Processing of Ceramic Optical

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Handbook of Materials Science Volume 1 Optical

Materials 1st Edition R. S. Ningthoujam

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Light Weight Materials Processing and Characterization

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Organic Ferroelectric Materials and Applications

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Processing and Characterization of Materials Select
Proceedings of CPCM 2020 1st Edition Snehanshu Pal

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Nanostructured Nonlinear Optical Materials: Formation

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Table of Contents
Cover
Title Page
Copyright Page
List of Contributors
Preface
1 Introduction
1.1 Introduction
1.2 Technical Problem of Conventional Single Crystal
1.3 Problem of Conventional Translucent and Transparent
Ceramics
1.4 Objective of Optical Grade Ceramics
1.5 Conclusions
References
2 Ceramic Laser/Solid‐State Laser
2.1 Background
2.2 Principle of Laser Generation
2.3 Laser Ceramics
References
3 Scintillators
3.1 Background
3.2 Physics of Scintillation
3.3 Inorganic Single Crystal Scintillation Materials
3.4 Fabrication of Advanced Single Crystal and Ceramics
Scintillators
3.5 Optimization of Single Crystal and Ceramic Scintillators
3.6 Residual Problems and Future Trends
Acknowledgments
 References
4 Magneto‐Optic Transparent Ceramics
4.1 Introduction
4.2 Theory of Magneto‐Optic Effect
4.3 Important Parameter for Application
4.4 Paramagnetic Magneto‐Optic Ceramic Materials
4.5 Ferrimagnetic Magneto‐Optic Ceramics
4.6 Summary
References
5 Solid‐State Lighting
5.1 Introduction
5.2 Light Emitting Diodes (LEDs)
5.3 Fundamentals of Phosphor‐Converted White LEDs
5.4 Optical Ceramic Phosphors for High‐Power Solid‐State
Lighting
References
6 Passive Application/Window, Dome, and Armor
6.1 Background
6.2 Important Parameters
6.3 Fabrication of Passive Ceramics
6.4 Performance for Various Applications
6.5 Residual Problems and Future
References
7 Other Important Technologies
7.1 Surface Polishing (Finishing) and Coating
7.2 Bonding Technology
7.3 Single Crystal Ceramics by SSCG (Solid‐State Crystal
Growth)
7.4 Applications Using Ceramic Laser Technology
7.5 New Applications Using Transparent Ceramics
 7.6 Residual Problems and Future
References
Conclusion Remarks
Index
End User License Agreement

List of Tables
Chapter 3
Table 3.1 Properties of heavy crystal scintillators used or
pursued by the hi...
Table 3.2 Scintillators commonly used for medical imaging
and their propertie...
Chapter 4
Table 4.1 Optical scattering of ceramic and single crystal
TGG samples [21].
Chapter 5
Table 5.1 Overview of radiometric and photometric
quantities:φ represent...
Chapter 6
Table 6.1 Properties of some selected transparent ceramics.
Table 6.2 Grain size and in‐line transmission (632.8 nm) of
Al2O3 samples aft...
Chapter 7
Table 7.1 Specification of the solid‐state laser for the
MALDI/TOF‐MS analyze...

