Lehigh University Lehigh University Lehigh Preserve 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- Lecture 9, Part 4: Nucleation, growth and transparent glass- ceramics - Transparent glass ceramics ceramics - Transparent glass ceramics Edgar Dutra Zanotto Federal University of Sao Carlos, Brazil Follow this and additional works at: https://preserve.lehigh.edu/imi-tll-courses-usjapanwinterschool Part of the Materials Science and Engineering Commons Recommended Citation Recommended Citation 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 This Video is brought to you for free and open access by the Semester Length Glass Courses and Glass Schools at Lehigh Preserve. It has been accepted for inclusion in US-Japan Winter School by an authorized administrator of Lehigh Preserve. For more information, please contact [email protected].
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Lehigh University Lehigh University
Lehigh Preserve 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-Lecture 9, Part 4: Nucleation, growth and transparent glass-
Edgar Dutra Zanotto Federal University of Sao Carlos, Brazil
Follow this and additional works at: https://preserve.lehigh.edu/imi-tll-courses-usjapanwinterschool
Part of the Materials Science and Engineering Commons
Recommended Citation Recommended Citation 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
This Video is brought to you for free and open access by the Semester Length Glass Courses and Glass Schools at Lehigh Preserve. It has been accepted for inclusion in US-Japan Winter School by an authorized administrator of Lehigh Preserve. For more information, please contact [email protected].
Transparent Transparent glass glass -- ceramicsceramicsEdgar 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
OUTLINEIntroduction to glass-ceramicsBrief literature review on TGCPotential applications of TGCConditions for transparencyMature TGC – nanocrystalsNew TGC: Properties
Cooking wareFire resistant platesSecurity 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.
OpticalOptical((potentialpotential))
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 SYSTEMSJournal of Applied Physics, 38 (11): 4243 1967
ConditionsConditions for for transparencytransparency
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 ParanalObservatory, Chile, Dec. 97/ Schott
Vitreous Materials Lab – www.lamav.ufscar.br
ROBAX – SchottNEOCERAM – NIPPONKERAGLASS- Corning/ St. Gobain CERAN- Schott
.
Vitreous Materials Lab – www.lamav.ufscar.br
NEWTRANSPARENT 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 withCsCl crystals
X. Zhang et. al. , J. Non-crystalline Solids 337 (2004) 130Lab. glasses and ceramics, University of Rennes, France
Vitreous Materials Lab – www.lamav.ufscar.br
Typical microstructure of IR glass-ceramics
Zhang et. al.
100nm CsClcrystals
Vitreous Materials Lab – www.lamav.ufscar.br
IR transmission versus crystallinity
0102030405060708090
100
0.5 1.0 1.5 2.0 2.5 3.0
Wavelength (µm)
Tra
nsm
issi
on (%
)
0 hour3 H7 H23 H31 H73 H144 H246 H
Zhang et. al.
0102030405060708090
100
0 1 2 3 4 5 6 7 8 9 10 11 12Wavelength (µm)
Tran
smis
sion
(%) 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 TanabeKyoto University, Kyoto, Japan
Shunsuke Fujita, Akihiko Sakamoto, Shigeru YamamotoNippon 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 illuminationEfficiency Life
Incadescent Light Bulb 16 lm / W 1000hFluorescent Lamp 80 lm / W 10,000hToday’s white LED 60 lm / W 20,000hFuture white LED 200 lm / W 100,000h
Laser crystallization in glassLaser crystallization in glass
RareRare--earth (Samarium) atom heat processingearth (Samarium) atom heat processing1. CW 1. CW Nd:YAGNd:YAG laser irradiation to Smlaser irradiation to Sm22OO33 or Dyor Dy22OO33 containing glassescontaining glasses2. Absorption and non2. Absorption and non--radiativeradiative relaxationrelaxation
Irradiated region is heatedIrradiated region is heated Crystallization Crystallization
S.D. Stookey et al. (1954) – Corning, USAL.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
UVexcitation
Photoionization
Valence change
ElectronTrapping
Valence change
LatentImage
Ag0
Ag0
kT
Ag0
Ag0
Ag0
Ag0
Ag0
kT kT
kT kT
kT
Ag0 Ag0
Ag0 Ag0
Silver atomsdiffusion
Growth of Silvernanocrystal
Ag0
Ag0
kT
Ag0
Ag0
Ag0
Ag0
Ag0
kT kT
kT kT
kT
Ag0 Ag0
Ag0 Ag0
Silver atomsdiffusion
Growth of Silvernanocrystal
Na+ F -
Na+
Na+ F -F
-
Na+Na+ F -
Na+F -F
-
F -
kT
Na+
kT
Na+
kT
F -
kTAg0 Ag0
Ag0 Ag0
Silvernucleationcenter
Sodiumfluoridecrystal
3D image (hologram) of object is transformedto 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 FloridaSchool of Optics - CREOL Laboratory of Photo-Induced Processes Ce3+
Ce4+
e-
hν
Absorption spectrum of photo-thermo-refractive glass
No detectable absorption in the range of 1 μmAbsorption of hydroxyl in the range of 4 μm
0
0.5
1
1.5
2
0 1000 2000 3000 4000
Wavelength, nm
Abs
orpt
ion,
cm-1 COIL
Nd, Yb, Er1-1.6 μm
DF3.6-4.2 μm
HF2.7 μm
Vitreous Materials Lab – www.lamav.ufscar.br
PTR glasses
Creol’s PTRGHologram
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. ZanottoLaMav- Federal University São Carlos, Brazil
Vlad Fokin ThianaBerthier
Vitreous Materials Lab – www.lamav.ufscar.br
STRATEGYSTRATEGY
New type of transparent glass-ceramic
Simultaneous compositional variation
small or large grain size high crystallizedvolume fraction
of solid solution crystals and glassy matrix
decreases Δn
Vitreous Materials Lab – www.lamav.ufscar.br
OPTICAL PROPERTIESOPTICAL PROPERTIES
200 nm – 1100 nm
Estimated parameters (P1 and P2): P1 = (1-R)2
P2 = (β+S)( )xPP
II
210
exp −=
Transmittance measured for different sample thicknesses
Crystal morphology
Grain size
Degree of crystallinity OM
TransmissionSpectra
Vitreous Materials Lab – www.lamav.ufscar.br
MICROSTRUCTURESMICROSTRUCTURES
The crystals are solid solutions: TA4+2xAE4-x[GF6O18] (0 ≤ x ≤ 1)