Advances in Nanostructured Functional Materials in São Paulo
José A. Varela
IQ UNESP and FAPESP varela@fapesp.br
Fronteras de la Ciência en Brasil y España
Madrid 13 y 14 diciembre de 2012
Ongoing Research Grants 124 Completed Research Grants 244 Ongoing scholarships in Brazil 258 Completed scholarships in Brazil 434 Ongoing scholarships abroad 12 Completed scholarships abroad 26
FAPESP – recent grants and scholarships on
Nanoscience Nanomaterials and Nanotechnology
Recent grants and scholarships (1992-2013)
0 100 200 300 400 500 600
PROJECTS BY AREA
Main subjects on nanoscience
- Nanoparticles, nanotubes and nanobelts
- Composite – nanotube/nanoparticle and nanotube/polymer - Molecular assembly
- Carbon nanostructured - Metallic nanoalloys
- Graphene layers on silicon carbide - Modeling and simulation
Functionality
- Energy: hydrogen storage, water splitting, solar cells, SOFCs - Catalysis
- Biotechnology
- Sensors: gas and bio - Memories
- Ferromagnetic, Piezoelectric, Ferroelectric and Multiferroics
PROPOSALS
RESEARCHER
INSTITUTION National Institute for Materials Science in Nanotechnology
E. Longo UNESP
Development and characterization of iron oxide nanoparticles
coated with polymeric cover complexing
H.E. Toma USP
Development of modified electrodes with carbon nanotubes and polyaniline composites
F.R. Simões UNIFESP Development of molecular devices composed of light synthesized
gold nanoparticle
J.A. Bonacin UNICAMP Canada Combining theory, simulations and experiments. applications in
nanotechnology
E. Longo UNESP
Spain
Modeling carbon nanostructured materials A.F. da Fonseca UNESP
Composites based on carbon nanostructures: an application in nanobiotechnology osteogenesis
P. Ciancaglini USP Computational nanoscience for energy materials: hydrogen storage
and production and ethanol catalysis through metallic nanoalloys
A. Antonelli UNICAMP Detection, removal and recovery of heavy metals with functionalized
magnetic nanoparticles
R.M.C. Peña USP
Third generation biosensors based on the interaction among reduced graphene oxide, ionic liquids and oxidase enzymes
S.I.C. de Torresi USP Study of the interaction of nanoparticles and nanotubes with cell
membrane models and possible applications
V. Zucolotto USP
Bond rupture and energy GAP engineering of graphene layers epitaxially grown on silicon carbide: ab-initio calculations
A. Fazzio USP
Some FAPESP Research Grants on Materials Nanoscience
and Nanotechnology
Metal Nanoparticle
Amorphous Mesoporous Silica Matrix
2m
20nm
“ Bottom-up ”
• Hybrid materials are composite materials (e.g. ceramic-metal) that have distinct properties or superior performance from the simple materials.
The NanoxClean
PROJETO COORDINATOR COMPANY
Filmes de DLC para aplicações em superfícies anti-
bacteriana, anti-atrito, espaciais, industriais e para tubos de perfuração de poços de petróleo
Alessandra V Diniz Clorovale Diamantes Indústria e Comércio S.A
Sistema híbrido de armazenamento de energia para
veículos elétricos Fellipe S. Garcia Ekion Tecnologia de Veículos Elétricos Ltda
Biochip micro e nano fabricado para liberação controlada
de fatores de crescimento para regeneração óssea Claudio R. C. Carvalho Nanobionics Biotecnologia e Bioengenharia Ltda
Desenvolvimento de sistema nanoestruturado de alta estabilidade para carreamento de ativos cosméticos com segurança e eficácia
Paula A. Barbugli Nanomed - Nanotecnologia em Saúde e Bem-Estar Ltda
Escalonamento e implementação de controle de qualidade para produção de antimicrobianos nanoestruturados para aplicação em cerâmicas e plásticos
Luiz G. P. Simões Nanox Tecnologia S/A
Nanotecnologia aplicada em catalisadores e filtros
automotivos de exaustão Melchior A. Momesso Nantex Nanotecnologia Experimental Ltda
Filmes com propriedades catalíticas para pistões
automotivos Melchior A Momesso Nantex Nanotecnologia Experimental
Ltda Desenvolvimento de um aditivo nanocompósito
modificador para o elastômero EPDM María V.. C. Oropeza Orbys Desenvolvimento de Tecnologia de Materiais Ltda
Produção de vacina gênica em nanoestrutura lipossomal
para a tuberculose Lucimara G. de la Torre
SMF Bioplus Desenvolvimento Pesquisas Tecnológicas Químicas Ltda EPP
Some FAPESP PIPE Grants on Materials Science and Nanotechnology
E
vE
CE
F0E
GE
B0 E
0ZnO Film Gas
E
vE
CE
F0E
GE
B0 E
0ZnO Film Gas
E
vE
CE
F0E
G E
0ZnO Film Gas E
B< E
B0E
vE
CE
F0E
G E
0ZnO Film Gas E
B< E
B0Semiconducting Metal Oxide (SMO) Gas Sensors
substrate contact
metal oxide
Oxygen Physisorption:
↑ surface density of states Chemisorption:
↑ surface trapped charge
20 30 40 50 60 70
(210) (202)
(301)(112)(310)
(002)
(220)
(211)
(200) (111)
(101)
Intensidade / u.a.