List of Illustrations
Chapter 1
Figure 1.1 Schematic design and transmission mechanism of
sodium lamp using ...
Figure 1.2 Schematic diagram of YAG single crystal grown
by CZ method.
Figure 1.3 (a) Optical quality image of Nd:YAG single crystal
ingot and (b) ...
Figure 1.4 Relationship between wavelength and in‐line
transmittance for com...
Figure 1.5 Illustration of optical scattering caused by
various microstructu...
Figure 1.6 (a) Reflection and (b) transmission microscopic
photograph of 1%N...
Figure 1.7 Relationship between optical scattering loss and
amplifying numbe...
Figure 1.8 (a) First demonstration of translucent alumina
ceramics by Dr. Co...
Figure 1.9 (a) Appearance of granulated Al2O3‐Y2O3
powders by spray drier an...
Figure 1.10 Pore distribution of Al2O3‐Y2O3 green body
after cold isostatic ...
Figure 1.11 (a) Image of removing pores from polycrystalline
ceramics by hot...
Figure 1.12 (a) TEM image of Y3Al5O12(YAG) ceramics
including excess SiO2 ne...
Figure 1.13 Transmission spectra of Nd:YAG single crystal
and polycrystallin...
Figure 1.14 (a) Fracture surface of Nd:YAG ceramics by
SEM and (b) lattice s...
Figure 1.15 (a) Schematic setup of laser tomography with 1
μm light source, ...
 Figure 1.16 (a) Appearance of Nd:YAG ceramics with 300
mm length, (b) Schlie...
Figure 1.17 Comparative data of (a) Polycrystalline and (b)
single crystal b...
Figure 1.18 Transmittance spectra between UV (vacuum) ~
infrared wavelength ...
Figure 1.19 (a) Optical loss at 1064 nm and laser
tomography at 633 nm of po...
Figure 1.20 (a) He–Ne laser irradiation test and (b‐1)
original and (b‐2‐4) ...
Figure 1.21 Optical inspection of polycrystalline Spinel
Ceramics by sinteri...
Chapter 2
Figure 2.1 Schematic energy diagram of (a) three‐level laser
(Yb‐doped) and ...
Figure 2.2 Light amplification by stimulated emission of
radiation in the op...
Figure 2.3 Fabrication flow sheet of Nd:YAG ceramics.
Figure 2.4 (a) First demonstration of Q‐CW laser oscillator
using Nd:YAG cer...
Figure 2.5 (a) Laser performance of 7%Yb:YAG ceramics
pumped by 940 nm LD....
Figure 2.6 (a) Appearance of 0.6%Nd:YAG slab ceramics
(165 × 55 × 6 mm) whic...
Figure 2.7 Emission cross sections of Nd:Y3ScxAl5−xO12
ceramics (x = 0...
Figure 2.8 (a) Schematic diagram for a mode‐locked system.
Source: Reprinted...
Figure 2.9 Appearance of Y2O3‐Tb2O3 (including Tb4+ ions)
single crystal by ...
Figure 2.10 Fabrication flow sheet of transparent Nd‐doped
Y2O3 ceramics.
Figure 2.11 Appearance of Nd‐ and Yb‐doped Y2O3, and Tm‐
and Er‐doped Lu2O3 ...
Figure 2.12 (a) External view, (b) Schlieren, and (c)
transmission spectrum ...
Figure 2.13 (a) Absorption and emission spectrum of
Er:Sc2O3 ceramics.(b...
Figure 2.14 (a) Appearance and microstructure, (b) cw laser
performance, and...
Figure 2.15 (a) Optical transmission of 2%Yb:CaF2
transparent ceramics windo...
Figure 2.16 Dependence of the average output power on the
absorbed pump powe...
Figure 2.17 Appearance of Cr‐doped ZnSe, and Fe‐doped
ZnSe ceramics by hot p...
Figure 2.18 Absorption and fluorescence spectra of (a) Cr‐
doped ZnSe, ZnS, a...
Figure 2.19 SEM micrographs of the surfaces of the
polycrystalline YAG fiber...
Figure 2.20 Output power as a function of input power for
the HR + Fresnel c...
Figure 2.21 (a) X‐ray diffraction pattern of FAP powder as a
raw material fo...
Figure 2.22 (a) Experimental configuration of the
confirming of laser grade ...
Figure 2.23 Schematics of optical scattering in fine‐grained
non‐cubic ceram...
Figure 2.24 Transmitted spectrum and loss coefficient of
Nd:FAP ceramics. Th...
 Figure 2.25 Effect of CAPAD temperature on the relative
density of undoped a...
Figure 2.26 (a) PL emission spectra for the 0.25 and 0.35
at.% Nd3+:Al2O3 sa...
Figure 2.27 Forward single pass experimental setup for
evaluating EDFA perfo...
Figure 2.28 Transmission Spectra of Sapphire Crystals with
3 mm thickness by...
Figure 2.29 Various configurations of producible composite
element and their...
Figure 2.30 (a) Appearance of YAG‐Nd:YAG‐YAG
waveguide structured composite ...
Figure 2.31 (a) Appearance of cylindrical clad‐micro‐core
structured composi...
Figure 2.32 (a) Appearance of end‐cap structured YAG‐
Nd:YAG‐YAG slab before ...
Figure 2.33 Nd:YAG (core)‐Sm:YAG (cladding =
supersaturated absorber) compos...
Figure 2.34 (a) YAG‐Nd:YAG‐YAG composite with 11 layers.
(b) Five‐layer comp...
Chapter 3
Figure 3.1 Development history of primary single crystal
scintillator [2, 3]...
Figure 3.2 Scintillation mechanism of activator‐doped
inorganic scintillator...
Figure 3.3 A photo showing different inorganic scintillation
single crystal ...
Figure 3.4 (a) Photograph of SrI2:Eu crystal grown by a
modified micro‐pulli...
Figure 3.5 Single crystal scintillation element used in CMS
calorimetric det...
Figure 3.6 Crystallographic structure of LSO showing 2 Lu
sites Lu1 and Lu2,...
Figure 3.7 Schematic diagram of LSO single crystal growth
by Czochralski met...
Figure 3.8 Top: A LYSO ingot grown by SIPAT with
constant diameter of 60 and...
Figure 3.9 Semitransparent LSO:Ce ceramic of the
thickness of 1 mm.
Figure 3.10 Schematic of garnet crystal structure.
Figure 3.11 Garnets single crystals: (a) LuAP:Pr with 20 mm
diameter and 50 ...
Figure 3.12 TEM morphologies of the LuAG nanopowders
synthesized by co‐preci...
Figure 3.13 (a) Transmittance of LuAG:Pr ceramic samples
with aliovalent sin...
Figure 3.14 Pictures of: (a) gel‐cast; (b) calcined; (c) vacuum
sintered; an...
Figure 3.15 Photos of the GGAG:Ce3+,xYb3+ (x = 0, 0.03,
0.09, 0.15, 0.3 at.%...
Figure 3.16 Depiction of the two Lu3+ symmetry sites in
Lu2O3.
Figure 3.17 Photographs and scatterometry of ceramics
after 1850 °C HIP trea...
Figure 3.18 (a) Normalized emission spectra under X‐ray
excitation of LYSO:C...
Figure 3.19 XANES spectra of LYSO:Ce,Mg and LYSO:Ce,Ca
single crystals compa...
Figure 3.20 TSL glow curves of the LuAG:Ce single crystals
SC‐1820, SC‐1700,...
Figure 3.21 (a) LuAl anti‐site defect in LuAG structure.
Insert upper figure...
Figure 3.22 Sketch of the scintillation mechanism at the
stable Ce3+ (left) ...
Figure 3.23 (a) LY of LuAG:Ce,Mg ceramics versus Mg2+ co‐
doping (measured wi...
Figure 3.24 Scintillation decay profiles of GGAG:Ce and
Ca2+‐co‐doped GGAG:C...
Figure 3.25 (a) Idealized fragment of LuAG crystal structure
by experiment....
Figure 3.26 Absorption spectra (a), TSL curves (b) and
pulse‐height spectra ...
Figure 3.27 XEL emission integrals of the 5d‐4f (250–450
nm), 4f‐4f (450–700...
Figure 3.28 Energy level scheme related to the “band‐gap
engineering”. VB an...
Figure 3.29 Energy spectra of GAGG:1 at.%Ce and LYSO:Ce
standard excited by ...
Figure 3.30 Pulse height spectrum acquired with a 137Cs
source shows that a ...
Figure 3.31 Afterglow ~5 sec after the removal of UV
excitation seen by the ...
Figure 3.32 (a) TSL glow curves for LuAG:Pr and LuYAG:Pr
integrated into the...
Figure 3.33 Afterglow intensity and light output as a
function of Ce content...
Figure 3.34 Energy band diagram of GOS and position of
the ground 4fn levels...
Figure 3.35 A comparison of radioluminescence spectra of
Lu2O3:5 at.%Eu scin...
Figure 3.36 The effect on luminescence intensity of doping
different lanthan...
 Figure 3.37 (a) Sketch of flat panel imaging. (b)
Photographs of laser‐cut c...
Figure 3.38 (a) The photograph of the polished bilayer
structure LuAG:Pr/LuA...
Chapter 4
Figure 4.1 (a) Electric field and magnetic field in
electromagnetic wave, (b...
Figure 4.2 Magnetic hysteresis image for ferromagnetic
(ferrimagnetic) and p...
Figure 4.3 Setup for measuring the Verdet constant of
paramagnetic materials...
Figure 4.4 Polarization characteristics of Dy2O3 ceramics
with 7 mm thicknes...
Figure 4.5 An example of measurement results for the
insertion loss and exti...
Figure 4.6 Image of thermal and refractive index
distribution in a medium fo...
Figure 4.7 Image of refractive index of light in index
ellipsoid.
Figure 4.8 Relationship between the laser fluence and
damage probability to ...
Figure 4.9 Damage cracks in (a) TGG single crystal and (b)
TGG ceramic sampl...
Figure 4.10 TGG ceramics samples.
Figure 4.11 A photograph of TGG ceramics samples [25].
Figure 4.12 A photograph of TGG ceramics samples (a) and
transmittance curve...
Figure 4.13 (a) Schematic showing the experimental setup
for investigating T...
Figure 4.14 A photograph of the TAG ceramics.
Figure 4.15 Transmittance calculated from Fresnel loss and
in‐line transmitt...
Figure 4.16 Appearance of (a) rod‐shaped ceramics and (b)
disk‐shaped TAG ce...
Figure 4.17 Temperature dependence of the Verdet constant
of different ceram...
Figure 4.18 Crystal structure characterization and effect on
optical transpa...
Figure 4.19 In‐line transmission spectra and photo of the
studied (DyxY0.95−...
Figure 4.20 (a) Appearance of the produced Dy2O3
ceramics, (b) outside view ...
Figure 4.21 Extinction characteristics of the Dy2O3 ceramics
with 7 mm thick...
Figure 4.22 In‐line transmittance curves of the
(Tb0.6Y0.4)2O3 and Tb2O3 cer...
Figure 4.23 Relationship between the concentration of Tb
ions in (TbxY1−x...
Figure 4.24 Faraday rotation characteristics of the TYO
ceramics in comparis...
Figure 4.25 (a) XRD patterns of Ho2O3 ceramics. The inset
is a photo of the ...
Figure 4.26 Wavelength dependence of the Verdet constant
of THO ceramics in ...
Figure 4.27 In‐line transmittance spectra of YIG ceramics
after pressureless...
Figure 4.28 (a) Open nicol and (b) crossed nicol of YIG
ceramics measured by...
Figure 4.29 (a) Transmittance spectra of Bi‐doped GIG
single crystal by LPE ...
 Figure 4.30 Faraday rotation angle of produced
(BixY3−x)Fe5O12 ceramic...
Figure 4.31 (a) Conventional TEM image and (b) lattice
structure around grai...
Figure 4.32 Faraday rotation angle of produced
(CexY3−x)Fe5O12 ceramic...
Chapter 5
Figure 5.1 (a) 1880s illustration of the nightly illumination
of a gaslight ...
Figure 5.2 (a) Lucalox (left) and regular alumina (right)
ceramic disk illus...
Figure 5.3 (a) The schematic market size of LEDs in Japan;
(b) temporal deve...
Figure 5.4 (a) Historical evolution of the performance
(lm/W) of commercial ...
Figure 5.5 (a) The LED operation principle, (b) radiative
recombination of a...
Figure 5.6 (a) Schematic imaging of a packaged round LED;
(b) schematic LED ...
Figure 5.7 Chip designs for blue‐emitting InGaN LEDs: (a)
schematic of a fli...
Figure 5.8 Approaches to solid‐state white sources for
general lighting appl...
