center for research, technology and education · v. n. bykov, o. n. koroleva and a. a. osipov...
TRANSCRIPT
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