Zanotto, Edgar Dutra

English

Lehigh University: Lehigh Preserve

Lehigh University 
Lehigh Preserve 
US-Japan Winter School Semester Length Glass Courses and Glass Schools 
Winter 1-1-2008 
Lecture 9, Part 4: Nucleation, growth and transparent glass-
ceramics - Transparent glass ceramics 
Edgar Dutra Zanotto 
Federal University of Sao Carlos, Brazil 
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Zanotto, Edgar Dutra, "Lecture 9, Part 4: Nucleation, growth and transparent glass-ceramics - Transparent 
glass ceramics" (2008). US-Japan Winter School. 27. 
https://preserve.lehigh.edu/imi-tll-courses-usjapanwinterschool/27 
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Transparent glass - ceramics
Edgar D. Zanotto
Vitreous Materials Lab
Federal University of São Carlos, Brazil
www.lamav.ufscar.br
Presented at the IMI-NFG US-Japan Winter School , Jan 14, 2008 and 
Reproduced by the International Materials Institute for Glass for use by the 
glass research community;  Available at: www.lehigh.edu/imi
Vitreous Materials Lab – www.lamav.ufscar.br
Vitreous Materials Lab – www.lamav.ufscar.br
OUTLINE
 Introduction to glass-ceramics
 Brief literature review on TGC
 Potential applications of TGC
 Conditions for transparency
 Mature TGC – nanocrystals
 New TGC:                             Properties
 Sintered aluminate GC      Opt & Mech
 IR transmitting CG             Opt & Mech
 Ce: YAG GC for lighting Opt
 Laser crystallized GC        Opt
 PTR GC Opt & Mech
 LGHC GC                            Opt & Mech
 Surprise....
 Conclusions
Vitreous Materials Lab – www.lamav.ufscar.br
Glass-ceramic synthesis
 Entropy vs. T plot
 Heat-treatment plot
Vitreous Materials Lab – www.lamav.ufscar.br
INTRODUCTION
GLASS-CERAMICS
controlled
volume
crystallization
null porosity
designed
microstructures:
size & shape & 
uniform grain size, 
% crystallinity, 
etc. 
reproducible 
properties
optical transparency
high thermal and 
chemical stability
tougher 
than glasses
interesting electrical
properties
Vitreous Materials Lab – www.lamav.ufscar.br
INTRODUCTION
Applications of transparent glass-ceramics
Cooking ware
Fire resistant plates
Security windows 
Telescope mirrors…
saturable absorber media; illumination devices using IR; 
heat-resistant materials that absorb UV,
that reflect infrared and are transparent to visible light; 
that absorb UV and fluoresce in red/IR;
second harmonics generating; 
substrates for LCD devices; optical amplifiers for up-conver; 
substrates for arrayed waveguide grating (AWG);
radiation sources of lamps; Laser pumps; Laser media; 
Materials for precision photolithography; ring laser 
gyroscopes; solar collectors; printed optical circuits; etc. 
Optical
(potential)
Thermo-mechanical
Vitreous Materials Lab – www.lamav.ufscar.br
The inventor of GLASS-CERAMICS
S.D. Stookey discovering GC 
in the middle 1950s
Vitreous Materials Lab – www.lamav.ufscar.br
LITERATURE REVIEW- PIONEERS OF TGC
STOOKEY,S.D. 
V Int. Congress on Glass, pp. V/1-8 1959
BORRELLI, N.F. ELECTRO-OPTIC EFFECT IN 
TRANSPARENT NIOBATE GLASS-CERAMIC SYSTEMS
Journal of Applied Physics, 38 (11): 4243 1967
BEALL, G.H.; DUKE, D.A.
TRANSPARENT GLASS-CERAMICS
Journal of Materials Science, 4 (4): 340 1969
Recent articles in the next slide
Vitreous Materials Lab – www.lamav.ufscar.br
LITERATURE REVIEW (TGC title )
 YEAR 112 ISI papers
 1967 1 
 1969 2
 1978 3
 1982 3
 1984 2
 1985 2
 1986 5
 1987 3
 1988 2
 1993 2
 1994 2
 1995 4
 1996 5
 1998 8
 1999 5
 2000 7
 2001 9
 2002 11
 2003 5
 2004 20
 2005 5
 2006 5
Derwent II
~90 patents
Corning
Schott
Nippon
Others
0
5
10
15
20
25
1960 1980 2000 2020
30 years
Vitreous Materials Lab – www.lamav.ufscar.br
Crystalline phases in TGC
 Β−quartz ss
 Β-eucriptite
 Mullite
 Spinel
 Willemite
 Ghanite
 Forsterite
 β-BBO
 LiNbO3
 NaNbO3
 PbF2
 LaF3
 ZnO
 Etc.
Most TGC have
nanosize crystals &
small crystallized
volume fraction
(~ 50% or less)
Vitreous Materials Lab – www.lamav.ufscar.br
THEORY
Light attenuation atomic absorption (β)
scattering (S)
+ surface reflection (R)
2
2
1
1
))(exp()1(
⎟⎠
⎞⎜⎝
⎛
+
−=
+−−=
n
nR
xSRII o β
Reflection losses (%)
0
2
4
6
8
10
12
1 1.2 1.4 1.6 1.8 2
n
R
scattered lightIncident
light
reflected light
fluorescence
Transmitted
light
reflected light
Io
Vitreous Materials Lab – www.lamav.ufscar.br
crystal size << wavelength of light
nglass ≅ ncrystal
Basic requirements
Transparent glass-ceramics
Conditions for transparency
low birefringence
Vitreous Materials Lab – www.lamav.ufscar.br
Examples of 
commercially mature
TGC
Vitreous Materials Lab – www.lamav.ufscar.br
Corning’s VISION
Vitreous Materials Lab – www.lamav.ufscar.br
VLT 8.2 m Zerodur mirror on its way to Paranal
Observatory, Chile, Dec. 97/ Schott
Vitreous Materials Lab – www.lamav.ufscar.br
ROBAX – Schott
NEOCERAM – NIPPON
KERAGLASS- Corning/ St. Gobain CERAN- Schott
 .
Vitreous Materials Lab – www.lamav.ufscar.br
NEW
TRANSPARENT GC
(yet on the development stage)
Vitreous Materials Lab – www.lamav.ufscar.br
Bulk glasses and ultrahard nanoceramics based on alumina and rare-earth 
oxides by A. Rosenflanz et al. Nature 430, 761 - 764 (August 2004).
a, b: no dopants; c 5wt% Nd2O3; d 5wt% Eu2O3; e 5wt% Er2O3. 
All except b were hot-pressed at 905 °C at 34 MPa for 360 s. 
Material b was hot-pressed for 1,200 s inducing partial crystallization, 
giving the opalescent appearance. 
 