Figure 5.9 External quantum efficiencies (EQEs) of
AlGaInP‐ and GaInAs‐based...
Figure 5.10 (a) “Full conversion” and (b) “partial
conversion” concepts of t...
Figure 5.11 (a) Article of the Japanese newspaper Nikkei
Sangyo Shimbun on t...
Figure 5.12 (a) Unit cell of garnet structure with
dodecahedron {A} site, oc...
Figure 5.13 (a) Simplified illustration of the effect of
Coulombic field, sp...
Figure 5.14 Schematic configurational coordinate diagram
of Ce3+ in YAG.
Figure 5.15 (a) Schematic model of energy shift of Ce3+ and
electron transfe...
Figure 5.16 (a) The flowchart to obtain quantum yield (QY)
of ceramic phosph...
Figure 5.17 Luminous efficacy (lm/W) of human eyes in
photopic vision (light...
Figure 5.18 The Commission Internationale de l'Eclairage
(CIE) 1931 color‐ma...
Figure 5.19 (a) CIE chromaticity diagram (color space)
including the color t...
Figure 5.20 (a) Test color samples from No.1 to 15.(b) a
depiction of an...
Figure 5.21 Three methods of generating white light from
LEDs: (a) red + gre...
Figure 5.22 Power‐conversion efficiencies versus input
power density of a st...
Figure 5.23 (a) Photographs, (b) In‐line transmittance, (c)
PL spectra and C...
Figure 5.24 (a) Surface SEM image of HSYAG2. (b)
Confocal laser scanning mic...
Figure 5.25 (a) Scanning electron microscopy (SEM) images
of the YAG:Ce–Al2O
Figure 5.26 (a) Photographs and (b) XRD patterns of Al2O3‐
Ce:TAG ceramics wi...
Figure 5.27 (a) Photographs of GAGG:xCe3+ transparent
ceramics. Normalized P...
 Figure 5.28 (a) Photographs of SPS‐processed ceramics on
back‐lit text. (b) ...
Figure 5.29 (a) Description of transparent LuAG:Ce
ceramics fabricating proc...
Figure 5.30 (a) Picture of as prepared transparent ceramics
(b) PL spectra o...
Figure 5.31 (a) Secondary and backscatter detector SEM
micrographs for sampl...
Figure 5.32 (a) Illustration of GRP‐coated PCP and white
LED under operation...
Chapter 6
Figure 6.1 Functional layers on transparent armor concept
design.
Figure 6.2 Schematic light transmission phenomena in a
polycrystalline ceram...
Figure 6.3 Diagram of the crystal structure of MgAl2O4.
Reproduced from [92]...
Figure 6.4 Phase diagram of magnesium aluminate spinel.
Figure 6.5 Appearance of MgAl2O4 transparent ceramics
fabricated in Raytheon...
Figure 6.6 Large‐sized transparent spinel ceramics
prepared in TA&T [100].
Figure 6.7 (a) Real in‐line transmittance as a function of the
sample thickn...
Figure 6.8 In‐line transmittance of the Co:MgAl2O4
ceramics pre‐sintered at ...
Figure 6.9 In‐line transmission of the MgAl2O4 spinel
ceramic and normalized...
Figure 6.10 Photograph (a) and the in‐line transmittance
(b) of the MgAl2O4 ...
Figure 6.11 Flexural strength of MgAl2O4 transparent
ceramics as a function ...
Figure 6.12 Microstructure of spinel ceramics by (a)
transmission, (b) trans...
Figure 6.13 Optical inspection of spinel ceramics by
sintering method and sp...
Figure 6.14 In‐line transmittance curves of spinel single
crystal by Vn and ...
Figure 6.15 Phase diagram for the Al2O3‐AlN composition.
Figure 6.16 Some mainstream applications of AlON
transparent ceramics: (a) i...
Figure 6.17 The photo (a) of commercial AlON transparent
ceramics and the tr...
Figure 6.18 (a) Optical images and (b) in‐line transmittance
of the transpar...
Figure 6.19 (a) Photographs and (b) in‐line transmittance of
the AlON transp...
Figure 6.20 Photograph of the AlON transparent ceramics
sintered by pressure...
Figure 6.21 FESEM micrographs and EBSD orientation
maps of the AlON ceramics...
Figure 6.22 Diagram of the crystal structure of Al2O3.
Figure 6.23 Comparison of transparency between (a) pure
TM‐DAR and (b) zirco...
Figure 6.24 Photographs of transparent Er: Al2O3 ceramics.
(the sample is ∼3...
Figure 6.25 Photographs of the transparent Al2O3 ceramics
before and after a...
Figure 6.26 Photographs and SEM micrographs of
transparent Al2O3 ceramics si...
Figure 6.27 Coordination structure of YAG crystal.
Figure 6.28 SEM micrographs of fracture surfaces of YAG
transparent ceramics...
Figure 6.29 Photograph and in‐line transmission curves of
Y3(1 + x)...
Figure 6.30 Diagram of the crystal structure of Y2O3.
Figure 6.31 Phase diagram of Y2O3.
Figure 6.32 Photographs and in‐line transmittance of Y2O3
ceramics doped wit...
Figure 6.33 Fracture surfaces of Y2O3 ceramics doped with
(a) 0 mol%, (b) 0....
Figure 6.34 “(a) TEM image of Y2O3 powders calcined at
1250 °C and (b) high‐...
Figure 6.35 In‐line transmittance of Y2O3 ceramics vacuum
sintered at 1800 °...
Figure 6.36 Photographs of the Y2O3 samples after HIP
treatment at (a) 1500 ...
Figure 6.37 Photograph of the HIP post‐treated Y2O3
ceramic (1 mm thick)....
Figure 6.38 Optical transmission micrographs of Y2O3
transparent ceramics pr...
Figure 6.39 Diagram of the three crystal structures of ZrO2.
Figure 6.40 The binary phase diagram of ZrO2‐Y2O3.
Figure 6.41 Photographs and in‐line transmittance curves of
transparent 8YSZ...
Figure 6.42 Photographs and in‐line transmittance curves
of transparent 10YS...
Figure 6.43 (a) Photograph and (b) in‐line transmittance of
the Y0.16Zr0.84O
Figure 6.44 Photograph of c‐YSZ disk produced by SPS at
1100 °C for 10 min u...
Figure 6.45 SEM image of the fracture surface of c‐YSZ
disks densified by SP...
Figure 6.46 Photographs of (a) the c‐YSZ ceramic produced
by SPS at 1100 °C ...
Figure 6.47 TEM images of the (a) as‐sintered c‐YSZ and (b)
annealed c‐YSZ. ...
Figure 6.48 (a) In‐line transmission of t‐YSZ ceramics (0.5
mm thick) presin...
Figure 6.49 SEM micrographs of the etched surface of the
HIP‐processed t‐YSZ...
Figure 6.50 Total forward transmission of (a) SPS‐HIPed
and (b) SPS‐HIP‐anne...
Figure 6.51 Fracture toughness and TFT at a wavelength of
640 nm of SPS‐HIP ...
Figure 6.52 Photograph of MgO ceramic HIPed at 1600 °C
for 0.5 h (1 mm thick...
Figure 6.53 Photograph of MgO and MgO‐CaO ceramics (1
mm thick).
Figure 6.54 Infrared and uv–vis/near‐infrared transmission
of nano‐grained M...
Figure 6.55 Photographs and transmission spectra of MgO
ceramics SPSed at 90...
Figure 6.56 The pseudo‐binary phase diagram of MgO‐
Y2O3 .
Figure 6.57 IR transmission spectra of the Y2O3‐MgO
nanocomposite ceramics w...
 Figure 6.58 IR transmission spectra of the as‐sintered
Y2O3‐MgO nanocomposit...
Figure 6.59 BSE photograph of MgO‐Y2O3 nanocomposite
ceramics sintered at 13...
Figure 6.60 IR transmission spectra of Y2O3‐MgO
nanocomposites (0.9 mm thick...
Figure 6.61 (a) Transmission spectra of single crystal MgO,
polycrystalline ...
Figure 6.62 MgF2 single crystal (left) and transparent
ceramic (right).
Figure 6.63 Transmittance spectra of MgF2 transparent
ceramic (red) and sing...
Figure 6.64 Typical transmission spectrum for transparent
polycrystalline sp...
Figure 6.65 Single‐hit high‐speed impact resistance of
potential strike face...
Chapter 7
Figure 7.1 Error map of the surface figure for the polished
laser gain mediu...
Figure 7.2 Error map of the surface roughness for the
polished laser gain me...
Figure 7.3 Image of subsurface damage (SSD) on the
surface that cannot be vi...
Figure 7.4 Pitch polishing with conventional machine.
Figure 7.5 (a) MRF polishing machine. (b) Polishing with
MR fluid. Cerium ox...
Figure 7.6 80‐in. IAD (ion‐assisted deposition) coating
chamber.
Figure 7.7 Ion beam generated by 66 cm RF linear ion
source.
Figure 7.8 Stoney equation.
Figure 7.9 Technical problem of diffusion bonding using
crystals.
Figure 7.10 Fracture surface of YAG‐Yb:YAG crystal
composite after laser osc...
Figure 7.11 Transmission microphotograph of (a) after
diffusion bonding with...
Figure 7.12 (a) Forming YAG‐Nd:YAG composite by
bonding powder compacts. (b)...
Figure 7.13 Various type of ceramic composite and testing
results.
Figure 7.14 (a) Appearance of YAG/Nd:YAG/YAG ceramic
composite formed by DB ...
Figure 7.15 (a) Three‐point bending strength of monolithic
YAG and Nd:YAG ce...
Figure 7.16 Optical properties of ceramic composites in
comparison with thei...
Figure 7.17 (a)–(c) Observation of scattering for bonding
interfaces of YAG/...
Figure 7.18 (a) Texture of crack for Nd:YAG single crystal
and polycrystalli...
Figure 7.19 Principle diagram of single crystal growth by
nonmelting process...
Figure 7.20 Reflection microscope photograph of Nd:YAG
with excess Al2O3 sin...
Figure 7.21 Relationship between heating temperature and
growth rate of Nd:Y...
Figure 7.22 XRD patterns of (a) <110> and <111> seeded
YAG samples heated at...
Figure 7.23 Comparative data of laser performance
concerning 2.4%Nd:YAG poly...
Figure 7.24 (a–c) samples show appearance of LGO apatite,
BaTiO3 and LSO sin...
Figure 7.25 XRD pattern of (a‐2) random orientation
polycrystalline, (a‐1) c
Figure 7.26 (a) Conventional MALDI system by N2 laser
and the advanced micro...
Figure 7.27 Results of application of the MALDI/TOF‐MS
analyzer using a cera...
Figure 7.28 (a) Device configuration of laser igniter. (b)
Nd:YAG ceramics a...
Figure 7.29 (a) Appearance of conventional spark plug and
microlaser spark p...
Figure 7.30 System image of space solar pumped solid‐state
laser using Nd,Cr...
Figure 7.31 Appearance of monolithic ceramic jewel with (a)
green and red, (...
Figure 7.32 Appearance of composite ceramic jewel with (a)
color gradation o...
Figure 7.33 Appearance of ceramic jewel with (a) blue
spinel ceramics and 10...
Figure 7.34 Appearance of ceramic jewel: (a) green +
colorless core with com...
Figure 7.35 (a) Appearance of ceramic heating element and
detail of heating ...
Figure 7.36 Machining of small ditch pattern for LED
lighting using wireless...
Figure 7.37 Difference of focusing distance using
conventional glass and hig...
Figure 7.38 Appearance of produced 10% Y, 3% Ti:ZrO2
ceramics with refractiv...
Figure 7.39 Comparable data of conventional glass (BK7),
Y‐stabilized ZrO2 s...
Figure 7.40 Comparable data for bending strength and
results after impact te...
Figure 7.41 (a) Sketch of impact test on test plate by
dropping a zirconia b...
Figure 7.42 Transparent Al2O3 with 0.5 mm and spinel
ceramics with 5 mm thic...
Figure 7.43 High‐strength transparent YAG ceramics with
0.3 mm thick produce...
Figure 7.44 Optical inspection of polycrystalline spinel
ceramics by sinteri...
Figure 7.45 (a) He–Ne laser irradiation test and (b‐1)
original and (b‐2–4) ...
Figure 7.46 In‐line transmittance curves of Spinel Single
crystal by Verneui...
Figure 7.47 (a) Appearance of large spinel ceramics (left: 60
× 60 × t25 mm,...
Processing of Ceramics

