03/06/2014

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New Developments in Glasses and Glass

Ceramic Systems of Technological Interest

Andrea S. S. de Camargo

Center for Research, Technology and Education in Vitreous Materials

Grupo de Ressonância Magnética, Espectroscopia e Magnetismo

Instituto de Física de São Carlos, IFSC/USP, Brazil.

Glasses and Glass-ceramics

En

trop

y.

T melt T g

Temp.

Re-inforcement Bio-glasses fast ion Optical CatalyticMaterials and ceramics conductors materials materials

Armor Implants Batteries Lasers Converters

CeRTEVE.D. Zanotto (UFSCar), DirectorH. Eckert (USP), Vice-director

E. B. Ferreira (USP), TechnologyA. C. Rodrigues (UFSCar) , Education

Structural Design and CrystallizationStructure <-> Dynamics <-> Properties Relationship

Functional Characterization and Optimization

Glass Ceramics for Armor Applications

03/06/2014

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Glass Ceramics for Armor Applications

Materials demands:

High flexural strength : Sf ~ 100-400 MPa

High fracture toughness: Kic ~ 1 - 5 MPa.m1/2

Lead Candidates:

Canasite: K2Na4Ca5Si12O30F2

Li disilicate: Li2Si2O5

I. Denry, J. A. Holloway, Materials 3 (2010), 351.

G. P. Ho, J. P. Matinlinna, Silicon 3 (2011), 109.

L. L. Hench, D. E. Day, W. Höland, V. M. Rheinberger, Int. J. Appl. Glass Sci. 1 (2010), 104

VP= 843 m/s VP= 845 m/s

GC 75-25 + 15 Kevlar

Double tt

2.7 g/cc

Hexoloy Saint-Gobain

SiC + 15 layers Kevlar

3.2 g/cc 115 layers of Kevlar

CeRTEV: Ballistic tests in GC75-25

Ceramics for Restorative Dentistry

Chemical durability

Biocompatibility

Mechanical strength

Toughness

Hardness

Thermal conductivity

Translucency

Color

Phosphorescence

similar to that

of natural teeth

Lithium Disilicate Dental Ceramics

Li-Disilicate Li-Metasilicate Li Disilicate

Glass Glass Ceramic Glass Ceramic

650 °C 900 °C

40-50% cryst.

Soft material

CAD-CAM

80-90% cryst.

Very hard

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CeRTEV: Monitoring phase evolution by 29Si solid state NMR

Li2Si2O5

Li2SiO3

Residual glass

C. Bischoff, H. Eckert, E. Apel, V. M. Rheinberger, W. Höland, PCCP 13 , (2011).

Re-inforcement Bio-glasses fast ion Optical CatalyticMaterials and ceramics conductors materials materials

Armor Implants Batteries Lasers Converters

CeRTEVE.D. Zanotto (UFSCar), DirectorH. Eckert (USP), Vice-director

E. B. Ferreira (USP), TechnologyA. C. Rodrigues (UFSCar) , Education

Structural Design and CrystallizationStructure <-> Dynamics <-> Properties Relationship

Functional Characterization and Optimization

Bioactive glasses and scaffolds

Osteoconduction: binding to hard tissue only

„human spare parts“

Osteoproduction: binding to hard and soft tissue

bone regeneration

Osteoinduction: induced bone growth via

stimulation of genes

Bioglass and Bioceramic Mechanisms

Scaffold design: hierarchically structured

meso/macroporous materials

via solution templating

D. Arcos, M. Vallet-Regi, Acta Biomater. 6 (2010), 2874 and references therein,

L. L. Hench, I. D. Xynos, J. M. Polak, J. Biomater. Sci Polym. Ed. 15 (2004), 543.

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Development of materials for medical and dental applications: synthesis, development of processing techniques and materials characterization.

Bioactive gel-glasses

in vitro bioactivity tests in simulated body fluid

air polishing for acrylic resin and stain removal

Biosilicate ®

CeRTEV: Bioactive glass-gel and biosilicates

CeRTEV: Bioactive gel glass - Clinical trial

4 µm

2 µm

2 µm

0 1 2 3 4 5 60

20

40

60

80

100

120

140

160

Tee

th b

y H

ype

rsen

sitiv

ity L

evel

Applications

SemHD Leve Média Alta Grave

n=160

Dentine tubules before and after treatment. No sensitivity- green Light - blue Medium- yellow High - orange Extreme – red Courtesy of Jessica Cavalle

CeRTEV: Bio G and GC under development

Flexible mantels

Powders Grains Optical (eye) prothesis Coated implants

Scaffolds Medium ear prothesis

Pinto, K.N.Z.; Tim, C.R.; Crovace, M.C.; Matsumoto, M.A.; Parizotto, N.A.; Zanotto, E.D.; Peitl, O.;

Rennó, A.C.M. Photomedicine and Laser Surgery 31 (6), pp. 252-260. 2013.

Renno, A.C.M.; Van De Watering, F.C.J.; Nejadnik, M.R.; Crovace, M.C.; Zanotto, E.D.; Wolke,

J.G.C.; Jansen, J.A.; Van Den Beucken, J.J.J.P. Acta Biomaterialia 9 (3), pp. 5728-5739. 2013.

