) and (b) sintered at 1150°C (2h). The impurity peaks are marked on the spectra with # or *. The large separation between (002) and (200) Bragg reflections suggest a large tetragonality, and therefore, a large spontaneous strain in the system.
Figure-2 Tetragonality versus Sn content in piezoelectric Pb_1-xSn_xTi_1-yMn_yO₃ ceramics. The tetragonality decreased drastically for the lightly doped sample. However, increased doping concentration resulted in a gradual increase in the tetragonality.
Figure-3(a), (c), (e), and (g) SEM micrographs of the samples sintered at 1050°C (2h) for Pb_1-xSn_xTiO₃ with x = 0.00, 0.10, 0.15, and 0.20, respectively. (b), (d), (f) and (h) SEM micrographs of the samples sintered at 1150°C for Pb_1-xSn_xTiO₃ with x = 0.00, 0.10, 0.15, and 0.20, respectively. The undoped PT (x = 0.00) was not sintered due to its high spontaneous strain as a result of large tetragonality. However, doped samples with reduced tetragonality exhibit evidence of densification.
Figure-4 Relative permittivity and loss tangent at 1 kHz as a function of x (Sn) for Pb_1-xSnTiO₃ ceramics at RT. The Sn modified PT samples exhibited higher loss tangent factor and reduced relative permittivity.

Figure-5 SEM micrographs of the Pb_1-xSn_xTi_1-yMn_yO₃ (x =0.10, 0.15, 0.20, y =0.05) ceramics sintered at 1150°C (2h). Mn and Sn co-doping resulted in a high density PT ceramic body.

Figure- 6 XPS-spectra recorded at RT for Pb_1-xSn_xTi_1-yMn_yO₃ (x = 0.10, 0.15, 0.20, y = 0.05) ceramics. These results suggest the presence of the Sn⁴⁺ in the modified PT systems. The increased intensity for Pb_1-xSn_xTi_1-yMn_yO₃ (x = 0.20, y = 0.05) ceramics can be attributed to the increased concentration of Sn doping.

Figure-7 Raman spectra recorded at RT for the Pb_1-xSn_xTi_1-yMn_yO₃ (x = 0.10, 0.15, 0.20, y = 0.05) ceramics. Note significant changes in the high frequency region. Sn substitution mainly perturbed the modes related to the octahedral dynamics.

Figure-8 Temperature dependence of the dielectric response at various frequencies for Pb_1-xSn_xTi_1-_yMn_yO₃ (0.10, 0.15, 0.20, y = 0.05) with (a)-(b) x = 0.10, (c)-(d) x = 0.15, (e)-(f) x = 0.20. Note the shift of the Curie temperature towards higher temperature with increasing Sn content.

Figure 9 P-E loop of Pb_1-xSn_xTi_1-yMn_yO₃ (0.10, 0.15, 0.20, and y = 0.05) at 1Hz for (a) x = 0.10, (b) x = 0.15, (c) x = 0.20. The P-E hysteresis loops for different systems were found to open at different temperatures indicating dissimilar activation energies.

Figure-10 PFM amplitude and phase images for Pb_1-xSn_xTi_1-yMn_yO₃ (0.10, 0.15, 0.20, y = 0.05) with (a)-(b) x = 0.10, (d)-(e) x = 0.15, (g)-(h) x = 0.20. The magnified view of the corresponding domain morphology is presented in (c), (f) and (i). The heavily doped samples exhibited smaller domain size due to finite interaction between domains and doping induced defects.

Chapter 10

Figure 1 : DTA/TGA curve for precursor powder of Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x = 0.05).

Figure 2 : XRD patterns of Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x = 0.00, 0.05, 0.15) sintered at 950 °C for 12 h.

Figure 3: SEM micrograph of fractured surface of sintered Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x =0.00, 0.05, 0.15).

Figure 4: EDX spectra of grain surface of sintered Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic,where x= (a) 0.00, (b) 0.05, (c) 0.15.