Breakthroughs in Optical Materials

Edited by

Akio Ikesue
World Lab. Co., Ltd., Nagoya, Japan
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List of Contributors
Yan Lin Aung
World‐Lab Co., Ltd. Mutsuno
Atsutaku
Nagoya
Japan
Penghui Chen
Key Laboratory of Transparent Opto‐functional Inorganic Materials
Shanghai Institute of Ceramics
Chinese Academy of Sciences
Shanghai
China
and
Center of Materials Science and Optoelectronics Engineering
University of Chinese Academyof Sciences
Beijing
China
Xiaopu Chen
Key Laboratory of Transparent Opto‐functional Inorganic Materials
Shanghai Institute of Ceramics
Chinese Academy of Sciences
Shanghai
China
and
Center of Materials Science and Optoelectronics Engineering
University of Chinese Academy of Sciences
Beijing
China
Akio Ikesue
World‐Lab Co., Ltd. Mutsuno
Atsutaku
Nagoya
Japan
Jiang Li
Key Laboratory of Transparent Opto‐functional Inorganic Materials
Shanghai Institute of Ceramics
Chinese Academy of Sciences
Shanghai
China
and
Center of Materials Science and Optoelectronics Engineering
University of Chinese Academy of Sciences
Beijing
China
Xin Liu
Key Laboratory of Transparent Opto‐functional Inorganic Materials
Shanghai Institute of Ceramics
Chinese Academy of Sciences
Shanghai
China
and
Center of Materials Science and Optoelectronics Engineering
University of Chinese Academy of Sciences
Beijing
China
Takuya Mikami
Okamoto Optics, INC.
Haramachi, Isogoku
Yokohama
Japan
Martin Nikl
Institute of Physics of the Czech Academy of Sciences
Prague
Czech Republic
Jian Xu
Graduate School of Human and Environmental Studies
Kyoto University
Kyoto
Japan
and
International Center for Young Scientists (ICYS)
National Institute for Materials Science (NIMS)
Tsukuba
Japan
Preface
I worked for a refractory company specializing in steelmaking and
was planning to retire as a refractory engineer after graduating from
the university (master's course) in 1983. In 1991, my boss, the
research director, said to me, “I want you to develop anything good
new technology.” New technology for refractory companies generally
means “development of refractories useful for steel smelting.”
However, as a young and motivated engineer at that time, “anything
good” was interpreted by me as “new development in any area of
expertise is okay!” I was very interested in ceramics at that time, but
I was quite an amateur, so if I have to do anything new, I chose a
research that is the most challenging in the world and in which no
one has succeeded until now. I had read a variety of literature and
judged that “laser oscillation with polycrystalline ceramics would be
the most difficult technology.” At that time I focused on the article
“Polycrystalline Ceramic Lasers, J. Appl. Phys. (1973)” by C.
Greskovich and J. P. Chernoch, but their results were distinctly
different from laser oscillation. Besides, similar research was not
reported by other researchers. I suddenly understood that this must
be a certainly difficult technology. I also understood that even single
crystals cannot oscillate laser with high efficiency in the case of lamp
excitation system. I thus interviewed several Japanese laser
specialists and scientists regarding the possibility of developing
ceramic lasers, but the only answer I received was “even glasses and
single crystal laser gain media have optical problems; ceramics with
lots of scattering sources aimed for laser gain media is absolutely
meaningless.” The same question was asked to material scientists as
well, and their answers were also similar that “translucent ceramics
has been developed, but its optical quality is low quality that cannot
be compared with single crystal. So, you should quit this foolish idea
to develop a ceramic laser.” Even from the viewpoint of scattering
theory, it seemed considerably impracticable, so I presumed that
“this must be a new technology,” and it became the starting point for
my new research topic i.e. the development of ceramic lasers.
However, since I was merely a refractory engineer with not much
expertise in ceramics or laser, I did not know what the fundamental
problems are and how to approach the development of ceramic
lasers, except that I had to create the material from scrap. The only
thing I could think was “first of all I just have to completely eliminate
the scattering sources and then the last remaining problem is the
existence of the grain boundary,” and I believed that “my challenge
will succeed if there is no optical problem with the grain boundary.”
The kamikaze challenge began in the summer of 1991, in autumn I
succeeded in making a transparent YAG (Y3Al5O12) sintered body,
and in December a transparent YAG ceramics doped with laser active
element Nd was successfully produced. Although I knew it was still
of insufficient optical quality, I requested the research institution
and companies for laser oscillation test using the samples, but they
all rejected it because of the only reason being that it was a
“polycrystalline material.” Finally, in late December, I brought my
ceramic samples to Osaka University, Laser Fusion Research Center,
which is the only university in Japan interested in ceramic lasers.
Prof. K. Yoshida also tested it with uncertainty, but the next day he
was able to oscillate the CW laser using my samples at room
temperature. This was the birth of the world's first ceramic laser.
However, one year after the first laser oscillation, research and
development was interrupted because I worked in a refractory
company where research and development of refractories is the main
focus. In 1994 I first presented the possibility of laser oscillation by
ceramics at a conference in Japan, but most researchers ignored the
results. For the purpose of summarizing my research results, I
submitted a paper titled “Fabrication and Optical Properties of High‐
Performance Polycrystalline Nd:YAG Ceramics for Solid‐State
Lasers” to the journal of American Ceramic Society in 1995, after
which the study was completely stopped. In order to continue the
development of ceramic lasers, I retired from the refractory company
in 1996, joined a private company, and later joined a research
institution; however, “ceramic laser” was not well recognized in
Japan. Eventually, there was no way but to establish my own
company in 2005 and continue the research and development of
ceramic laser. The research was suspended for 14 years from the
birth of ceramic lasers. Meanwhile, research on ceramic lasers, which
is more promising than single crystals for their higher performance
and high output power, has been active abroad and received a lot of
funding. I have attempted to resume ceramic laser development for
14 years, and fortunately, since 2007 I have been able to resume
research on “ceramic laser” with support from AOARD/AFOSR
(Asian Office of Aerospace Research and Development/Air Force
Office of Scientific Research), which are part of AFRL (Air Force
Research Laboratory). Bringing out truly new science and technology
on the basis of our understanding of the surroundings is not an easy
one, and in my case it took me a lot of endurance and perseverance.
Incidentally, ceramic lasers have grown into an important technology
that can replace a single crystal laser gain medium. Today, ceramic
laser has become a paradigm of solid‐state laser especially in
generation of a 100 kW class laser by a large medium that is difficult
to manufacture with a single crystal and high functionality by
forming composite gain medium (such as Nd:YAG‐Cr4+:YAG
composite that can simultaneously provide laser generation and
switching function); generation of megawatt/cm3 class power
density by a small medium that is resistant to laser damage; laser
generation by a new type of material such as Y2O3, Lu2O3, etc.,
which is difficult to manufacture with a single crystal; and so on. The
existence of super high‐quality single crystals capable of optical
amplification and the fact that ceramics comparable to that single
crystal was successfully developed have initiated the development of
other optical ceramics. One example is development of Pr:LuAG
(Lu3Al5O12) or Ce:LuAG ceramics as a high‐speed scintillator for
PET (positive electron tomography) or high‐energy physics, which
requires high transparency and gamma ray shielding function.
Although still under development, they are expected to have wide
applications in the future. Recently, the industrial application of 1
μm band fiber laser has advanced, and the demand for isolators has
also increased accordingly. Currently, the main material for this
application is TGG (Tb3Ga5O12) single crystal, but in recent years,
the same TGG ceramic has also been developed and commercialized.
Since this material has insufficient Verdet constant and tends to
generate thermal lenses, recently ceramic materials such as TYO
(Tb2O3‐Y2O3) and TAG (Tb3Al5O12), which are difficult to grow by
single crystal growth techniques, have been reported, and in the near
future market share of ceramics is expected to increase. Iron garnet
ceramic isolators have also been reported for telecommunication
(1.3–1.5 μm band), indicating the possibility of clearing the technical
and economic problems of current single crystal isolators.
Development and practical application of blue‐violet LED and LD are
advancing. In addition, LED lighting that can convert blue‐violet
light into white light was also commercialized by using organic–
inorganic composite phosphors in which Ce:YAG powder was
dispersed in silicone resin. However, the development of all‐ceramic
phosphors (Ce:YAG ceramics as a representative example) has been
carried out in response to the demand for long durability and high
power application, and some applications have begun to be applied
in automobile head lamps and projectors. In addition, for military
applications, the development of high strength and highly
transparent ceramic dome and ceramic armor to replace sapphire
single crystal has also been advanced, and the basic technology of
laser ceramics will be applied in various fields in the near future. It
has been thought that grain boundary scattering (Rayleigh
scattering) cannot be avoided even if scattering sources, excluding
grain boundaries, are completely eliminated in ceramics. It should be
noted that Rayleigh scattering is the theory of the scattering
phenomenon in the atmosphere and is not premised on scattering in
real substances (ceramics). Of course the theory is correct, but it
seemed that we, the material scientists, wrongly imagined the limits
of material development just by assumption, without confirming the
truth of natural science. Polycrystalline ceramics with optical
properties superior to high‐quality single crystals have been
developed in the wavelength range from ultraviolet to visible to
infrared recently, and the concept of optical material development
based on the conventional theory has been completely overturned.
This “technological innovation” has caused the trend in optics to
move from single crystal to polycrystalline ceramics.
This book “Breakthroughs in Optical Materials” not only introduces
research and development examples starting from the development
of ceramic lasers that broke through conventional common sense,
but also mentions historical background, theory, manufacturing
process, and applications. This book is a compilation of the
transparent ceramics revolution that I started working on since 1991.

Akio Ikesue
1
Introduction
Akio Ikesue and Yan Lin Aung
World‐Lab Co., Ltd. Mutsuno, Atsutaku, Nagoya, Japan

1.1 Introduction
Human beings have used ceramics symbolized by tableware from
ancient times, but the modernization of ceramics and the “ceramic
science” based on sintering began since the middle of the twentieth
century. In recent years, engineering ceramics used for bearing parts,
milling media, surface plate for semiconductor steppers, minor parts
of automobile engines, pyroelectric materials for infrared detection,
PTC (positive temperature coefficient), NTC (negative temperature
coefficient) thermistors as temperature sensors, inkjet printer, touch
panel, moreover, sonar for fish finder in fishery and military
application, piezoelectric material as ultrasonic diagnosis in medical
field, ionic conductors for air‐fuel ratio control in automobile and gas
sensor for oxygen detection in molten steel in steel production,
magnetic materials used in general motor and servomotor,
translucent ceramics as functional materials used in high‐pressure
sodium discharge lamps and optical shutters, and so on. Without
ceramics, the economic activity of modern society is impossible now.
The development of the translucent ceramics mentioned above was
initiated by the development of translucent alumina ceramics by Dr.
Coble in the 1950s and its application to high‐pressure sodium lamps
[1]. Principally, ceramics has been considered to be opaque, but he
controlled the microstructure of ceramics (that is, by controlling the
migration rate of pores and grain boundaries in the process of
sintering alumina), and was able to reduce the volume of residual
pores, characteristic light scattering sources in ceramics, and finally,
he succeeded in developing alumina ceramics which can transmit
visible light for the first time in the world. By applying this idea,
PLZT (lead lanthanum zirconate titanate) ceramics for flash
protection, MgF2 ceramics for infrared ray transmission, scintillation
optical ceramics such as Pr,Tb:GOS (Gd2O2S) ceramics and Eu:
(GdY)2O3 ceramics for X‐ray CT (computed tomography) etc. were
successively developed, and some of them are already applied in
industrial field. About 50 years have passed since the invention of
translucent alumina ceramics by Dr. Coble, and it has been applied
to high‐pressure sodium discharge lamp until today (2018).

