Laboratoire Laboratoire d’Electrochimie et de Physicochimie d’Electrochimie et de Physicochimie des Matériaux et des Interfacesdes Matériaux et des Interfaces Glasses : particularities, synthesis and applications

Jean Louis SOUQUET, Michel DUCLOT ELSA

Glassy materials : definition

and historical introduction

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I 2WHAT IS A MATERIAL ?Material utilitary aspect of matter for objects manufacturingMaterials science fundamental knowledge of materials and

engineering processesAtomisticChemical bondingMaterial strengthMechanical propertiesObjectsSynthesis and characterisationsMaterial

conception Shaping Thermodynamics Kinetics Electricity Magnetism Instrumentation Cristallography Chemistry and physics Sintering Moulding Plasticity Economy Human needs Ecology

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Traditional

bricks

porcelain

refractories

GLASSES : CERAMIC MATERIALSκεραμοσ : fired clay

( )keramos

Ceramics( )crystalline

Glass ceramicsGlasses( )non crystalline

Fine ceramicsAl2O3

BaTiO3

SnO2

SiCSi3N4

BN

Traditional flat glass

containersfiber

Special glasses optical fiber

photochromiclaser

chalcogenidesmetallic

, Si Se

oxidesnonoxides ⎧ ⎨ ⎪ ⎩ ⎪ ⎫ ⎬ ⎪ ⎭ ⎪ ⎫ ⎬ ⎪ ⎭ ⎪ ⎧ ⎨ ⎪ ⎩ ⎪

I 5 A SHORT HISTORY OF THE OLD GLASS INDUSTRY STONE AGE 20 000 TO 5 000 B.C.

Natural obsidian glasses : (quenched from volcanic lava) # 250 000 000 years old ! used for arrow head, knifes .....

Chemical composition (wt %) :

BasalticobsidianGraniticobsidian

Modernwindow glassFe2O3101.50.12Network formersSiO2

Al2O3

52.5167514

71.51.0

Network modifiersNa2O+K2O

CaOMgO

496

7.50.50.2

1494

Obsidian tools found everywhere :

- from Europe to Siberia

- South America : Aztecs and Mayas

THE FIRST GLASS INDUSTRY 5000 B.C. TO 1000 A.D.

Mesopotamy (5 000 B.C.)Egypt (1 500 B.C. by Pharaoh Thontmosis III)

Raw materials : sand + alga or vegetal ashes + schells(SiO2) (Na2O) (K2O) (CaO)

Coloring agents (# %) : iron, copper, manganese ...oxides for jewels, mummy eyes, jugs....

How to make a glass jug ?glass jugwet sand shapeshells +ashes mixture

CaCO3 CaO + CO 2

2NaOH Na 2O + H2O

SiO2 + CaO + Na 2O glass

# 1400°C

Glass blowing technique expansion : Egypt, Phenicie, Italy, Greece, Spain, Germany, Gallia ....

metallic tubeThe glass blowing technique (# 100 B.C. Syria)

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GLASS SCIENCE AND ART

THE PORTLAND VASE

Made in Roma in the 1 st century B.C....

I 7... But broken in 200 pieces by an unhinged man ;

restored in 1945.

THE GLASS TECHNOLOGY EMPIRICAL PROGRESSXth - XVIIth CENTURIES A.D. IN EUROPE

Glass and religion Stained glass windows : IX th to XVIth century and apogee while XII th - XIIIth century.

Coloring agents :- transition metals oxydes : Ni, Fe, Cu, Co- noble metals colloids : Au, Ag- "soap" MnO2

Stained glass : 5 to 10 % remaining XII th : 1 000 / 15 000 XIIIth : 10 000 / 250 000

Glass and science :1280 first spectacle glasses1609 Galileo telescope

Glass and art

"cristal" glasses(high n and dispersive power)

First mirrors : Sn, Hg (1600)

A secret industry and until XVII th century a dominant Italian industry (Venezia)

SiO 2 - PbO - K 2O (England 1620)

(53) (35) (12)

SiO 2 - CaO - K2O (Bohemia 1400)

Italy

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I 9THE OLD WINDOW GLASS MANUFACTURING

