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

dedz@ufscar.brSpring 2015

1

Center for Research Technology and Education in

Vitreous Materials

2Zanotto

Vitreous materials lab

3

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

6Zanotto

Reading assignments

E. D. Zanotto – Am. Ceram.

Soc. Bull., October 2010

7Zanotto

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

8Zanotto

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

Zanotto 10

“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

11Zanotto

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…

13

TC 7 members and guests

Photo by Mark Davis

S.D. Stookey

Crystallization symposium, Stone Mountain (2006)

14Zanotto

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/

16Zanotto

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.

17Zanotto

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

18Zanotto

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

20Zanotto

Glasses and Glass-ceramics

Vo

lum

e

Tmelt

Tg

Temp.

21Zanotto

Production steps

Time

Tem

pera

ture

melting

shaping

nucleation

growth

GC

Tg

TL

22Zanotto

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

25Zanotto

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