Figure 1.1 Schematic design and transmission mechanism of

sodium lamp using translucent Al2O3 ceramic tube.
As shown in Figure 1.1, the high‐pressure sodium lamp is illuminated
by discharging the metal sodium (Na) inside the alumina tube by
applying a high voltage and radiating the luminescent line to the
outside of the discharge tube. The radiation efficiency of high‐
pressure sodium lamp is about 14–20% which is very high compared
to 1–3% of the normal light bulb, has high power, and has a long life
(8–9000 hours) so it is used for lighting in tunnels and express
highway. The wall thickness of this alumina tube is at most about 1
mm, and the in‐line transmittance is only about 20–30%, and the
other discharge lights are radiated from the inside to the outside by
diffuse transmission.
Radiated light certainly generates Fresnel loss of about 7% inside the
discharge tube, and it is also radiated while repeating transmission
and reflection inside the tube. The total transmittance (i.e., amount
of light radiated to the outside of the discharge tube/total radiation
amount) of the alumina discharge tube is about 97–95%, and the
light energy of 3–5% is lost. That is, if calculated simply, optical loss
of 3–5%/mm (discharge tube thickness) is generated. The optical
quality of these alumina tubes is not a major problem for discharge
lamp application even if the in‐line transmission and scattering
characteristics are not sufficient. Because it is sufficient as long as
the total transmission (total of in‐line & diffuse transmission) is high.
Even in the translucent alumina ceramics that has been continuously
improved, there are still many scattering sources inside; for example,
residual pores, pinning agents such as MgO, Y2O3 situated at the
grain boundary portions, and also grain boundary phases (generally
spinel and YAG [Y3Al5O12]) due to the reaction between the pinning
agents and the host material. The optical loss of a laser gain medium
which requires extremely high optical properties such as high optical
homogeneity and extremely low optical scattering should be
preferably less than 0.1%/cm (basically scattering with nearly zero).
Even for crystal materials, it is very difficult to meet this strict
requirement. Therefore, it should be considered impossible to apply
ceramic laser with extension of Dr. Coble's technology developed in
the 1950s.
In 1974, Dr. Greskovich developed Nd:Y2O3‐ThO2 ceramics and
demonstrated laser oscillation, but the concentration of scatterers
(especially residual pores and segregated phases) inside the material
was too high and lasing efficiency was only less than 0.1% (pulse
oscillation only) because of lamp excitation system at that time. In
the 1980s, Dr. With of Philips developed translucent YAG
(Y3Al5O12), and in 1990, Dr. Sekita of NIRIM demonstrated Nd‐
doped YAG ceramics, but laser oscillation was not achieved.
Therefore, it was considered that significant laser oscillation by
polycrystalline ceramics is impossible in principle.
In 1991, the main author was not an expert in laser or ceramics, but
just a refractory engineer. I asked Japanese lasers and material
scientists, “Can laser oscillation with polycrystalline materials be
theoretically possible?” However, the laser scientist says, “Even with
glass or single crystals, homogeneity and scattering are being a
problem, so ceramic materials are out of question.” Material
scientists answered, “ceramics with many scattering sources in the
material are impossible to generate laser.” Judging from the level of
ceramic production technology at the time in 1991, their answers
were correct. However, my thinking is that “exploration on the truth
of natural science and prediction of the future is the mission of a
scientist” (at that time I was a refractory engineer and not holding a
Ph.D.), and I could not simply accept their opinion. So, I decided to
work on “potential of ceramics for future exploration in the optical
field.” The idea “laser oscillation by ceramics” started in the summer
of 1991 and confirmed the success of production in December of that
year, but since the author belonged to the private company, it could
be published in 1995.
In 1995, the author demonstrated highly efficient laser oscillation by
using polycrystalline ceramic materials with performance that could
match or surpass high‐quality single crystal [2], but materials and
laser experts at the time were highly skeptical about our report. One
of the reasons is that I was not an expert in ceramics and lasers, and
the invention was by a person from a different field (i.e., a refractory‐
related engineer working for steel smelting). Generally, a large
number of scattering sources (such as residual pores and
heterogeneous phases) are present in the common ceramics, causing
significant Mie scattering. Especially from the technical point of
view, no one proposed to remove those residual pores completely in
ceramics. The density of the transparent ceramics is much higher
than the opaque ceramics used for other applications, and it shows
good transparency, but even in this case, numbers of pores of more
than 1000 ppm are remained inside the ceramic material. Another
hurdle to overcome is even if we were able to remove those residual
pores completely, nobody had answers to “the problem of Rayleigh
scattering from grain boundary phase and grain boundary,” which is
the biggest technical problem in terms of technology. There were
many reports from ceramists at that time describing that a lot of
residual pores (scattering sources) are present in the ceramics
material, and also, structure defects certainly generated when the
granulated raw materials are pressed in molding process, and these
defects are definitely remained even in the final sintered body. They
have reported those descriptions with photographs of microstructure
of ceramics as evidence. However, the reports only described the
observation method for defects in ceramics and observed results, and
there were no discussion on the cause of defect formation and how to
solve this problem. The authors thought that structure defects in
materials were generated mainly by artificial factors, and we should
clarify the problem sources and modify the microstructures; finally,
we will be able to eliminate those defects including residual pores.
Once Mie scattering can be removed from the inside of the material,
the remaining problem will be only Rayleigh scattering. When I
attended a conference in ceramic society, I saw some researchers
reported that “This ceramic has a clean grain boundary,” but the
transparency of their ceramics was not as good as single crystals
although they showed a clean grain boundary. That was a basic
contradiction point noticed to me, and I simply interpreted their
“clean grain boundary” that during observation with an electron
microscope they could observe only the clean area where secondary
phase does not exist. Actually, we should pursue what is the
fundamental nature of Rayleigh scattering. Also, we should further
pursue that even if we can form a really clean grain boundary,
whether or not it will be possible to obtain ceramic material with
ultra‐low scattering or without scattering. To acquire such evidences
are the essence of good research work, and hence, there can be
progress in science and technology and there are roots that can
create the next innovation. At that time, I was an amateur (refractory
engineer) who knew nothing about lasers and ceramics, but when I
reconsidered now probably, I had a challenging spirit pursuing the
essence of material science because of lack of knowledge about laser
and ceramics. In this chapter, we will describe how the ceramic
material, which is a guideline for the development of various optical
ceramics, changed from the translucency level [3] to the optical
grade material, based on the development of ceramic laser materials.
1.2 Technical Problem of Conventional Single
Crystal
Since single crystal materials are widely applied in various industrial
fields and it is difficult to describe the technical problems of these
single crystals together at one time, firstly we will focus on laser
crystals that require the highest quality. In 1960, laser oscillation was
firstly demonstrated by Cr doped Sapphire by Maiman, and then,
laser oscillation at room temperature using Nd‐doped YAG
(Y3Al5O12) single crystal by Guesic in 1964 was a trigger for the birth
of solid‐state laser. After laser oscillation by YAG single crystal,
unique laser performance of various types of laser gain media, such
as YVO4, Cr:Forsterite (Mg2SiO4) KGW (KGd(WO4)2), Ti:Sapphire
(Al2O3), Cr:ZnSe, and Cr:ZnS, has been reported. However, new
laser gain materials, which can exceed the YAG, have not been found
in total performance including the quality of materials, and even
now, the mainstream of solid‐state lasers is YAG and it is still
unchanged. YAG materials are applied in most of solid‐state laser as
gain medium, and almost all of them are single crystals grown by the
Czochralski (CZ) method. A transition metal element such as Cr, Ti,
or a lanthanide element such as Nd, Yb, Er, Tm, and Ho is added to
the YAG single crystal as a laser (active) element. Among these active
elements, Nd is belonging to the four‐level system and it is easy to
create a population inversion (a state in which number of electrons
in the upper state is higher than the lower state) at the f‐f electron
transition of Nd by external excitation. The laser oscillation is
relatively simple in this system, and it has a fluorescent line with a
narrow spectral line width and high quantum efficiency; hence, it is
considered to be the most important laser active element in YAG
host crystal. In recent years, however, LD (laser diode) excitation
system became typical in these days and strong excitation became
possible as well; therefore, Yb with three‐level system with higher
quantum efficiency of 91% has also been used as laser gain material.
The CZ method shown in Figure 1.2 is generally used to grow the
YAG single crystal. The starting materials are Y2O3, Al2O3, and
Nd2O3 powders with high purity above 4 N (99.99 mass%) grade,
and these raw materials are weighed in YAG composition (not strict
stoichiometric composition) and mixed. Then the mixture is molded
and calcined. A relatively dense sintered body obtained by sintering
is used as a raw material for melting. It is filled in an iridium (Ir)
crucible. The Ir crucible is heated by high frequency induction and
melted at temperature higher than the melting point of YAG (1950
°C).
Figure 1.2 Schematic diagram of YAG single crystal grown by CZ
method.
Generally, YAG seed crystals with <110> orientation which has the
smallest surface‐free energy is used but <110> or <100> oriented
seed crystals are also applied in some cases. This seed crystal is
immersed in the molten YAG, and then, crystal growth is
continuously carried out at a rotation speed of 10 ~ 30 rpm and a
pulling rate of about 0.2 mm/hour. In the case of Nd‐doped YAG
crystal, Nd ions substitute Y sites in YAG lattice. The ionic radius of
Nd ion is too large compared with that of the Y ion, so it is well
known that it is not easy to dissolve the Nd ions in the YAG host
crystal as a solid solution. The segregation coefficient of Nd ion to
YAG host crystal is very small (that is, the concentration ratio of Nd
in crystal to Nd in the melt is very small). According to the literature,
since the segregation coefficient of Nd to YAG crystal is about 0.2
[4], normally the concentration of Nd ions in the melt is set to be
several times higher than the target Nd concentration (that is, the
concentration of Nd doping in the YAG sinter body which is used as
starting material for melting is prepared with higher than the target
composition). Even if the concentration of Nd in the melt is prepared
with very high, the concentration of Nd in the YAG crystal may not
be automatically increased homogeneously and simply in proportion
to its concentration. When the concentration of Nd in the YAG
crystal is increased to higher than 1 at.%, many precipitates
(scatterers) are generated in the crystal and it is difficult to utilize it
as a laser gain medium. Even in the case of the commonly used 1 at.%
Nd:YAG, (211) facets tend to be formed from the pulling axis of the
crystal (ingot) toward the outer periphery [4], and thus, only the
outer periphery of the columnar crystals can be used as a laser gain
medium. Also, when pulling YAG single crystal, the Nd concentration
in the growth crystal is significantly lower than that in the melt, so
the Nd concentration in the melt increases as the crystal grows. For
this reason, the concentration of Nd in the melt at the initial stage of
growth differs from the concentration of Nd at the middle to end
stage of the growth. So, the grown crystal also suffers this influence,
resulting in a gradient concentration change of Nd in the crystal
growth direction. Due to this drawback, each end face of the laser rod
is influenced by the composition variation accompanying the Nd
concentration change. Therefore, only crystals with nonuniform
refractive index are produced. This is a disadvantage in the principle
of crystal growth.
Figure 1.3a shows an image of the optical quality of a YAG crystal
(ingot) doped with about 1 at.% Nd. In the center part of the ingot,
there are a core (strong birefringence part), a large number of facets
(consecutive layers with different Nd concentrations = growth
striation) from inside the material to the outside peripheral part, and
almost no optically homogeneous part. Figure 1.3b shows the
appearance of a commercially available Nd:YAG slab and the
photograph of the same material observed under a polarizing plate
(crossed nicol). Commercially available Nd:YAG single crystals have
very high transparency, and they appear optically very uniform in the
naked eye observation. However, when observing through the
polarizing plate, the layered facets can be detected at irregular
intervals in the direction crossing the length direction of the slab. It
is not necessarily optically uniform that the optical quality of the
single crystal of the highest level at the present time that is
commercially available in the market. If an optically inhomogeneous
part is remained in the laser gain medium, the optical amplification
efficiency and beam quality will be extremely lowered. Therefore,
required characteristics for optical quality of single crystal for use of
laser gain media are set very strictly. The quality control at the actual
single crystal production is carried out in the following procedures.
First of all, positions with less thermal distortion and refractive index
change in the Nd:YAG ingot are searched by observing through a
polarizing plate or interferometer. Next, using a laser light, the
concentration of the scatterers existing in that part is inspected, and
then, a portion with good quality is taken out by boring and it can be
used as a laser gain medium. However, even if there are many
nonuniform portions, it is not a big problem when the laser emission
direction is perpendicular to the facet. The optical loss of the highest
quality Nd:YAG single crystal at present is 0.1%/cm level or less, and
this quality is remarkably higher than the same single crystal
synthesized by the Verneuil method in the 1964s. However, single
crystalline technology is already technically limited, and it is
principally difficult to obtain higher quality due to its technological
limitation. To grow a YAG single crystal, it requires not only a very
expensive Ir crucible and growing equipment, but also its growth
speed is very slow, and it takes about one month to grow an ingot
having a diameter of 4–6 in. and a length of 8 in. In addition, the
initial cost (very expensive growth equipment) and the running cost
(electricity, crucible recovery cost, etc.) are very high, and the yield of
the laser gain medium is very low, which is disadvantageous in
economy. On the other hand, it is difficult to obtain a large‐sized
laser rod or slab even from a technical point of view, thus leaving
technological problems such as difficulty in generating high output
laser.

Figure 1.3 (a) Optical quality image of Nd:YAG single crystal ingot
and (b) appearance of commercial Nd:YAG crystal slab and its
observation under polarizer and crossed nicol.
Source: Akio Ikesue, Yan Lin Aung, Voicu Lupei (2013), Ceramic Lasers,
Cambridge University Press. https://doi.org/10.1017/CBO9780511978043.

