glass processing - lehigh university€¦ · the discovery of gc natural glass-ceramics, such as...
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Glass Processing
Lectures available at:
www.lehigh.edu/imiSponsored by US National Science Foundation (DMR-0844014)
Lecture #15 Glass-ceramics: Nature, properties and
processing
Edgar Dutra ZanottoFederal University of São Carlos, Brazil
[email protected] 2015
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Center for Research Technology and Education in
Vitreous Materials
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Vitreous materials lab
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The Vitreous State
August – Nov. 2015 (15 weeks = 30+30h)
LaMaV - Federal University of São Carlos
Instructor: EDZ
Glass – nature and properties
Glass structure
Relaxation - glass transition
Liquid-liquid phase separation
Crystal nucleation kinetics
Crystal growth kinetics
Overall crystallization
Sintering with concurrent crystallization
Glass forming ability - CCR
Glass stability against devitrification
Glass-ceramics4Zanotto
Nucleation, Growth and Crystallization in Glasses
— Fundamentals and Applications
May 16-17, 2015 | 1:00 p.m. – 5:00 p.m.; 8:00 a.m.
– Noon | 8h
Hilton Miami Downtown
Instructor: EDZ
Fundamentals:
-Crystal nucleation
-Crystal growth
-Overall crystallization
Applications:
-Sintering with concurrent crystallization
-Glass forming ability - CCR
-Glass stability against devitrification
-Glass-ceramics 5Zanotto
Glass-ceramics: nature, applications
and processing (2.5 h)
High T reactions, melting, homogeneization and fining = previous
lectures!
Glass forming: previous lectures!
Glass-ceramics: definition, properties & applications
Thermal treatments – Sintering (of a glass powder compact) or
Controlled nucleation and growth in the glass interior
Micro and nano structure development
Concluding remmarks
IMI
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Reading assignments
E. D. Zanotto – Am. Ceram.
Soc. Bull., October 2010
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Properties of inorganic glasses
Isotropic
Transparent, opaque, colorless, colored.
Refractive index: 1.2 – 2.2
Electrical conductivity (Tamb): 106 - 1018 (ohm.cm)1
Tg: 150ºC - 1200oC.
Low thermal conductivity: k ≤ 1 W/m.K
Hardness: 3 -15GPa
Resistant to acids to soluble in H2O
Fragile: KIC < 1 MPa.m1/2
Conchoidal fracture ...
Metastable!
Tend to devitrify on slow cooling or heating
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Zanotto 9
J.C. Mauro & E. D. Zanotto - “200 years of glass research...”
IJAGS, 2014
8807
8390
3708
2854
2586
2028
1679
1578
1430
1417
1330
1190
1183
1152
1025
943
880
816
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Crystallization
Glass Transition
Composition
Thermodynamic Properties
Activation Energy
Structure
Phase Transitions
Nucleation
Diffusion
Sintering
Relaxation
Interfaces
Chemical Bonds
Reaction Kinetics
Energy Transfer
Phase Separation
Crystal Growth
Glass Forming Ability
Number of Publications
1850-2013
Most frequent keywords in the history of glass research
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“Devitrification is the chief factor which limitsthe composition range of practical glasses, it is an ever-present danger in all glass manufacture and working, and takes place promptly with any error in composition or technique”
G. W. Morey
The Properties of Glass
Reinhold Pub, NY
1938 & 1954
R.Muller, V. Fokin, E.D. Zanotto- J. Non-Crystalline Solids (2001)
Heterogeneous (surface) nucleation on silicate glasses
DevitriteLS + CS
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Defect: devitrification
250 m
12Sildes from E.B. Ferreira
The discovery of GC
Natural glass-ceramics, such as some types of obsidian “always” existed.
Volfram Hoeland and George Beall mention
in their book that: “knowledge of the literature,
good observation skills, and deductive reasoning
were clearly evident in allowing the chance events
to bear fruit”.
In 1953, Stanley D. Stookey, then a young
researcher at Corning Glass Works, USA,
made a serendipitous discovery when a furnace
containing a piece of a lithium silicate glass with
precipitated silver particles (meant to form a
permanent photographic image) accidentally
overheated to about 900°C, instead of 600°C…
René F. Réaumur – 1739 “porcelain”
experiments…
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TC 7 members and guests
Photo by Mark Davis
S.D. Stookey
Crystallization symposium, Stone Mountain (2006)
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15
ICG TC-7
TC 7
The next symp in the series
Crystallization 2015
11th International Symposium on
Crystallization in Glasses and Liquids
October 11-14, Nagaoka, Japan
http://crystallization-2015.jp/
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References
+ review articles by:
Beall & Pinckney, Hoeland, Pannhorst, James, Davis,
Zanotto, Dymshits…
From glass to crystal: nucleation, growth and phase separation, from
research to applications - D. Neuville et al. (2015)
Nano-Glass Ceramics: Processing, Properties and Applications.
Marghussian, V., 1st Edition, Elsevier, 2015.
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Statistics /scientific papers
July 2014 search
• Scopus database with the keywords
(glass-ceramic*) OR (“glass ceramic*) in
the title or abstract or keywords in all types
of docs: ~13,000 articles
or ~7,000 using only article titles
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GC: papers / year
0
100
200
300
400
500
600
700
800
900
1953 1963 1973 1983 1993 2003 2013
Nu
mb
er
of
Pap
ers
Year
Title
Title, Abstract & Keywords
Am. Cer. Soc. Bull. May 2015
A Statistical Overview of Glass-Ceramic Science and TechnologyMaziar Montazerian, Shiv P. Singh, Edgar D. Zanotto
19
Objectives
Critically comment on a number of exciting
new types of GC that are being currently
developed;
Discuss some critical issues regarding GC
processing
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Glasses and Glass-ceramics
Vo
lum
e
Tmelt
Tg
Temp.
