Open challenges in structure, dynamics, crystallization, and properties of glasses

Center For Research, Technology and Educationin Vitreous Materials

Edgar D. Zanotto

Outline

1- Overview of glass research in Brazil

2- The CeRTEV- examples of fundamental research

- technological research topics

% of “glass” papers authored by at least one researcheraffiliated to a Brazilian institution

0,00%

0,50%

1,00%

1,50%

2,00%

2,50%

3,00%

3,50%

4,00%

1970 1980 1990 2000 2010 2020

Year

.

100 papers/year

Saturatedor

diminished?

# Recent papers on glass by country

15th

17th

0

10

20

30

40

50

60

70

0 100 200 300 400 500 600 700

Web - total publications hindex

Total publications BR h indexBR

h index vs. #publications

h ~ visibilitysize of thecommunity,interest

# articles (level of activity )

75 Most prolific glass researchers in the world x “Brazilian” (o)

0

5

10

15

20

25

30

35

40

45

0 100 200 300 400 500 600 700

WoS- Cit / paper

Cit/ paper BR

Cit./paper vs. # publications

...

Upper bounds

World

Brazilian

75 Most prolific glass researchers

# articles (level of activity )

Summary

Brazilian glass research started only 40 years ago andhas grown significantly from 1985 until 2002.

Its % share in the world of glass research saturated at~2.7% in 2002 (or is it decreasing?...)

The absolute number of (inorganic, keyword in thearticle title) “glass” papers generated in Brazil saturatedat about 100/year in 2006.

The number of active glass researchers is estimated to be ~100.

Their h-indexes and #citations/article versusnumber of publications follow a similar trend as those of the world’s most prolific glassresearchers.

The upper bounds are still somewhat below theworld’s top in these 2 rankings.

Center for Research Technology and Education in Vitreous Materials

Vice-directorManager

2 secretaries1 informatics

CoordinadorTech &

InnovationDirector

CoordinatorEducation and

Outreach

14 professors

30 active collaborators~50 research students

One of the largest academic glass R & D units on this planet!

International Advisory

Board

6

1

7

CeRTEV´s activities will focus on multidisciplinary, relevant glass science, useful technology and

efficient education and outreach!

Science

Tech

Ongoing fundamental research

Glasses and glass-ceramics

Entr

op

y.

Tmelt

Tg

Temp.

1x109

2x109

3x109

4x109

5x109

Cry

stal

Gro

wth

Rat

e U

(m

/s)

Nucl

eati

on R

ate

I (m

-3.s

-1)

Li2O.2SiO

2

Nucleation

Crystal Growth

600 700 800 900 1000 1100 1200 1300 1400

2,0x10-5

4,0x10-5

6,0x10-5

8,0x10-5

1,0x10-4

T (K)

Crystal nucleation and growth rate curves

Imax

Umax

Solid knowledge about diffusion, viscous flow, relaxation and crystallization phenomena is key!

Na2O2CaO3SiO2

Scientific relevance

The intricate details of thediffusion mechanisms andkinetics controlling crystalnucleation and growth inoxide glasses are unknown!

Tk

GDfTU

B

U exp1

Li2O2SiO2

16

kT

WD

kTI

*

4exp

8.0x10-4

1.0x10-3

1.2x10-3

1.4x10-3

1.6x10-3

1.8x10-3

-22

-20

-18

-16

-14

-12

-10

1400 1200 1000 800 600

-22

-20

-18

-16

-14

-12

-10 DU: This work

DU: Neiman et al.

D = k

BT/

DSi: Schaeffer

DPb

: Lindner et al.

DPb

: Langanke & Schmalzrie

DSi: Langanke & Schmalzried

DPb

: Lindner et al.log

10 D

(m

2/s

)

1/T (K1

)

Tg = 403

oC

T (K)

PbOSiO2

DU, D, DSi & DPb

‘unpublished’

Td ~ 1.25Tg

Tg

Calculated diffusivities

~1Å

17

8.0x10-4

1.0x10-3

1.2x10-3

1.4x10-3

1.6x10-3

1.8x10-3

-22

-20

-18

-16

-14

-12

-10

1400 1200 1000 800 600

DO

DU: This work

DU: Barker et al.

DU: Burgner & Weinberg

DU: Deubener et al.

DU: Fokin

DU: Gonzalez-Oliver et al.

DU: James

DU: Matusita & Tashiro

DU: Ogura et al.

DU: Ota et al.

DU: Schmidt & Frischat

DU: Soares Jr.