YAG laser material has superior overall characteristics as compared

with other lasers but the Nd:YAG single crystal which is the most
critical part in the solid‐state laser system has economical (including
productivity) and technological problems as described above. It is
the actual condition that there are many unsolved problems. It is
difficult in principle to break through the current problems with the
conventional single crystal growth method, and hence, the creation
of new innovation is indispensable.
1.3 Problem of Conventional Translucent and
Transparent Ceramics
As mentioned above, regarding translucent ceramics, Dr. R. L. Coble
developed translucent alumina in 1959 [1], and GE applied it to arc
tube for high‐pressure sodium lamp in the 1960s [5]. Although
polycrystalline ceramics has been considered to be opaque up to
now, it was experimentally proved that light can be transmitted
(diffuse transmission in case of alumina) after reducing residual
pores and sintering until high density. After that, purity, particle size,
and homogeneity of the starting material were well controlled, and
the sintering process based on the sintering theory was improved to
produce sintered body with a high purity and high density, in which
the microstructure of the ceramics was controlled. Many studies on
synthesis of various translucent ceramics have been conducted under
such technical background, and some of them were applied in
practical applications such as Gd2O2S:Pr and (YGd)2O3:Eu as
scintillators for X‐ray CT (computed tomography), Ce:YAG ceramic
phosphors for whitening the GaN‐based blue‐violet LED (light
emitted diode), and LD (laser diode), and so on. But, these materials
are also not transparent, and they are just translucent quality. There
are many scattering sources in these translucent ceramics.
However, the translucent ceramics developed in the past only
showed “translucency or transparency” in appearance only when the
sample is thin, and there were almost no ceramics with high optical
quality. Very few studies have been reported about the optical
constants of transparent ceramics that have been successfully
synthesized. In the previous reports up to now, since the optical
properties of ceramics with grain boundaries are significantly
inferior to those of single crystals, only photographs of sample with
small thickness are shown in their reports to convince that their
ceramics apparently have high optical quality.
Transmittance curves of translucent alumina ceramics prepared by
hot pressed process and by normal pressure sintering are shown in
Figure 1.4 together with the transmittance curve of Sapphire single
crystal as a reference. In the case of alumina whose crystal structure
belongs to hexagonal system, even the thickness of samples is as thin
as 1 mm, their transmittances are very different to each other. This
means that there will be a significant difference in transmittance
when the thickness becomes larger. Optical loss is an important
factor for knowing the transparency of the material. Even for
materials with cubic crystal system such as MgO and Spinel
(MgAl2O4), the optical loss of these transparent ceramics is
remarkably larger than that of their single crystal counterparts. The
optical performance of transparent ceramics was very poor in the
material synthesis technology before laser ceramics was reported,
and therefore, industrial utilization of translucent ceramics was
extremely limited.
Another random document with
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 “Oh, I’m on the cross.” He knew that she was “pattering the flash”
for being in thievery; but he answered solemnly:
“Your mother is on the Cross, too, Molly.”
“Poor old thing! I’m sorry for her, but it don’t do her no good for me
to hang there with her.”
He entreated her to go home, and promised that the judge would
free her at his request, but Molly was honest enough to say:
“It wouldn’t work, Mister RoBards. I ain’t built for that life. I’ve
outgrowed it.”
He spoke to the judge, who sent her to the Magdalen Home
instead of to Sing Sing.
But the odor of sanctity was as stifling to Molly’s quivering nostrils
as the smell of new-mown hay, and she broke loose from pious
restraint and returned to her chosen career. She joined destinies with
a young crossman. As she would have put it in her new language,
she became the file of a gonof who was caught by a nab while
frisking a fat of his fawney, his dummy, and his gold thimble. Molly
went on a bender when her chuck was jugged, and a star took her
back to the Magdalen Home.
And of this it seemed to RoBards better to leave Mrs. Lasher in
ignorance than to certify the ghastly truth. He had trouble enough in
store for him within his own precincts.
War, for one thing, shook the nation. President Polk called for men
and money to confirm the annexation of the Texas Republic and to
suppress the Mexican Republic.
With a wife and children to support and the heritage of bills from
his father-in-law to pay, RoBards felt that patriotism was a luxury
beyond his means. But Harry Chalender went out with the first
troops, and by various illegitimate devices managed to worm himself
into the very forefront of danger.
Other sons of important families bribed their way to the zone of
death and won glory or death or both at Cerro Gordo, Chapultepec
and Churubusco. New York had a good laugh over the capture of
General Santa Ana’s wooden leg and the return of the troops was a
glorious holiday.
Harry Chalender had been the second man to enter the gates of
Mexico City and he marched home with “Captain” in front of his
name and his arm in a graceful sling.
When he met Patty he said: “Thank the Lord the Greasers left me
one wing to throw round you.”
He hugged her hard and kissed her, and then wrung the hand of
RoBards, who could hardly attack a wounded hero, or deny him
some luxury after a hard campaign. RoBards saw with dread that his
wife had grown fifteen years younger under the magic of her old
lover’s salute; her cheek was stained with a blush of girlish
confusion.
That night as she dressed for a ball in honor of the soldiers, Patty
begged her husband once more to lend a hand at pulling her corset
laces. When he refused sulkily, she laughed and kissed him with that
long-lost pride in his long-dormant jealousy. But her amusement cost
him dear, and his youth was not restored by hers.
For months his heart seemed to be skewered and toasted like the
meat on the turning spit in the restaurant windows.
And then the word California assumed a vast importance, like a
trumpet call on a stilly afternoon. It advertised a neglected strip of
territory of which Uncle Sam had just relieved the prostrate Mexico.
People said that it was built upon a solid ledge of gold. Much as
RoBards would have liked to be rich, he could not shake off his
chains.
But Harry Chalender joined the Argonauts. His finances were in
need of some heaven-sent bonanza, and he had no scruples against
leaving his creditors in the lurch.
When he called to pay his farewells RoBards chanced to be at
home. He waited with smoldering wrath to resent any effort to salute
Patty’s cheek. The returned soldier had perhaps some license, but
the outbound gold-seeker could be knocked down or kicked on his
way if he presumed.
 The always unexpectable Chalender stupefied him by fastening
his eyes not on Patty, but on Immy, and by daring to say:
“You’re just the age, Immy, just the image of your mother when I
first asked her to marry me. The first nugget of gold I find in
California I’ll bring back for our wedding ring.”
This frivolity wrought devastation in RoBards’ soul. It wakened him
for the first time to the fact that his little daughter had stealthily
become a woman. He blenched to see on her cheek the blush that
had returned of late to Patty’s, to see in her eyes a light of enamored
maturity. She was formed for love and ready for it, nubile, capable of
maternity, tempting, tempted.
The shock of discovery filled RoBards with disgust of himself. He
felt faint, and averting his gaze from his daughter, turned to her
mother to see how the blow struck her. Patty had not been so
unaware of Immy’s advance. But her shock was one of jealousy and
of terror at the realization that she was on the way to
grandmotherhood.
RoBards was so hurt for her in her dismay that he could have
sprung at Chalender and beaten him to the floor, crying, “How dare
you cease to flirt with my beautiful wife?”
But this was quite too impossible an impulse to retain for a
moment in his revolted soul. He stood inept and smirked with Patty
and murmured, “Good-by! Good luck!”
They were both pale and distraught when Chalender had gone.
But Immy was rosy and intent.
 CHAPTER XXXI