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Production steps
Time
Tem
pera
ture
melting
shaping
nucleation
growth
GC
Tg
TL
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Glass-ceramics (GC) =
glass ceramics, vitrocerams, pyrocerams, vitrocerâmicos,
vitroceramiques or sittals
GC always contain a residual glassy phase and
one or more embedded crystalline phases – with
widely varying crystallinity between 0.5% and
99.5%, most frequently 30-70%.
Advantages of CGs:
- can be mass produced by any glass forming
technique
- it is possible to design the material’s nano or
microstructure
- most have zero or very low porosity,
- It is possible to combine desired properties 23
GLASS-CERAMICS
Microstructural Design
grain size distribution & shape, texture,
porosity, %crystallinity, type and #
crystal phases…
Combination of
properties
optical transparency
bioactivity
controllable TEC
high thermal and
chemical stability
harder and tougher
than glasses
controllable
electrical properties 24Zanotto
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Zanotto 26
Designed micro and
nanostrucureslead to...
Donald Stookey
(2000)
Otawa Dental Lab.
Zerodur
HD Substrate
Cooktop
glass-ceramic products
27
<rms> 1nm28
Patents granted per year extracted from the DWPI by
searching for “glass-ceramic*” OR “glass ceramic*”
keywords in the patent title.
0
50
100
150
200
250
1968 1973 1978 1983 1988 1993 1998 2003 2008 2013
Nu
mb
er
of
Pat
en
ts
Year
Am. Cer. Soc. Bull., May 2015
Statistical Overview of Glass-Ceramic Science and Technology
Maziar Montazerian, Shiv P. Singh, Edgar D. Zanotto
Derwent Innovation Index search
~5,000 granted patents on GCs
29
Number of granted patents and patent applications extracted manually
from the FPO website using the keywords “glass ceramic” or “glass-
ceramic” in the patent title. Jan 2001 - July 2014
Per intended application
0
20
40
60
80
100
120
140
160
Nu
mb
er
of
Pat
en
ts
Usage or Property
Granted
Application
Am. Cer. Soc. Bull., May 2015
Statistical Overview of Glass-Ceramic Science and Technology
Maziar Montazerian, Shiv P. Singh, Edgar D. Zanotto
30
44
47
53
54
55
57
61
63
66
69
70
71
75
91
92
104
181
260
378
493
0 100 200 300 400 500 600
NEC
IVOCLAR
MURATA MFG
NGK
MATSUSHITA DENKI
HITACHI
OWENS-ILLINOIS
FUJITSU
EGO ELEKTRO
3M INNOVATIVE
EUROKERA
MATSUSHITA ELEC
ASAHI
OHARA
BOSCH & SIEMENS
ZEISS
NIPPON
KYOCERA
CORNING
SCHOTT
Number of Patents
Twenty most prolific companies with largest number of glass-ceramic patents
granted from 1968 to 2014. “Glass-ceramic*” or “glass ceramic*” keywords
were searched in the patent title. Source: DWPI
Am. Cer. Soc. Bull., May 2015
Statistical Overview of Glass-Ceramic Science and Technology
Maziar Montazerian, Shiv P. Singh, Edgar D. Zanotto 31
Company Products Crystal type Applications
SCHOTT,
Germany
Foturan® Lithium-silicate Photosensitive and etched patterned
materials
Zerodur® β-quartz ss Telescope mirrors
Ceran® / Robax® β-quartz ss Cookware, stovetops, cooktop and
oven doors
Nextrema® Lithium Aluminosilicate Fireproof windows and doors
Corning, USA
Pyroceram® β-Spodumene ss Cookware
Fotoform® /
Fotoceram®Lithium silicate
Photosensitive and etched patterned
materials
Cercor® β-Spodumene ss Gas turbines and heat exchanger
Centura® Barium silicate Microwave tableware
Vision® β-quartz ss Cookware and cooktop
9606® Cordierite Radomes
MACOR® Mica Machinable glass-ceramic
9664® Spinel-enstatite Magnetic memory disk substrate
DICOR® Mica Dental restoration
Nippon
Electric Glass,
Japan
ML-05TM Lithium disilicate Magnetic memory disk substrate
Neoparies® β-wollastonite Architectural glass-ceramic
FireliteTM β-quartz ss Architectural fire-resistant windows
NeoceramTM N-11 β-Spodumene ss Cooktop and kitchenware
Narumi® β-quartz ss Low thermal expansion GC
NeoceramTM N-0 β-quartz ss Color filter substrates for LCD
panels
Cerabone® A-W Apatite-wollastonite Bioactive implant
Zanotto
Fabricação – via cristalização volumétrica
Misturadas Matérias Primas
FusãoHomogeneização/Refino
Conformação(prensagem, sopro,
estiramento de placas)
Tratamento TérmicoCristalização
Resfriamento
Produto Acabado
Nucleantes!
5 m
From E.B. Ferreira - 33
Fabricação – via sinterização
Misturadas Matérias Primas
FusãoHomogeneização/Refino
Fritagem/Granulação
Cominuição
Ajuste Granulométrico
Mistura + Aditivos
Conformação do Pó
Tratamento TérmicoSinterização/Cristalização
Retífica e Polimento
Produto Acabado Polido
Produto Acabado
From E.B. Ferreira - 34