Figure 5: TEM bright field image of sintered (a) Y_2/3Cu₃Ti₄O₁₂ (b) Y_2/3Cu₃Ti_3.90Fe_0.10O₁₂ (c) Y_2/3Cu₃Ti_3.85Fe_0.15O₁₂ ceramic (d) corresponding SEAD pattern for Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x= 0.05).

Figure 6: Plots of dielectric constant (ε′) and loss tangent (tan δ) vs temperature at few selected frequencies for sintered Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x = 0.00, 0.05, 0.15).

Figure 7: Plots of (a) real dielectric constant (ε′) and (b) imaginary dielectric constant (ε″) with frequency at different temperature for Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x = 0.00, 0.05, 0.15).

Figure 8: Plots of loss tangent (tanδ) vs frequency at few selected temperature for Y_2/3Cu₃Ti_4-xFe_xO₁₂ ceramic (where x = 0.00, 0.05, 0.15).

Chapter 11

Figure 1. TGA for pure-CCTO pre-calcined precursors at a heating rate of 5 °C/min in static air from room temperature to 900 °C show no further loss beyond 700 °C.

Figure 2. XRD patterns of CCTO with the composition of CaCu₃Ti_4-xAl_xO_12-x/2, where, x=0, 0.06, 0.1, and 0.5 for (a) pure CCTO pre-calcined and calcined powders (at 650 – 950 °C for 6 h) forming phase pure CCTO at 850 °C and (b) Al-doped CCTO (x=0.0.6, 0.1, and 0.5) calcined at 850 °C for 6 h respectively.

Figure 3. SEM micrographs of pure-CCTO powders calcined at 850 °C for 6 h showing the particle size as small as 250 - 500 nm. Different magnifications of the calcined powders are shown in (a) and (b) respectively.

Figure 4. SEM micrographs show evolution of microstructure of pure-CCTO sintered ceramics prepared at different sintering temperatures of (a) 1050 °C, (b) 1060 °C, and (c) 1080 °C for 5 h. Figure 3 (d), (e), and (f) are the different magnifications of images (a), (b), and (c)respectively.

Figure 5. SEM micrographs of pure-CCTO sintered at 1115°C for 4 h show the completed grain growth with clear grain boundaries, where (a) and (b) are two different magnifications of the sintered sample.

Figure 6. Density of the sintered pure CCTO ceramics (a) at various temperatures from (a) 1050°C to 1080°C for 5 h show density is maximum 4.691 g/cm³ and then decreases to a minimum 4.563 g/cm³ and (b) the same trend for various holding times from 3 – 15 h at 1060°C.

Figure 7. XRD for sintered CaCu₃Ti_4-xAl_xO_12-x/2, where, x = 0, 0.06, 0.1, and 0.5 ceramics at 1060°C for 5 h show no Al containing phase up to doping x=0.5 with (a) CuO traces in as-sintered samples up to x=0.1 and (b) no such traces in polished samples.

Chapter 12

Figure 1. A schematic showing the experimental procedure for synthesis of Mg₂Si powder.

Figure 2. Images of (2Mg+Si) and Mg₂Si pellets before and after sintering at 500 °C and 5 min.

Figure 3. XRD spectra of (a) 2Mg + Si, & (b) Mg₂Si powders from sintering at 500 °C for 5 min.

Figure 4. SEM image of Mg₂Si powder obtained from sintering at 500 °C for 5 min.

Figure 5. EDS spectrum of Mg₂Si powder obtained from sintering at 500 °C for 5 min.

Figure 6. Specific heat vs. temperature of Mg₂Si obtained at 500 C and 5 min.

Figure 7. Change in Gibbs energy vs. temperature for Mg₂Si obtained at 500 °C and 5 min.

Chapter 13

Fig 1. Isothermal sintering data for (a) 3YSZ and (b) 8YSZ with n_3YSZ=2.37 and n_8YSZ=2.36. Data from the literature²⁰.