2 mm tick
50-90% Al2O3
Nd Eu Er
IR transparent
Vitreous Materials Lab – www.lamav.ufscar.br
High alumina glasses and GC
.
Hardness against Al2O3 
content. High-alumina 
glasses and glass-
ceramics surpass other 
oxides : BeO, MgO, 
Y2O3, ZrO2, TiO2, 
Y3Al5O12, Corning 9606 
and 9608 GC, and are 
comparable to pure  a-
Al2O3 and b-Si3N4. 
These compositions 
were crystallized directly 
from the melt during 
slow cooling.
Ultra hard
Vitreous Materials Lab – www.lamav.ufscar.br
IR transmitting chalco-sulfide glass-
ceramics
Ge-Sb-S-Cs-Cl glass with
CsCl crystals
X. Zhang et. al. , J. Non-
crystalline Solids 337 (2004) 
130
Lab. glasses and ceramics, 
University of Rennes, 
France
Vitreous Materials Lab – www.lamav.ufscar.br
Typical microstructure of IR glass-ceramics
Zhang et. al.
100nm CsCl
crystals
Vitreous Materials Lab – www.lamav.ufscar.br
IR transmission versus crystallinity
0
10
20
30
40
50
60
70
80
90
100
0.5 1.0 1.5 2.0 2.5 3.0
Wavelength (µm)
T
r
a
n
s
m
i
s
s
i
o
n
 
(
%
)
0 hour
3 H
7 H
23 H
31 H
73 H
144 H
246 H
Zhang et. al.
0
10
20
30
40
50
60
70
80
90
100
0 1 2 3 4 5 6 7 8 9 10 11 12
Wavelength (µm)
T
r
a
n
s
m
i
s
s
i
o
n
 