SOMETHING more precious than gold came to light in 1846,

something of more moment to human history than a dozen Mexican
wars—a cure for pain.
It came divinely opportune to Patty’s need, for her next child was
about to tear its way into the world through her flesh suffering from
old lacerations, and she prophesied that she would die of agony and
take back with her into oblivion the boy or girl or both or whatever it
was or they were that she was helplessly manufacturing.
And just then there came to RoBards a letter from a Boston client
stating that a dentist named Morton had discovered a gas that
enabled him to extract a tooth without distress; another surgeon had
removed a tumor from a patient made indifferent with ether; and that
the long deferred godsend would make childbirth peaceable. Patty
sang hosannas to the new worker of miracles.
“1846 is a greater year than 1776—or 1492. That man Morton is a
bigger man than Columbus and there should be a holiday in his
honor. What did the discoverer of America, or the inventor of the
telegraph or anything else, do for the world to compare with the
angel of mercy who put a stop to pain? The Declaration of
Independence!—Independence from what?—taxes and things. But
pain—think of independence from pain! Nothing else counts when
something aches. And the only real happiness is to hurt and get over
it.”
She repeated her enthusiasm to Dr. Chirnside when he happened
in on his pastoral rounds. To her dismay the old clergyman was not
elated, but horrified.
Dr. Chirnside, who opposed everything new as an atheism,
everything amusing as a sin, declared that God decreed pain for his
own inscrutable purposes in his own infinite love. Since Holy Writ
had spoken of a woman crying aloud in travail it would be a sacrilege
to deny her that privilege. The kindly old soul would have crucified a
multitude for the sake of a metaphor. He had in his earlier days
preached a sermon against railroads because God would have
mentioned them to Moses or somebody if he had approved of having
his creatures hurled through space at the diabolic speed of twenty
miles an hour. He had denounced bowling alleys for the same
reason, and also because they were fashionable and more crowded
than his own pews.
RoBards having seen operations where the patient had to be
clamped to a board and gagged for the sake of the neighbors’ ears,
could not believe that this was a pleasant spectacle to any
respectable deity.
He almost came to a break with Dr. Chirnside, who seemed to see
nothing incongruous in calling that divine which men called inhuman.
All of the learned men called “doctors,” whether of divinity,
medicine, law, philosophy, or what-not, seemed to fight everything
new however helpful. Martyrdom awaited the reformer and the
discoverer whether in religion, astronomy, geography, chemistry,
geology, anything.
The names of well-meaning gentlemen like Darwin, Huxley,
Tyndall had recently been howled at with an irate disgust not shown
toward murderers and thieves.
For the next twenty years a war would be waged upon the pain-
killers, and the names of Morton, Jackson, and Wells would inspire
immediate quarrel. Each had his retainers in the contest for what
some called the “honor” of discovering the placid realm of
anæsthesia; and what some called the “sacrilege” of its discovery.
It was written in the sibylline books of history as yet undisclosed
that Wells should be finally humbled to insanity and suicide; and that
Morton, after years of vain effort to get recognition, should retire to a
farm, where he would die from the shock of reading a denial of his
“pretensions.” They would put on his tombstone the legend: “By
whom pain in surgery was averted and annulled; before whom, in all
time, surgery was agony since whom science has had control of
pain.” Yet one’s own epitaph is a little late, however flattering.
RoBards shared Patty’s reverence for the Prometheus who had
snatched from heaven the anodyne to the earth’s worst curse. He
made sure that she should have the advantage of the cloud of
merciful oblivion when she went down into the dark of her last
childbed.
Her final baby was born “still,” as they say; but Patty also was still
during the ordeal. That was no little blessing. RoBards was spared
the hell of listening in helplessness to such moans as Patty had
hitherto uttered when her hour had come upon her unawares.
But the high hopes from this discovery were doomed to sink, for
man seems never to get quite free from his primeval evils, and
RoBards was to find that the God or the devil of pain had not yet
been baffled by man’s puny inventions.
Longing for opportunities to exploit the suppressed braveries in his
soul, RoBards found nothing to do but run to fires. There were
enough of these and the flames fell alike upon the just and the
unjust. Christ Church in Ann Street went up in blazes; the Bowery
Theatre burned down for the fourth time; a sugar house in Duane
Street was next, two men being killed and RoBards badly bruised by
a tumbling wall. The stables of Kipp and Brown were consumed with
over a hundred screaming horses; the omnibus stables of the
Murphys roasted to death a hundred and fifty horses, and took with
them two churches, a parsonage, and a school. While this fire raged,
another broke out in Broome Street, another in Thirty-fifth Street and
another in Seventeenth. The Park Theatre was burned for only the
second time in its fifty years of life; but it stayed burned.
And then Patty succeeded in persuading her husband to resign
from the volunteers and remove his boots and helmet from the
basket under the bed.
This was the knell of his youth and he felt that he had been put out
to grass like an old fire horse, but his heart leaped for years after
when some old brazen-mouthed bell gave tongue. He left it to
others, however, to take out the engine and chase the sparks.
He had come to the port of slippered evenings, but monotony was
not yet his portion. For there were domestic fire bells now.
Patty and Immy were mutual combustibles. They had reached the
ages when the mother forgets her own rebellious youth as
completely as if she had drunk Lethe water; and when the daughter
demands liberty for herself and imposes fetters on her elders.
Patty developed the strictest standards for Immy and was amazed
at the girl’s indifference to her mother’s standards. All of Patty’s
quondam audacities in dress and deportment were remembered as
conformities to strict convention. Immy’s audacities were regarded
as downright indecencies.
Immy, for her part, was outraged at the slightest hint of
youthfulness in her mother. With her own shoulders gleaming and
her young breast brimming at the full beaker of her dress, Immy
would rebuke her mother for wearing what they called a “half-high.”
Both powdered and painted and were mutually horrified. Immy used
the perilous liquid rouge and Patty the cochineal leaves, and each
thought the other unpardonable—and what was worse, discoverable.
Breathless with her own wild gallopades in the polka and dizzy
from waltzing in the desperate clench of some young rake, Immy
would glare at her mother for twirling about the room with a gouty old
judge holding her elbow-tips; or for laughing too loudly at a joke that
her mother should never have understood.
Finally, Patty had recourse to authority and told her husband that
the city was too wicked for the child. She—even Patty—who had
once bidden New York good-by with tears, denounced it now in
terms borrowed from Dr. Chirnside’s tirades.
Immy was mutinous and sullen. She refused to leave and
threatened to run off with any one of a half dozen beaux, none of
whom her parents could endure.
This deadlock was ended by aid from a dreadful quarter. By a
strange repetition of events, the cholera, which had driven Patty into
RoBards’ arms and into the country with him—the cholera which had
never been seen again and for whose destruction the Croton Water
party had taken full glory—the cholera came again.
It began in the pus-pocket of the Points and drained them with
death; then swept the town. Once more there was a northward
hegira. Once more the schoolhouses were hospitals and a thousand
poor sufferers died in black agony on the benches where children
had conned their Webster’s spelling books. Five thousand lives the
cholera took before it went its mysterious way.
Coming of a little bolder generation, Immy was not so panic-
stricken as her mother had been. But since all her friends deserted
the town, she saw no reason for tarrying.
The country was not so dull as she had feared. The air was spicy
with romance; fauns danced in the glades and sat on the stone
fences to pipe their unspeakable tunes; nymphs laughed in the
brooks, and dryads commended the trees.
The railroads made it easy for young bucks to run out on a train
farther in an hour or two than they could have ridden in a day in the
good old horseback times. A fashion for building handsome country
places was encouraged by the cholera scare. White Plains began to
grow in elegance and Robbin’s Mills changed its homely name to
Kensico, after an old Indian chief.
Before many days Immy was busier than in town. Young men and
girls made the quiet yard resound with laughter. The tulip trees
learned to welcome and to shelter sentimental couples. Their great
branches accepted rope swings, and petticoats went foaming toward
the clouds while their wearers shrieked and fell back into the arms of
pushing young men.
Picnics filled the groves with mirth, dances called gay cliques to
lamplit parlors and to moonlit porches. Tuliptree Farm began to
resemble some much frequented roadside tavern. It was as gay as
Cato’s once had been outside New York.
Immy seemed to gather lovers as a bright candle summons foolish
moths. Patty and her husband were swiftly pushed back upon a shelf
of old age whence they watched, incredulous, and unremembering,
the very same activities with which they had amazed their own
parents.
Two lovers gradually crowded the rest aside. The more attractive
to Immy’s parents was a big brave youth named Halleck. He had
joined the old Twenty-seventh Regiment, recently reorganized as the
Seventh, just in time to be called out in the Astor Place riots.
The citizens had lain fairly quiet for a long while and had not
attacked a church or a minister or a theatre for nearly fifteen years.
But the arrival of the English actor Macready incensed the idolators
of Edwin Forrest and developed a civil war.
Young Halleck was with the Seventh when it marched down to
check the vast mob that overwhelmed the police, and drove back a
troop of cavalry whose horses were maddened by the cries and the
confinement. The populace roared down upon the old Seventh and
received three volleys before it returned to civil life.
This exploit in dramatic criticism cost the public thirty-four deaths
and an unknown number of wounds. The Seventh had a hundred
and forty-one casualties. Halleck had been shot with a pistol and
battered with paving stones. To RoBards the lawyer he was a civic
hero of the finest sort. The only thing Immy had against him was that
her parents recommended him so highly.
Love that will not be coerced turned in protest toward the youth
whom her parents most cordially detested, Dr. Chirnside’s son,
Ernest, a pallid young bigot, more pious than his father, and as cruel
as Cotton Mather. Patty wondered how any daughter of hers could
endure the milk-sop. But Immy cultivated him because of his very
contrast with her own hilarity.
His young pedantries, his fierce denunciations of the wickedness
of his companions, his solemn convictions that man was born lost in
Adam’s sin and could only be redeemed from eternal torment by
certain dogmas, fascinated Immy, who had overfed on dances and
flippancies.
 RoBards could not help witnessing from his library window the
development of this curious religious romance. Even when he
withdrew to his long writing table and made an honest effort to
escape the temptation to eavesdropping, he would be pursued by
the twangy sententiousness of Ernest and the silvery answers of
Immy. There was an old iron settee under his window and a
rosebush thereby and the young fanatics would sit there to debate
their souls.
It was a godlike privilege and distress to overhear such a
courtship. His daughter bewildered him. At times Immy was as wild
as a mænad. She danced, lied, decoyed, teased, accepted
caresses, deliberately invited wrestling matches for her kisses. She
rode wild horses and goaded them wilder. She would come home
with a shrieking cavalcade and set her foam-flecked steed at the
front fence, rather than wait for the gate to be opened.
Seeing Immy in amorous frenzies RoBards would be stricken with
fear of her and for her. He would wonder if Jud Lasher had not
somehow destroyed her innocence; if his invasion of her integrity
had not prepared her for corruption. How much of that tragedy did
she remember? Or had she forgotten it altogether?
He would shudder with the dread that Jud Lasher, who was lying
beneath his feet, might be wreaking a posthumous revenge,
completing his crime with macaberesque delight.
Then Immy’s mood would change utterly. She would repent her
youth as a curse, and meditate a religious career. There was a new
fashion for sending missionaries to Africa and she was tempted to
proselytize the jungle. Ernest rescued her at least from this. He told
her that she must make sure her own soul was saved before she
went out to save Zulus.
Sometimes RoBards, listening with his pen poised above an
unfinished word, would seem to understand her devotion to young
Chirnside, her acceptance of his intolerant tyranny and the insults he
heaped upon her as a wretch whom his God might have foredoomed
from past eternity to future eternity. He would talk of election and the
conviction of sin and of salvation.
 And Immy would drink it down.
At last there came an evening when young Chirnside called in
manifest exaltation. He led Immy to the settee beneath the library
window, and RoBards could not resist the opportunity to overhear
the business that was so important.
He went into his library and softly closed the door. He tiptoed to a
vantage point and listened.
Young Chirnside coughed and stammered and beat about the
bush for a maddening while before he came to his thesis, which was
that the Lord had told him to make Immy his wife. He had come to
beg her to listen to him and heaven. He had brought a little ring
along for the betrothal and—and—how about it? His combination of
sermon and proposal ended in a homeliness that proved his
sincerity. After all that exordium, the point was, How about it?
That was what RoBards wanted to know. He waited as
breathlessly as his prospective son-in-law. Immy did not speak for a
terrible while. And then she sighed deeply, and rather moaned than
said:
“Ernest, I am honored beyond my dreams by what you have said.
To be the wife of so good a man as you would be heaven. But am I
good enough for you?”
“Immy!” Chirnside gasped, “you’re not going to tell me you’ve been
wicked!”
“I’ve been wicked enough, but not very wicked—considering. The
thing I must tell you about is—it’s terribly hard to tell you, dear. But
you ought to know, you have a right to know. And when you know,
you may not think—you may not think—you may feel that you
wouldn’t care to marry me. I wouldn’t blame you—I’d understand,
dear—but——”
“Tell me! In heaven’s name, tell me!”
RoBards was stabbed with a sudden knowledge of what tortured
her thought. He wanted to cry out to her, “Don’t tell! Don’t speak! I
forbid you!”
 But that would have betrayed his contemptible position as
eavesdropper. And, after all, what right had he to rebuke such
honesty? She knew her soul. She was inspired perhaps with the
uncanny wisdom of young lovers.
The wish to confess—though “confess” was not the word for her
guiltless martyrdom—was a proof of her nobility. It would be a test of
this young saint’s mettle. If he shrank from her, it would rescue her
from a pigeon-hearted recreant. If he loved her all the more for her
mischance, he would prove himself better than he seemed, more
Christlike than he looked.
And so RoBards, guessing what blighting knowledge Immy was
about to unfold, stood in the dark and listened. Tears of pity for her
scalded his clenched eyelids and dripped bitter into his quivering
mouth.
Unseeing and unseen, he heard his child murmuring her little
tragedy to the awesmitten boy at her side. She seemed as pitifully
beautiful as some white young leper whispering through a rag,
“Unclean!”
What would this pious youth think now of the God that put his love
and this girl to such a test? Would he howl blasphemies at heaven?
Would he cower away from the accursed woman or would he fling
his arms about her and mystically heal her by the very divinity of his
yearning?
RoBards could almost believe that Jud Lasher down there in the
walls was also quickened with suspense. His term in hell might
depend on this far-off consequence of his deed.
 CHAPTER XXXII