Fig. 2. Theoretical density vs. holding time for fast-fired YSZ samples at 1400°C in comparison to the model prediction.

Chapter 14

Figure 1: PXRD of rock salt from 20 to 80° 2Theta with the corresponding Miller indices.

Figure 2: Particle size distribution of milled rock salt resulting in a mean particle size of 30 μm.

Figure 3: Thermogravimetric (TGA, red) and Differential Thermal Analysis (DTA, blue) of the rock salt.

Figure 4: ESEM images as comparison of compressed rock salt samples at 100 MPa (A) and 560 MPa (B).

Figure 5: Hot stage microscopy of rock salt, with the height change (blue), the width change (red) and the area change (black).

Figure 6: ESEM images of rock salt at different sinter temperatures of T=550°C (A), 640°C (B), 700°C (C), and 750°C (D).

Figure 7: SEM images of sintered rock salt samples with the powder compacted at p = 100 MPa (A,B), 200 MPa (C,D), 300 MPa (E,F), 400 MPa (G,H) and 500 MPa (I,K).

Figure 8: ESEM images of rock salt for different sinter times; 30 min (A) and 20 h (B).

Figure 9: FESEM of cut through the elongated material running along the crystal boundaries.

Chapter 15

Figure 1: Cubic zirconia 3-particle atomic model. The cut half particle shows the “particle core”region in yellow. Red atoms are oxygen, and blue atoms are zirconium.

Figure 2: Configurational evolutions of the three-particle model sintered at 2800 K. (a) 0 ps, (b) 4 ps, (c) 35 ps, (d) 100 ps. Red atoms are oxygen, and blue atoms are zirconium.

Figure 3: Configurations at temperature of (a) 2700 K, (b) 2800 K, and (c) 2900 K. Red atoms are oxygen, and blue atoms are zirconium.

Figure 4: Point defects during the sintering process at (a) 0 ps, (b) 4 ps. Red atoms are oxygen, and blue atoms are zirconium.

Figure 5: Mean square displacements of particle core at different temperatures during the 100 ps sintering simulation

Figure 6: Mean square displacement of particle shell at different temperatures during the 100 ps sintering simulation

Figure 7: Temperature dependence of diffusion coefficients

Chapter 16

Figure 1: Process measurements for the three trials: a) Die wall temperature, b) Die vs. central temperature (through the end of hold stage), c) Electrical power, d) Ram position.

Figure 2. Microstructures of TiB ceramic sintered by direct current heating: (a) low and (b) high magnifications.

Figure 3. Microstructures of TiB ceramic sintered by indirect current heating: (a) low and (b) high magnifications.

Figure 4. Microstructures of TiB ceramic sintered by combined heating: (a) low and (b) high magnifications.

Figure 5: X-ray diffraction analysis

Figure 6: EDS analysis of direct heating specimen showing the distribution of elements Ti, Fe, and Mo; white rectangle defines area of analysis in remaining images.

Figure 7: EDS analysis of indirect heating specimen showing the distribution of elements Ti, Fe, and Mo; white rectangle defines area of analysis in remaining images.

Figure 8: EDS analysis of combined heating specimen showing the distribution of elements Ti, Fe, and Mo; white rectangle defines area of analysis in remaining images.

Chapter 17

Fig.1 The background of this study–Geothermal Generation.

Fig.2 Biofilm and scale formations.

Fig.3. Experimental apparatus

Fig.4. The LBR

Fig.5. 3D imaging optical microscope.

Fig.6. Raman analysis.

Fig.7 Iron specimens immersed in the LBR for one and two days.

Fig.8 Iron specimens in the LBR for one day with and without the application of high frequency.

Fig.9. 3D imaging of iron specimens.

Fig.10 Copper specimens in the LBR for one day with and without the application of high frequency.

Fig.11 3D imaging for copper specimens.

Fig.12 Aluminum specimens in the LBR for one day with and without the application of high frequency.

Fig.13. 3D imaging of Al specimens.