(
%
)
sample A
sample B
sample A sample B
Vitreous Materials Lab – www.lamav.ufscar.brJacques Lucas
Night vision
Vitreous Materials Lab – www.lamav.ufscar.br
Resistance to fracture propagation
10 µm 10 µm
Zhang et. al.
GC Glass
Vitreous Materials Lab – www.lamav.ufscar.br
Glass-Ceramic for Solid State 
Lighting - White LED
Ce:YAG-GC
Setsuhisa Tanabe
Kyoto University, Kyoto, Japan
Shunsuke Fujita, Akihiko Sakamoto, Shigeru Yamamoto
Nippon Electric Glass, Otsu, Japan
Presented at the ACerS meeting, Baltimore, April 2005
Vitreous Materials Lab – www.lamav.ufscar.br
Solid-State Lighting (future)
Promise of LEDs for illumination
Efficiency Life
Incadescent Light Bulb     16 lm / W 1000h
Fluorescent Lamp 80 lm / W 10,000h
Today’s white LED 60 lm / W 20,000h
Future white LED 200 lm / W 100,000h
Efficiently bright, broad spectrum, long-lifetime…
S. Tanabe et al.
Vitreous Materials Lab – www.lamav.ufscar.br
As-made Cerammed
SEM 0
1000
2000
3000
4000
5000
6000
7000
10 20 30 40 50 60
2θ 　/ 　°
i
n
t
e
n
s
i
t
y
　
/
　
c
p
s
XRD
YAG
60% 
Crystalinity    
(wt％)
YAG
20μm
1cm
YAG-GC from glass- microstructure
S. Tanabe et al.
Vitreous Materials Lab – www.lamav.ufscar.br
380 480 580 680 780
wavelength　／　nm
i
n
t
e
n
s
i
t
y
／
a
r
b
.
u
n
i
t
Emission
ｔ = 0.5mm .Transmission
Moderate transmission of blue
Yellow fluorescence
a) Ce:YAG GC
a) b)
b) White light emission from Ce:YAG G.C.
10mm 10mm
White light
Excitation (460nm)it ti  
Transmission.i i Emissioni i
Ce:YAG G.C.. .
(540nm)
Vitreous Materials Lab – www.lamav.ufscar.br
Laser crystallization in Nagaoka
Takayuki Komatsu & collaborators
(Benino, Ihara, Fujiwara, et al.)
Department of Chemistry
Nagaoka University of Technology
Japan
Example: Appl. Phys. Lett., 82 (2003) 892, 83 (2003) 2796.
Vitreous Materials Lab – www.lamav.ufscar.br
Laser crystallization in glass
Rare-earth (Samarium) atom heat processing
1. CW Nd:YAG laser irradiation to Sm2O3 or Dy2O3 containing glasses
2. Absorption and non-radiative relaxation
Irradiated region is heated Crystallization 
○ Sm2O3-BaO-B2O3 → β-BaB2O4
○ Sm2O3-Bi2O3-B2O3 → SmxBi1-xBO3
○ Sm2O3-MoO3-B2O3 → β’-Sm2(MoO4)3
○ Sm2O3-K2O-P2O5 → KSm(PO3)4
Writing of nonlinear optical/ferroelectric crystal dots and lines
Polarization optical microscope
Sm2O3-Bi2O3-B2O3 glass
SmxBi1-xBO3 crystal
Power: 0.66W
Scanning speed: 10μm/s
Nagaoka
20,000 
J/cm2
Vitreous Materials Lab – www.lamav.ufscar.br
10Sm2O3.35Bi2O3.55B2O3 glass
Tg=474oC, Tx=574oC
Temp. < Tx
crystal
Refractive index change
Temp. >> Tx
50μm
0.6 W
0.66 W
0.9 W
0.8 W
SmxBi1-xBO3
J. Am. Ceram. Soc. 88 (2005) 989
Komatsu
Vitreous Materials Lab – www.lamav.ufscar.br
Laser crystallization in São Carlos
C. A. C. Feitosa, L. J. Q. Maia, A. L. Martinez, 
A. C. Hernandes, Valmor R. Mastelaro, 
IFQSC, 
University of
São Paulo, São 
Carlos, Brazil
Vitreous Materials Lab – www.lamav.ufscar.br
40BaO - 45B2O3 - 15 TiO2 (BBT)
Microstructures from two crystallization 
processes
BBT GC in resistive 
furnace at 620oC.
BBT glass after irradiation with CO2 
laser (λ= 10.6 μm) 4 min, 40 W/cm2.
= 10,000 J/cm2
Glass at  300oC (Tg = 580 oC) 
Mastelaro et. al.
Vitreous Materials Lab – www.lamav.ufscar.br
Surface crystallization of BBT glass
5 μm
20 μm
200 μm
10 20 30 40 50 60
Vidros 4% e 15%
# (006)
* (009)
* (006)
* (003)
# (006)
# (104) 15% de TiO2
4% de TiO2
 