Re-inforcement Bio-glasses fast ion Optical CatalyticMaterials and ceramics conductors materials materials

Armor Implants Batteries Lasers Converters

CeRTEVE.D. Zanotto (UFSCar), DirectorH. Eckert (USP), Vice-director

E. B. Ferreira (USP), TechnologyA. C. Rodrigues (UFSCar) , Education

Structural Design and CrystallizationStructure <-> Dynamics <-> Properties Relationship

Functional Characterization and Optimization

03/06/2014

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T. Minami, A. Hayashi, M. Tatsumisago, Solid State Ionics 177 (2006), 2715.

J. W. Fergus, J. Power Sources 195 (2010), 4554.

Scheme of a Lithium Ion Battery

Energy density:

∼ 300 Wh/kg

The Lithium/Air Battery

Theoretical Capacity 11140 Wh/kg

P. Stevens et al., Electrochem . Soc. Trans. 28 (32), 1 (2010)

Li-super-ion-conducting Glass Ceramics

with the NASICON Structure

Use as separator membranes

Li1+xAlx(Ge/Ti)2-x(PO4)3

L. Puech, C. Cantau, P. Vinatier, G. Toussaint, P. Stevens, J. Power Sources 214, 330 (2012)

80 60 40 20 0 -20 -40 -60 -80

δ 27Al / ppm

20 10 0 -10 -20 -30 -40 -50 -60 -70

δ 31P / ppm( ) ( )

glass

crystal

-10 0 10 20 30 40 50 60 70 80 90 1000,30

0,35

0,40

0,45

0,50

0,55

0,60

0,65

0,70

0,75

0,80

Ea Log Sigmat

Tempo (h)

Ea

(eV

)

-12,5

-12,0

-11,5

-11,0

-10,5

-10,0

-9,5

-9,0

-8,5

-8,0

-7,5

-7,0

Log Sigm

at (Ω−1 cm

-1)

CeRTEV: Li1.5AlxGe1.5(PO4)3 glass ceramic

64 h at Tg:

σ increases

abruptly

31P NMR:

10% crystallinity

31P 27Al

C. Schröder, J. Ren, A. C. M. Rodrigues, H. Eckert, J. Phys. Chem. C. 118, 9400 (2014).

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Re-inforcement Bio-glasses fast ion Optical CatalyticMaterials and ceramics conductors materials materials

Armor Implants Batteries Lasers Converters

CeRTEVE.D. Zanotto (UFSCar), DirectorH. Eckert (USP), Vice-director

E. B. Ferreira (USP), TechnologyA. C. Rodrigues (UFSCar) , Education

Structural Design and CrystallizationStructure <-> Dynamics <-> Properties Relationship

Functional Characterization and Optimization

Single Crystal Lasers

• For high power lasers: Glasses and glass-ceramics doped with trivalent

rare-earth ions (Nd3+, Yb3+, Er3+, Tm3+, Eu3+, Tb3+)

Borates, oxyfluorides, phosphates, silicates, etc.

lasers, amplifiers, upconverters, waveguides, etc.

10

x 1

0 x

2 c

m3

1

0 x

10

x 2

cm

3

…are being replaced by glasses and glass ceramics

24

CeRTEV: Oxyfluoride G and GC for IR lasing, optical

temperature sensors, and white light generation

400 450 500 550 600 650

Inte

nsity

(R

el. 5 D

3, 5 G6-

7 F5)

λexc

= 360 nm

λexc

= 359 nm

λexc

= 358 nm

λexc

= 357 nm

λexc

= 356 nm

λexc

= 355 nm

Wavelength (nm)

Emission Ba-Sr-Al-P-Y glassComp.: AlF

3/Al(PO

3)3(10%/20%)

(Tb3+/Eu3+)F3(0.25%/0.25%)

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CeRTEV: Sol gel host-guest luminescent hybrid systems

25

Some interesting molecular emitters… • Rhodamine 6G laser dye (broad emission in the red)

• Neutral and cationic Ir(III)-complexes (blue to green emissions)

• Neutral nine-coordinated Eu(III) complex (discrete red emission)

… and explored sol-gel hosts:

MCM-41

(t-UPTS)

Solid state dye lasers: Rhodamine

6G (Rh6G) dispersed in silicates

• Tunable, random lasers, displays, bio-sensors

Ir-complexes based materials (OLEDs, LEECs and bio/O2 sensors)

- Efficient triplet emitters in the visible range

- High photoluminescence quantum yield

- Relatively short excited state lifetimes

- Facile color-tuning through ligand design

Re-inforcement Bio-glasses fast ion Optical CatalyticMaterials and ceramics conductors materials materials

Armor Implants Batteries Lasers Converters

CeRTEVE.D. Zanotto (UFSCar), DirectorH. Eckert (USP), Vice-director

E. B. Ferreira (USP), TechnologyA. C. Rodrigues (UFSCar) , Education

Structural Design and CrystallizationStructure <-> Dynamics <-> Properties Relationship

Functional Characterization and Optimization

Porogenic agents as sacrifice templates for porous glass-

ceramics (biomaterials, catalysis applications)

+ Heat

treatment

Organic

Porogenic

Agent

Ceramic

matrix

conformation

Gas evolution

Gas evolution

macroporous

Ceramic or GC

Entire sphere Surface detail Cut sphere

03/06/2014

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A B

A) Porogenic grain: calcium alginate + sodium silicate + phosphates

B) Pore in an alumina matrix after thermal elimination of the porogenic grain and

incorporation of its elements into the pore surface

CeRTEV: Designing porogenic agents for

porous functionalized glass-ceramics:

Metal NPs and oxides for catalysis.

Acknowledgements

Center for Research, Technology and Education in Vitreous Materials

Thank you for your attention!!

Thank you for your

attention!!