A STRANGE thing, a word: and stranger, the terror of it. Stranger

still, the things everybody knows that must never be named.
Strangest of all, that the mind sees most vividly what is not
mentioned, what cannot be told.
Immy, for all her rebellious modernness and impatience of old-
fashioned pruderies, was a slave of the word.
And now she must make clear to a young man of even greater
nicety than she, an adventure it would have sobered a physician to
describe to another. She gasped and groped and filled her story with
the pervividness of eloquent silences:
“It was when I was a little girl—a very little girl. There was a big
terrible boy—a young man, rather—who lived down the road—ugly
and horrible as a hyena. And one day—when Papa was gone—and I
was playing—he came along and he spoke to me with a grin and a—
a funny look in his eyes. And he took hold of me—it was like a
snake! and I tried to break loose—and my little brother fought him.
But he knocked and kicked Keith down—and took me up and carried
me away. I fought and screamed but he put his hand over my mouth
and almost smothered me—and kept on running—then—then——”
Then there was a hush so deep that RoBards felt he could hear
his tears where they struck the carpet under his feet. His eyelids
were locked in woe, but he seemed to see what she thought of; he
seemed to see the frightened eyes of Ernest Chirnside trying not to
understand.
Immy went on:
“Then Jud Lasher heard Papa coming and he ran. Papa caught
him and beat him almost to death—but it was too late to save me. I
didn’t understand much, then. But now—! Papa made me promise
never to speak of it; but you have a higher right than anybody, Ernest
—that is, if you still—unless you—oh, tell me!—speak!—say
something!”
The boy spoke with an unimaginable wolfishness in his throat:
“Where is the man?—where is that man?”
“I don’t know. I never saw him after that—oh, yes, he came back
again once. But Papa was watching and saved me from him—and
after that I never heard of him. Yes, I did hear someone say he went
to sea.”
Another hush and then Ernest’s voice, pinched with emotion:
“I believe if I could find that villain I could almost kill him. My soul is
full of murder. God forgive me!”
He thought of his own soul first.
Poor Immy suffered the desolation of a girl who finds her hero
common clay; her saint a prig. But with apology she said:
“I ought never to have told you.”
He dazed her by his reply:
“Oh, I won’t tell anybody; never fear! But don’t tell me any more
just now. I must think it out.”
He wanted to think!—at a time when thinking was poltroon; when
only feeling and impulsive action were decent! Immy waited while he
thought. At length he said:
“If that man still lives he’ll come back again!”
“No! no!”
“He’ll come back and get you.”
“You wouldn’t let him, would you?”
“You belong to him, in a way. It is the Lord’s will.”
He could say that and believe it! The young zealot could worship a
god who could doom, ten thousand years before its birth, a child to a
thousand, thousand years of fiery torment because of an Adam
likewise doomed to his disobedience.
 The young man’s own agony had benumbed him perhaps, but
RoBards could have leapt from the window and strangled him as a
more loathsome, a clammier reptile than Jud Lasher. But he, too,
was numb with astonishment.
Then the boy went human all at once and began to sob, to wail,
“Oh, Immy, Immy! my poor Immy!”
RoBards stepped forward to the window in a rush of happiness,
and saw Immy put out her hands to her lover. He pushed them away
and rose and moved blindly across the grass. But there was a heavy
dew and he stepped back to the walk to keep his feet from getting
wet.
He stumbled along the path to the gate and leaned there a
moment, sobbing. Then he swung it wide as he ran out to where his
horse was tied. And the gate beat back and forth, creaking, like a
rusty heart.
RoBards stood gazing down at his daughter, eerily beautiful in the
moonlight through the rose leaves. He saw her dim hands twitching
each at the other. Then they fell still in her lap and she sat as a worn-
out farm-wife sits whose back is broken with overlong grubbing in the
soil and with too heavy a load home.
For a long time he sorrowed over her, then he went stealthily
across his library into the hall, and out to the porch where he looked
at the night a moment. He discovered Immy as if by accident, and
exclaimed, “Who’s that?”
“It’s only me, Papa, only me!”
“Only you? Why you’re all there is. You’re the most precious thing
on earth.”
He put his arm about her, but she sprang to her feet and snapped
at him:
“Don’t! If you please, Papa, don’t touch me. I—I’m not fit to be
touched.”
She stood away from him, bracing herself with a kind of pride.
Then she broke into a maudlin giggle, such as RoBards had heard
from the besotted girls in the Five Points. And she walked into the
house.
He followed her, and knocked on her door. But she would not
answer, and when he tried it, it was locked.
 CHAPTER XXXIII

THE next morning RoBards heard her voice again. It was loud and
rough, drowning the angry voice of her brother, Keith. She was
saying:
“I was a fool to tell him! And I was a fool to tell you I told him!”
“I’ll beat him to death when I find him, that’s all I’ll do!” Keith
roared, with his new bass voice.
“If you ever touch him or mention my name to him—or his name to
me,” Immy stormed, “I’ll—I’ll kill—I’ll kill myself. Do you understand?”
“Aw, Immy, Immy!” Keith pleaded with wonderful pity in his voice.
Then she wept, long, piteously, in stabbing sobs that tore the heart of
her father.
He knew that she was in her brother’s arms, for he could hear his
voice deep with sympathy. But RoBards dared not make a third
there. It was no place for a father.
He went to his library and stood staring at the marble hearthstone.
Somewhere down there was what was left of Jud Lasher. He had not
been destroyed utterly, for he was still abroad like a fiend, wreaking
cruel harm.
Immy spoke and RoBards was startled, for he had not heard her
come in:
“Papa.”
“Yes, my darling!”
“Do you think Jud Lasher will ever come back?”
“I know he won’t.”
“How do you know?”
“Oh, I just feel sure. He’d never dare come back.”
 “If he did would I belong to him?”
“Would a lamb belong to a sheep-killing dog that mangled it?”
“That’s so. Thank you, Papa.” And she was gone.
A boy on a horse brought her a note that afternoon. She told no
one its contents and when Patty asked who sent it, Immy did not
answer. RoBards was sure it came from Ernest Chirnside, for the
youth never appeared. But RoBards felt no right to ask.
Somehow he felt that there was no place for him as a father in
Immy’s after-conduct. She returned to her wildness, like a deer that
has broken back to the woods and will not be coaxed in again.
How could he blame her? What solemn monition could he parrot
to a soul that had had such an experience with honesty, such a
contact with virtue?
Young Chirnside never came to the house. But he was the only
youth in the countryside, it seemed, that kept away. Patty tried to
curb Immy’s frantic hilarities, but she had such insolence for her
pains that she was stricken helpless.
Then Immy decided that the country was dull. The young men
went back to town, or to their various colleges. Keith went to
Columbia College, which was still in Park Place, though plans were
afoot for moving it out into the more salubrious rural district of Fiftieth
Street and Madison Avenue.
Keith met Chirnside on the campus, but he could not force a
quarrel without dragging Immy’s name into it. So he let slip the
opportunity for punishment, as his father had let slip the occasion for
punishing Chalender. Father and son were curiously alike in their
passion for secrets.
Keith had little interest in the classic studies that made up most of
the curriculum. He could not endure Latin and the only thing he
found tolerable in Cæsar was the description of the bridge that
baffled the other students with its difficulties.
He was an engineer by nature. He had never recovered from his
ambition to be an hydraulic savior of the city. And it looked as if the
town would soon need another redemption.
The citizens had treated the Croton as a toy at first. The hydrants
were free and the waste was ruinous. This blessing, like the
heavenly manna, became contemptible with familiarity. Children
made a pastime of sprinkling the yards and the streets. The habit of
bathing grew until many were soaking their hides every day. During
the winter the householders let the water run all day and all night
through the open faucets, to prevent the pipes from freezing. There
were twelve thousand people, too, who had water in their houses!
Already in 1846 the Commissioners had begun to talk of a costly
new reservoir as a necessity. For thirteen days that year the supply
had to be shut off while the aqueduct was inspected and leaks
repaired. What if another great fire had started?
In 1849 the Water Commissioners were dismissed and the Croton
Aqueduct Department entrusted with the priesthood of the river god
and his elongated temple.
So Keith looked forward to the time when he should be needed by
New York and by other cities. And he studied hard. But he played
hard, too. The students were a lawless set, and drunkenness and
religious infidelity were rival methods for distressing their teachers.
Up at New Haven the Yale boys in a certain class, feeling
themselves wronged by a certain professor, had disguised
themselves as Indians and with long knives whittled all the study
benches into shavings while the terrified instructor cowered on his
throne and watched.
Vice of every sort seemed to be the chief study of such of the
students as were not aiming at the ministry. As one of the college
graduates wrote:
“Hot suppers, midnight carousals were too frequent with us and
sowed the seed of a vice that in a few years carried off a fearful
proportion of our members to an untimely grave.”
There was grave anxiety for the morals of the whole nation. The
city was growing too fast. By 1850 it had passed the half-million
mark! The churches were not numerous enough to hold a quarter of
the population, yet most of them were sparsely attended.
The American home was collapsing. Dr. Chirnside preached on
the exalted cost of living, and stated that church weddings were on
the decrease. The hotel was ruining the family. Rents were so
exorbitant, servants so scarce and incompetent, that people were
giving up the domesticity of the good old days.
Business detained the husband downtown, and he took his
midday dinner at Sweeny’s or Delmonico’s, where he could have
poultry or sirloin steak for a shilling and sixpence. And his wife and
daughters, unwilling to eat alone, went to Weller’s or Taylor’s and
had a fricandeau, an ice, or a meringue. Ladies’ saloons were
numerous and magnificent and wives could buy ready-made meals
there; so they forgot how to cook. The care of children no longer
concerned them. Women were losing all the retiring charm that had
hitherto given them their divine power over men.
The clergy bewailed the approaching collapse of a nation that had
forgotten God—or had never remembered him. There was a
movement afoot to amend the Constitution with an acknowledgment
of the Deity and “take the stain of atheism from that all-important
document.”
These were the Sunday thoughts.
In contrast were the Fourth of July thoughts, when the country
sang its own hallelujahs and, like another deity, contentedly
meditated its own perfections. On these occasions every American
man was better than any foreigner, and American women were all
saints.
And there were the Election Day moods, when the country split up
into parties for a few weeks, and played tennis with mutual charges
of corruption, thievery, treason. Then there was Christmas, when
everybody loved everybody; and New Year’s Day, when everybody
called on everybody and got a little drunk on good wishes and the
toasts that went with them.