Fig.14. Raman shifts for iron specimens.

Chapter 18

Figure 1: Schematic diagram of the microwave transmission system.

Figure 2: The microwave processing casket with susceptor and insulating materials labeled. The total size of the casket is approximately 8 inches tall and 6 inches in diameter.

Figure 3: A schematic diagram showing the cores and indicating the labeling of the various density cores. Cored samples were cut from each of the sintered specimens for tensile, density and metallographic anlaysis. The cores were cut from the specimens with EDM.

Figure 4: Temperature and reflection coefficient variation with time measured for a pre-alloyed powder compact CIP'd at 90 ksi and sintered for 120 minutes. The blended compacts showed a similar behavior as do compacts with different CIP pressures.

Figure 5: The green and sintered density of specimens of pre-alloyed (a) and blended Ti64 powder compacts which were CIP'd at different pressures and sintered at 1250 °C for different times. In each chart, the first three groups of bars are for 30 ksi CIP, the second three for 60 ksi CIP and the last three for 90 ksi CIP. The dotted line indicates 99% density.

Figure 6: Density variations as measured from cores taken from different locations in the cylinders sintered from the pre-alloyed powder. The core identifiers are the same as in Fig. 3.

Figure 7: Density variations of pucks sectioned from a density core. Each density core was sliced into five pucks. The pucks were labeled a, b, c, d, e (from top to bottom). The measurements shown here are for P1 cores from pre-alloyed powder specimens.

Figure 8: A typical optical micrograph of the sintered Ti-6Al-4V showing α and β phase. The specimen shown here was from a blanded powder specimen that was CIP'd at 30 ksi and sintered for 60 minutes.

Chapter 19

Figure 1. A conductive particle (c) surrounded by an insulating shell (i) and a spherical void (v) in the effective medium (e).

Figure 2. Effective dielectric permittivity ɛ_eff of copper powder with insulating oxide layers on particles vs. relative volumetric concentration of solid: (a), (b) powder particle radius 1 μm, oxide layer thickness 1 nm, (c), (d) powder particle radius 10 μm, oxide layer thickness 10 nm. Frequency 24 GHz. Solid line corresponds to the wave EMA approach, and dashed line–to the quasi-static EMA; for the real part of ε_eff (figs. (a) and (c)) both appoaches give the same result. Note log scale in figs. (c) and (d).

Figure 3. Imaginary part of the effective dielectric permittivity of compacted metal powder with insulating oxide layers vs. conductivity of metal: (a) at a frequency of 2.45 GHz, (b) at 24 GHz. Powder particle radius 10 pm, oxide layer thickness 100 nm, relative volumetric concentration of solid Cs = 1. Solid line corresponds to the wave EMA approach, and dashed line - to the quasi-static EMA.

Figure 4. Imaginary part of the effective dielectric permittivity (solid line) and imaginary part of the effective magnetic permeability (dashed line) of compacted metal powder with insulating oxide layers vs. conductivity of metal: (a) powder particle radius 1 pm, frequency 2.45 GHz; (b) powder particle radius 10 pm, frequency 2.45 GHz; (c) powder particle radius 1 pm, frequency 24 GHz; (d) powder particle radius 10 μm, frequency 24 GHz. Oxide layer thickness 3 nm, relative volumetric concentration of solid C_s = 0.5.

Chapter 20

Figure 1. SEM image of the agglomerated Y₂O₃ powder after annealing at 1100 °C.

Figure 2. Relative density of the sintered Y₂O₃ samples (dashed line) and microwave power input to the applicator (solid line) vs. heating rate at the high-temperature stage of sintering. The maximum sintering temperature 1400 °C.

Figure 3. The temperature of the sample (T) and the microwave power (P) input to the applicator for the sample vs. time during the high-temperature sintering stage of the process with the heating rate 25 °C/min and the maximum sintering temperature T_max = 1400 °C.

Figure 4. Same as in Fig. 3 but the maximum sintering temperature T_max is 1500 °C.