* BaTi(BO3)2
# β-BBO
I
n
t
e
n
s
i
d
a
d
e
 
(
u
.
a
.
)
2 θ Graus
It is possible to produce
policrystalline lines. 
Details; crystals within the line
and diffraction pattern
Mastelaro et. al.
Vitreous Materials Lab – www.lamav.ufscar.br
Laser beam
Nd:YAG (λ = 1064 nm)
Second harmonic generation
SHG in partially crystallized BBT glass
Mastelaro et. al.
Vitreous Materials Lab – www.lamav.ufscar.br
PTR Glasses
Oxy fluor bromide glasses
 Composition
 Major: SiO2, Na2O, ZnO, Al2O3
 Minor: K2O, F, Br
 Dopants (~200 ppm): Ag, Ce, Sb, Sn
 Impurities ( < 2 ppm): transition metals
S.D. Stookey et al. (1954) – Corning, USA
L.B. Glebov et al.   (1990) - Vavilov SOI, Russia + Creol/ UCF, USA
Vitreous Materials Lab – www.lamav.ufscar.br
Ce3+
Ce4+
e-
hν
PTR glass is a F-Br sodium-zinc-aluminum-
silicate glass doped with Ag, Ce, Sn and Sb
Current technology at UCF/CREOL - optical quality PTR 
glasses with aperture up to 50 mm.
Vitreous Materials Lab – www.lamav.ufscar.br
Ce3+
Ce4+
e-
hν
Mechanism of photo-thermo-crystallization
Ce3+
Ce4+
e-
hν
Ag+ Ag0
UV
excitation
Photoionization
Valence change
Electron
Trapping
Valence change
Latent
Image
Ag0
Ag0
kT
Ag0
Ag0
Ag0
Ag0
Ag0
kT kT
kT kT
kT
Ag0 Ag0
Ag0 Ag0
Silver atoms
diffusion
Growth of Silver
nanocrystal
Na+ F -
Na+
Na+ F -F -
Na+Na+ F -
Na+F -F -
F -
kT
Na+
kT
Na+
kT
F -kT
Ag0 Ag0
Ag0 Ag0
Silver
nucleation
center
Sodium
fluoride
crystal
3D image (hologram) of object is transformed
to the phase pattern (refractive index variations)
caused by selective NaF crystal 
distribution in accordance with the UV 
intensity distribution in glass interior.
Vitreous Materials Lab – www.lamav.ufscar.br
PTRG (only the active ions are shown) 
Proposed mechanism of photo induced
crystallization .
Vitreous Materials Lab – www.lamav.ufscar.br
University of Central Florida
School of Optics - CREOL   Laboratory of Photo-Induced Processes Ce
3+
Ce4+
e-
hν
Absorption spectrum of photo-thermo-refractive glass
No detectable absorption in the range of 1 μm
Absorption of hydroxyl in the range of 4 μm
0
0.5
1
1.5
2
0 1000 2000 3000 4000
Wavelength, nm
A
b
s
o
r
p
t
i
o
n
,
 
c
m
-
1    COIL
Nd, Yb, Er
1-1.6 μm
        DF
3.6-4.2 μm
   HF
2.7 μm
Vitreous Materials Lab – www.lamav.ufscar.br
PTR glasses
Creol’s PTRG
Hologram
Corning’s Fotalite
Leon Glebov et. al.
S.D. Stookey et. al.
Vitreous Materials Lab – www.lamav.ufscar.br
LARGE GRAIN, HIGHLY CRYSTALLINE, HIGHLY 
TRANSPARENT GC
T. Berthier, V.M. Fokin, E.D. Zanotto
LaMav- Federal University São Carlos, Brazil
Vlad Fokin ThianaBerthier
Vitreous Materials Lab – www.lamav.ufscar.br
STRATEGY
New type of transparent glass-ceramic
Simultaneous compositional variation
small or large grain size high crystallized
volume fraction 
of solid solution crystals 
and glassy matrix
decreases Δn
Vitreous Materials Lab – www.lamav.ufscar.br
OPTICAL PROPERTIES
200 nm – 1100 nm
Estimated parameters (P1 and P2): P1 = (1-R)2
P2 = (β+S)
( )xPP
I
I
21
0
exp −=
Transmittance measured for different sample thicknesses
Crystal morphology
Grain size
Degree of crystallinity OM 
Transmission
Spectra
Vitreous Materials Lab – www.lamav.ufscar.br
MICROSTRUCTURES
The crystals are solid solutions: TA4+2xAE4-x[GF6O18] (0 ≤ x ≤ 1)
T = trace element
A = alkali
AE = alkaline earth
GF = Si, P, B
Their morphology can vary from
J, spherical   to V8, cubic
Vitreous Materials Lab – www.lamav.ufscar.br
TRANSMITTANCE
Distinct crystal shapes Different transmittances
Best transmittance                  Cubic crystals
V8, cubic 5-6 μm
J, spherical 7-8 μm
Morphology
crystal/crystal 
Interfaces are 
quite different for 
spherical and 
cubic crystals
Vitreous Materials Lab – www.lamav.ufscar.br
TRANSMITTANCE
Crystal size
Importance of
thermal history
* Same crystalline fraction
Affects P2
I(λ) dependence
glass J, spherical crystals, ~42% crystallized
Grain size
Vitreous Materials Lab – www.lamav.ufscar.br
TRANSMITTANCE
glass V8, cubic crystals  (3-5 μm)
Degree of crystallinity
Glass V8 & T6, maximum
transmission for ~ 95-
97% OM crystallinity
Vitreous Materials Lab – www.lamav.ufscar.br
Glass GC 97% crystallinity 50% crystallinity
The beasts! Transparency
of 4 mm thick specimens
Vitreous Materials Lab – www.lamav.ufscar.br
DISCUSSION
alkali content in 
crystals
30% > glassy matrix
EDS measurements
5 10 15 20 25 30 35
1.54
1.56
1.58
1.60
1.62
1.64
2
1
glass phase
crystal
n
Alkali oxide, wt%
0,0 0,2 0,4 0,6 0,8 1,0
10
12
14
16
18
C
A
,
 