2graus
a) b)
(110)
XRD data show SnO
2phase with preferential orientation for (101) planes.
White deposit
SEM shows nanobelts
2.6 A
TEM: Nanobelts grow in the (101) planes
SnO 2
SEM: Nanobelts
Black Deposit
TEM: single crystal
Nanobelts: orthorhombic SnO
[110]
110 growth direction
10 20 30 40 50 60 70 80
0 2000 4000 6000 8000 10000
# +
# +
* *
#*# +%
*
*
#
*
*
*
*
*
*
* SnO2
Intensidade / cps
2 / graus
# +
SnO Sn
XRD: SnO only
Sensor Response to NO 2 – Tin Oxides
Tin oxide nanobelts (SnO
2, SnO and Sn
3O
4).
Suman P.H. et al, manuscript in preparation.
High Selectivity– Tin Oxides
Tin oxide nanobelts (SnO
2, SnO and Sn
3O
4)
Sensor Signal – SnO
SnO nanobelt vs SnO disks
Disks presents Giant Chemo-response (GCR)
Sensor Signal – SnO Disks
Sensor signal and selectivity of SnO disks.
Over 1000x increase in resistance even with
relatively low surface area !!
CaCu 3 Ti 4 O 12 (CCTO)
Ca +2 Cu +2 O -2
• TiO6
Non ohmic property Chung, 2004
Dielectric property Subramanian, 2000
• Intrinsic: electronic states
• Extrinsic: point, linear and planar defects,
electrode/sample interface
effects, microstructural and
general morphology (domains).
467 466 465 464 463 462 461 460 459 458 457 456 455 CCTO 72h
CCTO 20h 2p1/2
2p3/2
CCTO 3h
458
458.4
457.6 458.9
457.9
Intensity (a.u.)
459.1
Ti 2p
Binding Energy (eV)
946 944 942 940 938 936 934 932 930 928
Binding Energy (eV)
Intensity (a.u.)
933.2
934.8 934.5
933.3
CCTO 72h CCTO 20h CCTO 3h
2p1/2
2p3/2
931.5 931.6 935.2
933.4
931.7
Cu 2p
Samples TiO
5. /TiO
6Cu
+1/Cu
+2Dielectric constant (1KHz)
CCTO 3 h 0.21 0.80 k
3h= 13134
CCTO 20 h 0.27 0.85 k
20h= 27268
CCTO 72 h 0.52 0.92 k
72h= 380760
V
OCu
+2Cu
+1TiO
5.
V
OTiO
6Area ratio of the components detected by XPS
X-RAY
PHOTOELECTRON SPECTROSCOPY (XPS)
TiO
5. V
Oe
-C u Cu
Creation of polarons electronic defects
AFM and EFM of CCTO after sintering at 1100 °C for different times
Breakdown electrical field (E
b), leakage current (I
l) calculated at 20 % of the breakdown electrical field and nonlinear coefficient () obtained for the CCTO system
J (current density) versus E (electric field) plot obtained for the CCTO polycrystalline system
-50 -40 -30 -20 -10 0 10 20 30 40 50
-0,03 -0,02 -0,01 0,00 0,01 0,02 0,03
compliance: 10 mA
E (V.cm-1)
CCTO 72 h
= 3 Il = 260 A Eb = 14 V.cm-1
J (A.cm-2 )
1 mA.cm-2 -2500 -2000 -1500 -1000 -500 0 500 1000 1500 2000 2500
-0,03 -0,02 -0,01 0,00 0,01 0,02 0,03
E (V.cm-1) J (A.cm-2 )
= 5
Compliance: 10 mA
Eb = 1181 V.cm-1
1 mA.cm-2
Il = 177 A
CCTO 3 h
-1600 -1200 -800 -400 0 400 800 1200 1600 -0,03
-0,02 -0,01 0,00 0,01 0,02 0,03
Compliance: 10 mA
CCTO 20 h
E (V.cm-1) J (A.cm-2 )
= 3
Il = 250 A Eb = 600 V.cm-1
1 mA.cm-2