UNIVERSITY OF SO PAULO

SCHOOL OF DENTISTRY
DEPT. OF BIOMATERIALS AND ORAL BIOLOGY

Reinforcement of Y-TZP with carbon nanotubes

using different coprecipitation techniques
L. Silva, D. Lazar, V. Ussui, W. Yoshito, R. Tango, U. Lohbauer, P. Cesar*

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INTRODUCTION
Reinforcement of ceramics with second-phase particles/fibers

Sgura et al., 2012

 Reinforcement of dental ceramics:

Cesar et al., 2012

Mechanical behavior

Kaizer et al., 2015

Optical properties

 Reinforcement of dental ceramics with Al2O3/GdAlO3 particles

Al2O3/GdAlO3 particles

dental porcelain

Medeiros et al., 2009

J Mech Behav Biomed Mater

Addition of saphire to dental porcelain

Kaizer et al., 2015

Addition of saphire to dental porcelain

saphire

dental porcelain

Control

Porcelain
+
saphire

Addition of potassium titanate whiskers to dental porcelain

Addition of potassium titanate whiskers to dental porcelain

Flexural strength (MPa)

Translucency

Control

51.3 4.9b

Porcelain
+
Whiskers

76.5 11.0a

Translucency Parameter

30
25
20
15

10
5
0

control

Porcelain
+
whiskers

Effect of processing method on porosity (%) of dental porcelains

Sintered: 4.0 1.1a

Hot-Pressed : 0.3 0.2b

Addition of Nanotubes to Y-TZP

Multi-Wall Carbon NanoTube
(MWCNT)

Y-TZP

+
Yu et al. (2000)

Borba et al. 2010

 MWCNT (Multi-Wall Carbon NanoTube)

Hardness: ~500 GPa

MWCNT

Strength: ~30 GPa

Elastic Modulus: 950 GPa
Yu et al. (2000); Ando (2010)

Addition of Nanotubes to Y-TZP

Crack bridging
Hinders Low-Temperature Degradation

Garmendia et al. (2010)

Functionalized nanotubes (white shade)

MWCNT-COOH
Jagadeesan et al. (2010)

Technological challenge re: adding nanotubes to Y-TZP

Avoiding CNT degradation during processing;

Achieving good dispersion of CNT on the Y-TZP matrix.

 Achieving good dispersion of CNT on the Y-TZP matrix

Synthesis of Y-TZP powders

Zr(OH)4 + Y(OH)3

Nanotube

+ Nanotube
150C
150 RPM
6.8 atm
pH 10
16 h

Y-TZP

WATER OR ALCOHOL

???

OBJECTIVES
To compare two synthesis techniques:
Water-based (hidrothermal)
Alcohol-based (solvothermal)

used to facilitate the dispersion of multi-walled carbon nanotubes

(CNT) into an yttria-stabilized tetragonal zirconia pollycristal (Y-TZP).

Hypothesis: both techniques will be sucessful in producing the new

composite.

METHODS
Coating of Nanotubes with zirconia/yttria (synthesis)

Zr(OH)4 + Y(OH)3
4g

Nanotube
75 mg (~5 vol%)

 Functionalized nanotubes (Nanoshell)

 Coating of Nanotubes with zirconia/yttria (synthesis)

150 C
150 RPM

6.8 atm
pH 10

16 h

WATER OR ALCOHOL

 Coating of Nanotubes with zirconia/yttria

Y-TZP powder coating nanotubes (CNT/ZYO)

 Coating of Nanotubes with zirconia and yttria

Y-TZP powder coating nanotubes (CNT/ZYO)

After filtering, washing and drying

Breaking clusters

 Transmission electron microscopy

Y-TZP powder coating nanotubes (CNT/ZYO)

 Experimental groups (starting powders):

1. Control: Y-TZP commercial powder from Tosoh (TZ3YE)

2. Composite A: 1 vol% of CNT/ZYO (processed in water) + TZ3YE
3. Composite B: 1 vol% of CNT/ZYO (processed in alcohol) + TZ3YE

 Specimen production
Green discs (15 x 2 mm)
Uniaxial pressing (67 MPa)

n=3

 Sintering in argon atmosphere

Inert atmosphere (argon)
1,400 C /4 h
Heating rate: 5 C/min

 Mirror polishing

 Characterization of experimental groups

Density (Archimedes principle)

Relative Density (based on Helium picnometry)
Indentation fracture toughness and Vickers hardness
Optical properties (Contrast Ratio, L*a*b*, and color difference)

Data analyzed by t-Student test (alpha = 0.05)

RESULTS
Macroscopic aspect after sintering

Control (Y-TZP)

Y-TZP + Nanotubes
(processed in water)

Y-TZP + Nanotubes
(processed in alcohol)

 Density
(p=0.14)

(RD:95.3%)

(RD:94.9%)

 Hardness
(p=0.25)

 Fracture toughness
(p=0.39)

 Optical properties (contrast ratio)

(p=0.12)

 Optical properties (color difference)

D E = 6.0 3.1

Control (Y-TZP)

Y-TZP + Nanotubes
(processed in water)

 Optical properties (CIE L*a*b* coordinates)

(more white)

(less yellow)

(more red)

CONCLUSION
Solvothermal technique (i.e., using alcohol) caused
severe discoloration of the Y-TZP/nanotube composite;
Hydrothermal technique (i.e., using water) resulted in
Y-TZP/nanotube composite with small color difference
in comparison to the control;
However, mechanical properties of the produced YTZP/nanotube composite were not significantly
improved by the addition of CNT.
Supported by FAPESP
2012/16027-2

Thank you!
paulofc@usp.br