Figure 5. Same as in Fig. 3, but the heating rate is 100 °C/min and the maximum sintering temperature Tmax is 1500 °C.

Figure 6. Relative density of the sintered Y₂O₃ samples vs. heating rate at the high-temperature stage of sintering. The maximum sintering temperature 1500 °C.

Figure 7. Same as in Fig. 3, but the heating rate is 100 °C/min and the maximum sintering temperature T_max is 1700 °C.

Figure 8. SEM images of the surfaces of the Y₂O₃ samples obtained in rapid microwave sintering processes with a heating rate of 100 °C/min: (a) maximum sintering temperature T_max = 1600 °C, (b) T_max = 1700 °C.

Figure 9. XRD spectra of (a) the initial Y₂O₃ powder; (b) grinded surface of a microwave sintered sample (heating rate 100 °C/min, maximum temperature T_max = 1700 °C); and (c) as-sintered sample (150 °C/min to T_max = 1700 °C).

Chapter 21

Figure 1. Process (reaction) feasibility and kinetics.

Figure 2. Promotion of reaction feasibility under CPR microwave irradiation. The final-state free energy remains essentially unchanged during the process (^fG° ≈ ^fF) due to the insignificant polarizability of the products ( is negligible) under the irradiation.

Figure 3. Process-kinetics enhancement under CPR microwave irradiation. This scenario illustrates that the kinetics of both the irradiated and the purely thermal processes take place under identical driving forces (-ΔF = -ΔG°).

Chapter 22

Figure 1. (a) Geometry of the sample and (b) direction of current and magnetic field for a winding used in the electromagnetic compaction. (Rendering by NHMFL Public Relations Dept.)

Figure 2. Densities of as-sintered and electromagnetic compressed FL-5305 PM parts.

Figure 3. SEM micrographs of (a) as-sintered, and (b) electromagnetic compressed FL-5305 compacted at 50 tsi and sintered at 1150°C.

Figure 4. Microhardness of as-sintered and electromagnetic compressed FL-5305 PM Parts.

Figure 5. Optical micrographs of (a) as-sintered, and (b) electromagnetic compressed FL-5305 after thermal cycling in the dilatometer at 1000°C. Red dashed arrow shows Widmanstatten ferrite, blue dotted arrow shows allotriomophic ferrite, and black arrow shows pearlite.

Figure 6. Dimensional change for as-sintered FL-5305 during thermal cyclic heat-treatment in the dilatometer.

Figure 7. Rate of dimensional change for as-sintered FL-5305 during thermal cyclic heat-treatment.

Figure 8. Dimensional change for electromagnetic compressed FL-5305 during thermal cyclic heat-treatment.

Figure 9. Rate of dimensional change for electromagnetic compressed FL-5305 during thermal cyclic heat-treatment.

Figure 10. Comparison of the dimensional change of the as-sintered and electromagnetic compressed FL-5305 during (a) first thermal cycle, and (b) fourth thermal cycle.

Chapter 23

Figure 1. Zirconia particle size by electron microscopy. The top figure shows a plurality of particle images, the bottom is an image of a single particle.

Figure 2. Particle size distribution chart of 7.5% Yttria stabilized zirconia by

Figure 3. Yttria distribution in yttria stabilized zirconia. The image of high resolution transmission electron microscopy showed that yttrium and zirconium material became completely solid solution. Top, middle and bottom panels are shown in different resolutions.

Figure 4. The X-ray diffraction test report of zirconia particles. Results showed that with the standard card (PDF # 50-1089) comparative analysis, crystal planes (101) (110) (112) (211) are the tetragonal phase. It indicated that the zirconia particles were 100% tetragonal crystal phase.

Chapter 24

Figure 1. SEM photographs for the room temperature-fractured surfaces of B₄C/CNF composites sintered at 2173K/10min/50MPa: B₄C/CNF =(a) 100/0, (b) 95/5, (c) 90/10 and (d) 85/15 vol%.