I 101665 Colbert

1688 L. de Nehou

# 1500 Euro/kg

2000

# 0.5 Euro/kg

Toward an industrial product (window glass)TOWARD A MODERN GLASS INDUSTRY

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AlglassTM burners

THE MODERN FLAT GLASS INDUSTRY (# 10 8 t/YEAR)

Alumina bricksFrom the glass melting furnace ....Refining zoneRaw materials (SiO2, CaCO3, Na2CO3, Na2SO4.....)and recycled glassFlame burnersSilica bricksMelting zoneMaximum temperature

... to the glass sheets by the float glass techniqueribbon

600°C

molten glass

1100 °C

top railsmolten tinN2 + H2 atmosphereAbout 120 float glass furnaces in the world producing from

100 t/ day to 1000 t / day :

Europe 29 %

USA 32 %

Asia 25 %

(Japan)

Other 14 %

(Brasil)

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molten glasscircular burnersfiberscentrifugal

spraybindersprays

rotary processing(discontinuous fibers)

continuous fibers windingplatinumdraw-platebinding agent coatingwindingglass ballswindingwindingGLASS FIBERS PROCESSING AND COMPOSITION FOR :- Insulation (acoustic and thermal)

- Filtration (air and liquids)

- Reinforcement (composite materials)

Glass compositions wt % E R S SiO2 Al2O3 B2O3 CaO MgO

54

16

8

17

5

60

25

-

9

6

65

25

-

-

10

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SiOOROCH3CH3CH3-H2O HOW WORKS A B INDING AGENT AT

THE GLASS / POLYMER INTERFACE.

SiSiSiHOOHROHOHSiHOOHROHOHSiSiSiOOROSiOROBasically, contain a silane :Example :

R : (CH2)3 NH2, react with epoxy CH2 CH groups of the

resin.

O+ H2OSiHOOHROH+ 3 CH3OHAfter silane and glass surface hydrolysis a surface polycondensation :The R radical react then with the organic resin allowing the binding with glass fiber :(CH2)3 N CH2 CHSiOHO

H

glasschemical bindingresin

GLASS CONTAINERS PROCESSING :

from molten glass.....

.... to the bowl pressingchiselsmolten glasscooling fluid

punchmouldbowlspringcooling fluidsucker

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THE MODERN GLASS INDUSTRY

(EUROPE, USA, ASIA) 100.106 t/year of traditional products (1997)

- glass containers and bottles 60 106 t/year

- flat glass (automotive and architectural products) 23 106 t/year

- glass fibers for insulation or composites 5 106 t/year

- special glass and "crystal" glass 12 106 t/year

new technology and products- special oxide glasses (lighting, TV tubes, optical fibers)- glass surface treatments

. chemical strengthening by ionic exchange

. reflecting and absorbing layers (TiO2, SnO2, Si) by dipcoating, spray or

sputtering techniques.- glass ceramics

. cooking surface and ustensils

. dielectric components- non oxides glasses

. chalcogenide glasses

. amorphous Si and Se

. metallic glasses

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THE GLASS INDUSTRY IN EUROPE (15/2003) 106 t/year

- Glass containers and bottles 18.4 - Flat glass (fabrication and transformation) 7.8 - Table ware 1.21 - Special glass 1.17 - Reinforcement fibers 0.65

- Total glass industry 29.12

The largest groups in Europe :

- SAINT GOBAIN (FR)- PILKINGTON (GB)- SCHOTT (DE)- DANONE (FR)

Employment : 162 000 for about 1000 companies

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MORE GLASS, LESS ENERGY AND CO2 EMISSION WITH FURNACES IMPROVED AND GLASS RECYCLING

10% in recycled glass 3% decrease in energy5% decrease in CO2 emission

19601970198019902000100020003000400050006000Specific energy (kWh/glass ton)CO2 (ton/1000)Glass production (kilo ton)Specific CO2 (kg/glass ton)calcin (kiloton)

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GLASS RECYCLING IN EUROPE (2003) Country Collected (kilotons) Recycling percentage

AustriaBelgiumDenmarkSpainFinlandFranceGermanyGreeceIrelandItalyNorgeHollandPortugalSwedenSwissTurkeyUnited Kindom

20630915062250

1 9772 689

4175

1 25050

41214015130178

875

86%88%71%38%73%58%88%30%67%59%86%81%38%92%96%22%36%

Total 7 648 60%(An EEC directive 94/62/CE)

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