a
t
%
α
 crystals
 glassy matrix
Vitreous Materials Lab – www.lamav.ufscar.br
DISCUSSION
Main reasons for improved
transparency in these new TGC
Simultaneous variations of the
glass-matrix and s/s-crystal compositions
during crystallization
refractive indexes
of crystal and glass
verge
reduced
crystal / glass
interface
High crytallized
fraction
Vitreous Materials Lab – www.lamav.ufscar.br
Mechanical behaviour of
HCHTGC
A new, specially designed, 
method of impact testing!
Vitreous Materials Lab – www.lamav.ufscar.br
Impact testing of glass
Courtesy of Leo Siiman, Creol/ UCF
Vitreous Materials Lab – www.lamav.ufscar.br
Don’t try this
experiment in your
lab!
Vitreous Materials Lab – www.lamav.ufscar.br
Kic versus volume fraction crystallized
2
3
2
1
 016.0
c
F
H
EKIC ⎟⎠
⎞⎜⎝
⎛=
c
Anstis
Eglass
71 GPa
⎟⎟⎠
⎞
⎜⎜⎝
⎛
⎟⎟⎠
⎞
⎜⎜⎝
⎛⎟⎠
⎞⎜⎝
⎛=
−−
φφ
aH
E
H
a
lkic
5
2
2
1
035,0
Nihara
φ~3, 
a,l,c [um]
Average grain size
from 3 to 6 um
Ecr ~105
0 20 40 60 80 100
0.5
1.0
1.5
K
i
c
 
(
M
P
a
.
 
m
1
/
2
)
Fr. cristalizada (%)
 Kic Anstis
 Kic Niihara
 kic Anstis (Thiana)
 Kic Niihara (Thiana)
Vitreous Materials Lab – www.lamav.ufscar.br
Why do the transparency
and impact strength drop
significantly for > 97% 
crystallinity?
Vitreous Materials Lab – www.lamav.ufscar.br
SPONTANEOUS CRACKING for > 97% crystallinity!
accelerated 300X
 .
Vitreous Materials Lab – www.lamav.ufscar.br
CONCLUSIONS
New 
type of TGC 
- highly transparent in the visible ~ 90% 
for 1mm 
- nm to μm grain size
- up to 97% crystallized volume fraction
- chemical durability OK
- good mechanical properties, which can
probably be much improved by ion-
exchange.
- can be drawn into fibers
- luminescence ? doping with Cr and
RE ions should be tested...
Vitreous Materials Lab – www.lamav.ufscar.br
On the origem of misterious biomorphs
and geoglyphs in Nazca, Peru, 200 B.C.
.
Vitreous Materials Lab – www.lamav.ufscar.br300 μm
Sm2O3-Bi2O3-B2O3 glass
SmxBi1-xBO3 crystal
Crystals
Bird in Nazca, Peru
SHG
Courtesy of
T. Komatsu
Vitreous Materials Lab – www.lamav.ufscar.br
VITREOUS MATERIALS LAB, UFSCar, São Carlos
BRAZIL
Thank you!


Lecture 9, Part 4: Nucleation, growth and transparent glass-ceramics - Transparent glass ceramics

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Lecture 9, Part 4: Nucleation, growth and transparent glass-ceramics - Transparent glass ceramics

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