Figure 2. Bending strength σ_b of the present B₄C/CNF composites at high temperatures.

Figure 3. SEM photographs for the fractured surfaces of B₄C/CNF ceramics at 1873 K: B₄C/CNF= (a) 100/0, (b) 95/5, (c) 90/10 and (d) 85/15 vol%.

Figure 4. Microstructural changes of B₄C/CNF=87.5/12.5 vol% composites after the high-temperature bending test.

Figure 5. Load-displacement curves for the B₄C/CNF composite ceramics at 1373, 1573, 1773 and 1973 K.

Figure 6. Elastic strain energy density of B₄C/CNF composites evaluated using the areas formed by the load-displacement curves measured at high temperatures.

Figure 7. Seebeck coefficient S of B₄C/CNF composites as a function of temperature.

Figure 8. Electrical conductivity _σe of B₄C/CNF composites with various compositions: as a function of temperature.

Figure 9. Thermal conductivity λ of B₄C/CNF composites as a function of temperature.

Figure 10. Dimensionless figure of merit ZT of B₄C/CNF composites as a function of temperature.

Chapter 25

Figure 1. SEM image showing intermetallic phases and precipitates in cross-section near tip.

Figure 2. Series of FIB cross-sections obtained at instrument tip. (Note 15 μm scale bar.)

Figure 3. SEM image of reconstructed volume element at tip region (scale bar = 15 μm), revealing intermetallic phases and some porosity.

Figure 4. Nanoscale NiTi grains in tip region oriented parallel to instrument axis. Intermetallic phases, similar to those shown in Figure 3, can also be seen. (Scale bar = 15 μm)

Chapter 26

Figure 1. TEM micstructure of mixture from different sample preparation methods. (a) carbon coated precursors, (b) conventional mixing method.

Figure 2. DSC curves for mixtures of carbon coated TiO₂ with B₄C and conventional mixing samples. Samples were heated in alumina crucible at 20 °C/min in flowing argon.

Figure 3. Weight loss of sample from different preparing method.

Figure 4. XRD patterns for samples from carbon coated precursors mixture at different temperature, (a) 1100°C, (b) 1200°C, (c) 1300°C, (d) 1400°C, (e)1500°C.

Figure 5. XRD patterns for samples from conventional carbon black mixing mixture at different temperature, (a) 1100°C, (b) 1200°C, (c) 1300°C, (d) 1400°C, (d)1500°C.

Figure 6. BET surface area of samples from carbon coated and carbon mixed precursors as a function of reaction temperature.

Figure 7. TEM micrographs of synthesized TiC-TiB₂ composite from carbon coated precursors at L500°C for 2 hours and their diffraction patterns, (a)mixture of TiC and TiB₂, (b) enlarge view of TiC particles, (c) diffraction patterns of selected single panicle TiB₂, (d) diffraction patterns of selected single particle TiC.

Figure 8. TEM micrographs of synthesized TiC-TiB₂ composite from conventional mixing at 1500°C for 2 hours. (ajmixttire of TiC and TiB₂, (b)enlarge view of TiC particles.

Figure 9. XRD patterns of composite powders with different content, (a) 40 wl. %TiB₂) and 60 wt. % TiC, (b) 60 wt. % TiB₂, and 40 wt. % TiC, (c) 80 wt. % TiB₂; and 20 wt. % TiC.

Figure 10. BSD micrographs of polished surface for sintered sample sintering with 5 wt. % Ni.