DU: Zanotto & Leite

D=k

BT/

DLi

: Beier & Frischat

DO: Sakai et al.

log

10 D

(m

2/s

)

1/T (K1

)

Tm=1034

oC

Tg = 454

oC

DLi

T (K)DU, D, DLi & DO

Li2O2SiO2

Tb ~ 1.1Tg

Tg

Oxygen

Lithium

Calculated diffusivities

18

Viscosity curves of some glasses used here20 < m < 100

Fragilities

19

)(/)()(/)()( 12121212exp12 TDTDTUTUT Udec

20

Experimental and calculated fractions of Q3 units in disilicate glasses

400 600 800 1000 1200 1400 1600 18000.44

0.48

0.52

0.56

0.60

0.64

0.68

0.72

0.76

0.80

0.84

K2Si expNa2Si exp

Ba2Si calc

Li2Si calc

Th

e f

ractio

n o

f Q

3 u

nits

T, K

The exp. curves are from:

V. N. Bykov, O. N. Koroleva and A.

A. Osipov “Structure of silicate

melts: Raman spectroscopic data

and thermodynamic simulation

results”, Geochemistry International

47 (2009) 1067-1074.

Tg

21

Tg

Tg

Tg

The entropy of glass

TK

The Kauzmann paradox!

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

Al / ppm

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

P / ppm( ) ( )

glass

crystal

-10 0 10 20 30 40 50 60 70 80 90 100

0,30

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 S

igm

at (

c

m-1)

Superionic glass NASICON-type glass-ceramics

Ana C. Rodrigues – Hellmut Eckert

Crystallization of Lithium Disilicate CeramicsQuantified by Advanced (Cross Polarization) Solid State NMR

H. Eckert, E.D. Zanotto + PD & studentsJNCS (2014)

20 40 60 80

0

10000

20000

30000

Inte

nsi

tät

/ co

unts

p. se

cond

2 / o

Experiment

Anpassung des Profils

Anpassung des Hintergrundes

-60 -70 -80 -90 -100 -110 -120 -130 -140

500°C 50 Stunden

500°C 75 Stunden

500°C 90 Stunden

/ ppm

500°C 120 Stunden

7Li->29Si NMR XRD Rietveld

On going applied research

Glass-ceramics

LaMaV’s micrograph gallery Crystals in glass

Lithium disilicate:the “Drosophila”

of glass crystallization studies

Photos by Vlad Fokinand Ed Zanotto

Na-Ca-Si-Ox glass

LaMaV’s micrograph gallery

HammingbirdsIn a Li2O-CaO-SiO2 glass

Photo by Vlad FokinLaMaV

PTR glasses

Creol’s PTRGHologram

Corning’s Fotalite

Leon Glebov et. al.

S.D. Stookey et. al.

LARGE GRAIN, HIGHLY CRYSTALLINE, HIGHLY TRANSPARENT GC

Thiana Berthier and Vlad Fokin

Berthier T.; Fokin V. M.; Zanotto E. D. - “New large grain, highly crystalline, transparent glass–ceramics” - J. Non-Cryst. Solids 354 (2008) 1721-1730.

Da Cunha T. B.; Wu J. P., Peitl, O.; Fokin V. M.; Zanotto E. D.; Iannucci L.; Boccaccini A. R. –“Mechanical properties and impact resistance of a new transparent glass-ceramic” - Ad. Eng. Materials 9 (2007) 191-196.

LARGE GRAIN, HIGHLY CRYSTALLINE, HIGHLY

TRANSPARENT GC

Grain size ~20 µm

50% crystal97% crystalglass

Large grain (~10-50 µm), highly crystalline (97% crystallinity), transparent glass-ceramic.

Armor glass-ceramicsPeitl-Rodrigues-Zanotto-students

Programa de Pós-Graduação em Ciência e Engenharia de Materiais - PPGCEM/UFSCar

75-25 9.7MPa

Programa de Pós-Graduação em Ciência e Engenharia de Materiais - PPGCEM/UFSCar

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

Ballistic tests

GC 75-25 + 15 KevlarDouble tt2.7 g/cc

Hexoloy Saint-GobainSiC + 15 layers Kevlar3.2 g/cc

115 layers of Kevlar

New (dental) GC? Soares, Pereira, Crovacce, Serbena, Zanotto et al.

Kic ~3.5 MPa.m1/2

Bioactive G and GC under study and development

Blanquet

Powder GrainsEye Prosthesis

Coatings for Ti

ScaffoldsEar prothesis

0 20 40 60 80 10050

100

150

200

250

D

Flex

ural

Stre

ngth

(MPa

)

Fraction Crystallized (%)

4-point bending, average of 6 specimens. Polished with CeO2 - 1um

Grain size ~13 umBioglass

CeRTEV´s BioG Network

• 54 Researchers

• 20 Departments

• 15 Institutions

lamav.weebly.com

INVITATION

There are several relevant scientific openproblems in the field of glass and glass-ceramics. We are are open tocollaboration with experts on glassstructure studies/simulations at hightemperatures (T>Tg), thermodynamics,etc. to continue this great work!

40

Acknowledgements

São Paulo Research Foundation FAPESP

Grant # 2013/07199-6

Thanks LaMaV!

Thanks CeRTEV!