Chapter 27

Figure 1: Sintering profiles of 8YSZ, Ni(NO₃)₂ infiltrated 8YSZ, MoO₂ doped 8YSZ, and MoO₂ doped Ni(NO₃)₂ infiltrated 8YSZ sintered up to and held at 1200°C for one hour with heating rates of 5°C per minute (A, C, and E), and 10°C per minute (B, D, and F) according to the temperature profile indicated in each figure by the solid black line (-)

Figure 2: XRD patterns with indexed peaks of (A) Cubic (8YSZ) and tetragonal (3YSZ) YSZ sintered at 1200°C for one hour³², and (B) XRD patterns of 8YSZ with the addition of 1, 5, and 10 mol% MoO₂ and Ni(NO₃)₂ also sintered at 1200°C for one hour

Figure 3: (A) 10 mol% MoO₂ doped 8YSZ (B) 1 mol% MoO₂ doped Ni(NO₃)₂ infiltrated 8YSZ (C) 5 mol% MoO₂ doped Ni(NO₃)₂ infiltrated 8YSZ (D) 10 mol% MoO₂ doped Ni(NO₃)₂ infiltrated 8YSZ, where all samples were sintered up to and held at 1200°C for one hour

Figure 4: (A) Grain structure and (B) formed nano rods on surface of 10 mol% MoO₂ doped Ni(NO₃)₂ infiltrated 8YSZ sintered at 1200°C for one hour

Chapter 28

Figure 1: a) SEM cross-section micrograph of alumina coating on the NiCrAlY layer sprayed by APS. b) The magnified image at 2000x showing the different defects within the alumina, more details can be seen on the upper right of the image on globular pores (GP), fine pores (FP) and interlamellar crack.

Figure 2: a) SEM image of alumina coating at 2000X magnification. b) Final image was extracted and used as sample for an input into the model (512 × 512 pixels, 0.132 μm/pixel) and c) Conversion into the binary image.

Figure 3: Comparison of porosity measurements for different values of threshold determined by both covariance and imageJ.

Figure 4: Covariance of the alumina microstructure (binarized image) with porosity of 20.52%. The COV is measured in tow orthogonal directions (OX: parallel, OY: vertical to the coating).

Figure 5: Finite element mesh generated by OOF2D. White and red areas denote alumina and pore phases respectively. A finer mesh and higher node density (266070 nodes and 93323 elements) along the interface between two phases can be seen in the zoomed view. Homogeneity index = 0.9934.

Figure 6: Influence of the porosity fraction on ETC of alumina coating ANISOTROPIE

Figure 7: Influence of the porosity fraction of alumina coating on ETC for both directions, x is parallel to the substrate (longitudinal) and y through the thickness of coating (transverse).

Chapter 29

Fig.l The EB-PVD equipment at Japan Fine Ceram ics Center for the Nano-Coating Project (METI/NEDO) in Japan.

Fig.2 Microstructure and therm al conductivity of zirconia base ceramics layer fabricated by electron beam PVD process for thermal barrier coating in jet engine.

Fig.3 Images of simulation for ceramics coating in SIP project.

Chapter 30

Figure 1 Phase diagram of MgO-Al₂O₃-SiO₂ System [From Muan¹⁹]. F indicates the forstetite castable, P the periclase, and S the spinel castable and B is the common band phase

Figure 2. Flow diagram of the synthesis of magnesium aluminosilicate glass

Figure 3. Transparent Ce-activated magnesium aluminosilicate glass

Figure 4 shows the Ce-activated glass with Li⁶ dopant added

Figure 5. Emission spectrum of the cerium doped magnesium aluminosilicate glass without ⁶Li (upper) and with ⁶Li (lower).

Figure 6. Pulse height spectra of a ⁶Li-doped glass-ceramic scintillator under neutron and gamma-ray excitation. The neutron peak is clearly visible in the full spectrum (Neutron + Gamma) shown in the upper curve, and vanishes when the neutrons from the source are attenuated with boron-loaded rubber sheets.

Figure 7. Scintillation pulse decay traces of a ⁶Li-containing glass scintillator measured under gamma-ray (slow decay) and neutron (fast decay) excitation. Note the difference in the lifetimes for gamma-ray and neutron excitation, which is needed to provide n-γ pulse shape discrimination.

Figure 8. Pulse shape discrimination scatter plot of the ⁶Li-containing glass scintillator

Figure 9. TEM image of CeF₂ glass ceramic [Chen²⁶]

Chapter 31

Figure 1. Typical powder X-ray diffraction patterns of Pr-doped SiON (a-c) and SiAlON (d) sintered at different temperatures. (a) Si/Pr=46/1; (b) Si/Pr=62/1; (c) Si/Pr=90/1; (d) (Si+Al)/Pr=(83+7)/1. The standard lines of α-Si₃N₄, β-Si₃N₄ and Si₂N₂O are included for comparisons.

Figure 2. The X-ray diffraction patterns of Pr-doped SiON (a) and Pr-doped SiAlON (b) re-plotted at an expanded scale for 2θ=10°-50°.

Figure 3. The excitation and emission spectra of Pr-doped SiON (a-c) and Pr-doped SiAlON (d) sintered at different temperatures. (a) Si/Pr=46/1; (b) Si/Pr=62/1; (c) Si/Pr=90/1; (d) (Si+Al)/Pr=(83+7)/1.

Figure 4. The photoluminescence decay curves of Pr-doped SiAlON phosphors sintered at different temperatures.

Figure 5. Deconvoluted XPS spectra of Al 2p (a) and Pr 3d (b) for SiAlON:Pr

Chapter 32

Figure 1. Overview of spark plug construction.

Figure 2. Typical microstructure of 96% alumina ceramic used to produce spark plug insulators.

Figure 3. Evolution of spark plug design. Increases in the size of valves and cooling passages in engines limits the available space for spark plugs, necessitating smaller diameter insulators with reduced thickness.

Figure 4. Flow chart of spark plug insulator manufacturing process.

Figure 5. Electric field modeling shows that the maximum electric field occurs at transitions in the internal and exterior profile of the insulator in close proximity to contact points with the shell and center electrode.

Figure 6. SEM images of a dielectric puncture through an insulator showing the effects of thermal breakdown. The puncture propagated radially from the center electrode to the shell and generated sufficient heat to melt the ceramic. The insulator was carefully broken to reveal the path of the puncture.

Figure 7. Electrical resistivity of alumina ceramic is dependent on the composition of the glassy phase. Ternary diagram (a) shows the glass phase composition of two typical spark plug insulator compositions. Electrical resistivity (b) decreases with increasing temperature and differs by a factor of 10 for these two compositions.

Figure 8. Weibull plots with 95% confidence interval showing dielectric performance of two sets of spark plugs using insulators produced under different conditions. Testing was conducted on complete spark plugs using an automotive ignition coil to provide the voltage, using pressurized gas to suppress normal sparking at the firing tip in order to force puncture through the ceramic insulator.

Chapter 33

Figure 1: Tested Zuram sample geometries.

Figure 2: Probe with mounted Calcarb sample.

Figure 3: Plasma wind tunnel PWK 1 (left)⁷ and geometry for the photogrammetry (right)¹⁸.

Figure 4: Camera with lens on tripod head.

Figure 5: Total recession and recession rate of the carbon felt sample over time.

Figure 6: Total recession and recession rate over the radius of the carbon preform sample.

Figure 7: Total recession and recession rate over time for the flat sample.

Figure 8: Total recession and recession rate over the radius of the flat sample.

Figure 9: Total recession and recession rate over time for the spherical surface sample

Figure 10: Total recession and recession rate over the radius of the spherical sample.

Figure 11: Total recession and recession rate over time for the indented spherical sample.

Figure 12: Total recession and recession rate over the radius of the indented spherical sample

Figure 13: Total recession and recession rate over the radius of the indented sample evaluated over the first 12.3 s of the test.

Figure 14: Total recession and recession rate over the radius of the indented sample evaluated over the time from 12.3 s to 25 s.

Figure 15: Total recession and recession rate over time for the indented spherical sample evaluated at the edge of the indentation.

Processing, Properties,
and Design of Advanced
Ceramics and Composites

Ceramic Transactions, Volume 259

Preface

Controlled Synthesis, Processing, and Applications of Structural and Functional Nanomaterials