Goals

-conduct high level research work on relevant subjects that pushthe frontiers of knowledge;

- develop or improve glasses and glass-ceramics and (sustainable) processes jointly with industry;

- train highly qualified engineers and researchers;

- attract young people to the field of glass;

- render relevant services to schools, research instituions andcompanies and society in general

- Increase the number and quality of Brazilian glass research and its influence at international level.

Challenges

-Increase interaction/ collaborative workamong the 14 CeRTEV professors and theirstudents and post-docs

- Attract new researchers to the network

- Built a strong network with industries

- Develop or use efficient strategies for teaching and outreach- Etc????

Ranking in the world (2013)

• A June 2013 search on the SCOPUS database for the number of published articles with relevant keywords indicates that some of CeRTEV´s faculty rank:

• first in the world with the keywords glass* and NMR*

• first with glass* and nucleation

• second with glass* and crystal growth

• fourth with glass* and crystallization

• 26th with bio* and glass-ceramic*

• 28th with glass* and sinter*

• 31th with glass-ceramic*

Metas e desafios

METAS-Tornar, divulgar e consolidar o CeRTEV um dos 10 mais respeitados centros de P&D mundiais

em materiais vítreos;-Desenvolver pesquisas que avancem significativamente as fronteiras do conhecimento emtemas relevantes;

-Desenvolver ou melhorar tecnologias relevantes e sustentáveis para a indústria;-Formar engenheiros e pesquisadores de alta qualificação ;-Prestar relevantes serviços a escolas, prefeituras, universidades, instituições de pesquisa e empresas, isto é, à sociedade em geral!- Aumentar the # and quality of Brazilian glass research and its influence at international level

Desafios:-Aumentar a interação entre os 14 integrantes do grupo-atrair renomados pesquisadores para integrar a rede de pesquisa do CeRTEV-construir e consolidar uma forte e duradoura rede com empresas-Desenvolver e utilizar mecanismos eficientes para a atração de bons estudantes para a área-Desenvolver e aplicar eficientes estratégias de ensino e divulgação científica

Ações já efetuadas e planejamento:-Serão apresentados em seguida pelo gestor

Glass research in Brazil

Glass research in Brazil started in the mid seventies. Only 40 years ago!---------------------------------------------------------------------------

1975 – 2014 (SCOPUS – Physical sciences search, “glass*” in the articletitle, October 26th, 2014)

1,500 articles on inorganic glasses authored by researchers affiliated to Brazilian institutions in a total of 100,000 articles.

140 “Brazilian” authors have published more than 10 articles on glass.

100 “Brazilian” authors published at least 1 “glass” article/year in the last 3 years, they are thus considered as being active in this field

Fapesp talk March 2014 Programa de Pós-Graduação em Ciência e Engenharia de Materiais - PPGCEM/UFSCar

TN = 693°C – 1 dia Tc = 901°C – 3h

TN = 693°C – 3 dias Tc = 901°C – 3h

TN = 693°C – 5 diasTc = 901°C – 3h

75-25 – TN = 693°C / Tc = 901°C – 3h

Education and Outreach

New course for glass techniciansInternational glass science courses

Educative web site (www.certev.ufscar.br)Glass museumComic booksAndroid app

(Glass) science and tech fairsLab visits and talks to high school kids

Outreach via theather plays

And the future?

Andrea S. Stucchi de Camargo

Structure-Property Correlations in Optical Glasses and Ceramics

* Rare earth doped laser glasses and glass-ceramics* Porous sol-gel hosts doped with dyes and organo-metalic (f-, d-) complexes

O BB O AlSi

Solid State NMR Techniques nuclear “spies”

0 10 20 30 40 501E-5

1E-4

1E-3

0.01

0.1

1 Excited State Lifetime: O2-Free

DMSO

DCM

Si2AlNaO

6

Si6AlNaO

14

Si9AlNaO

20

Lo

g(C

ou

nts

) /1

05

Time [s]

0 -20 -40 -60 -80 -100 -120 -140 -160

Si9AlNaO

20

Si6AlNaO

14

Si2AlNaO

6

29Si NMR - SPMAS (4kHz)

B0 = 7.0T (

29Si at 59.6MHz)

(ppm)

Q4

29Si NMR

hn

B E radiowaves

0 1000 2000 3000 4000 5000 6000 7000

0.5F

Magnetic Field (G)

2F

3F

5F

10F

Fe2O3 nanoclusters in Sb-Phosphate glass detected by EPR

Pedro Donoso – Claudio Magon –Marcelo Nalin

Isolated Fe3+

clusters

Early “glass” papers produced in thiscountry

SMALL-ANGLE X-RAY-SCATTERING STUDY OF PHASE

SEPARATION IN A B2O3-PbO-Al2O3 GLASS

CRAIEVICH, A.F.

PHYSICS AND CHEMISTRY OF GLASSES

Vol. 16 Ed. 6 Pgs 133-138, 1975

Only 40 years ago! Institute of PhysicsUSP, São Carlos