Sintering of Yttria-Stabilized Zirconia Studied by Scanning Electron Microscopy

Roberto Salgado Amado1 *, Francisco M. S. Garrido1**, Rosa Cristina. D. Peres1, Paulo Emlio V. de Miranda2 and Marta Elosa Medeiros1
1

Institute of Chemistry UFRJ, Brazil.

2

COPPE UFRJ, Brazil. ** chico@iq.ufrj.br

* roberto@iq.ufrj.br

Introduction At room temperature, the zirconia has a monoclinic crystalline structure. Nevertheless, the addition of a certain amount of aliovalent oxides such as calcium, magnesium or yttrium oxides, could stabilize zirconia cubic structure, at room temperature, increasing the mobility of oxygen ions. This enhancement in the ionic conductivity makes the stabilized zirconia useful for electrochemical devices such as oxygen sensors and as solid electrolyte in fuel cells [1], Figure 1.

Figure 1: Solid Oxide Fuel Cell (SOFC) Objective

This work used scanning electron microscopy (SEM) to study the sintering of 8 mol% yttria stabilized zirconia (YSZ) for solid oxide fuel cell.

Experimental - A commercial YSZ (Kerafol) was used inthe preparation of cylindrical samples. - Surface micrographies were obtained for YSZ samples sintered during 3 hours at temperatures in the range of 1000 to 1400 C.

Results and Discussion The beginning of the sintering process was observed between 1000 (Figure 2) to 1100 C (Figure 3a), densities of 2.80 g.cm-3 (46.94%) and 2.92 gcm-3 (48.83%) respectively.

Figure 2: SEM of YSZ sintered at 1000 C.

Figure 3: SEM of YSZ sintered at 1100 (a) and 1200 C (b).

The formation of necks and edges between the particles was observed for the sample sintered at 1200 C (Figure 4), density of 3.79 g cm-3 (65.11%).

Figure 4: SEM of YSZ sintered at 1200 C.

The closing of almost all the pores is observed at 1300 C (Figure 5), density of 5.43 g cm-3 (92.93 %).

Figure 5: SEM of YSZ sintered at 1300 C.

At 1400 C (Figure 6), the sintering process was completed, with a small increment in the density (5.83 gcm-3 or 99.70 %).

Figure 6: SEM of YSZ sintered at 1400 C.

The sintered densities for each sintered sample were calculated from its size and mass, being expressed as a percentage of the theoretical density, Figure 7.

Figure 7: The effect of sintering temperature on the sintered density.

Conclusion - The best temperature for densification of YSZ (Kerafol) was 1400 C, sintered density of 5.83 g cm-3 (99.70% of the theoretical density). - These results were similar to the ones reported at the literature for other types of YSZ commercial powders sintered at 1500 C, which presented sintered densities between 98.2 to 99.7% [2,3].

Acknowledgements The authors gratefully acknowledge the Laboratory of Eletron Microscopy

PEMM/COPPE/UFRJ, Capes and CNPq.

References [1] Amado, R.S.; Malta, L.F.B.; Garrido, F.M. S. e Medeiros, M. E., Qumica Nova, 2007, 30, 189. [2] Badwal, S. P. S., Solid State Ionics, 1995, 76, 67. [3] Gibson, I.R., Dransfield, G.P., Irvine, J.T.S., Journal of Materials Science, 1998, 33, 4297.

SINTERING OF NANOCRYSTALLINE SAMARIA DOPED CERIA

F.R. Caldas, L.B. Alves, J.O. Guimares, R.C.D. Peres, F.M.S.Garrido, M.E.Medeiros.

Instituto de Qumica/UFRJ, Rio de Janeiro, Brazil

e-mail:chico@iq.ufrj.br

Ceria based oxides are highly refractory in nature, sintering of these compounds to obtain high density ceramics is a challenging task. The high sintering temperatures around 1400 1600 0C of these materials can cause the reduction of Ce 4+ to Ce3+ and promote the formation of large grains and poor mechanical stability. To overcome these problems, in this work nanocrystalline samaria doped ceria (SDC) based oxides have been prepared by a soft chemical route for getting dense ceramics at lower sintering temperatures. A nanocrystalline precursor of samarium doped cerium hidroxicarbonate were prepared by the addition of a samarium and cerium nitrate solution over a ammonium carbonate solution, the solid formed was isolated by centrifugation and washed with water to pH = 7.0. The thermal behavior of the nanocrystalline precursor was studied in the 500-1000 0C temperature range. Nanocrystalline NiO and cobalt doped NiO (NiOC) were prepared by a sol-gel method using nickel or nickel and cobalt nitrate solution and starch as a gel former, the xerogel formed was calcined at 400 0C for 4 hours. Samples of SDC calcined at diferent temperatures or a mixture of 53% (w/w) of SDC and 47% (w/w) of NiO or NiOC were pressed under 200 Mpa and sintered in the temperatures of 1200 or 1250 0C. The samples were characterized by X-ray diffraction (DRX) and infrared spectra (IR). The densities of the sintered bodies were measured by the Archimedes method. The crystallite sizes for the SDC samples thermal treated at 500 and 700 0C were 8 and 16 nm (Scherrer formula), respectively. The results of relative density for the sintered bodies were in the range between 62.2 (SDC heated at 700 0C) and 98.6 % (SDC/NiO), for the samples sintered at 1200 0C. From ours results we could conclude: i) the SDC crystallite size was dependent of the thermal treatment; ii) was observed an increase in the sintered degree with the decrease of the SDC crystallite size and iii) the presence of NiO or NiOC increases the sintered degree for the bodies prepared with the oxide mixture.

SINTERING OF NANOCRYSTALLINE SAMARIA DOPED CERIA

Fernanda R. Caldas (PG), Luana B. Alves (IC), Julliana O. Guimares (IC), Marta E. Medeiros (PQ) e Francisco M. S. Garrido (PQ). chico@iq.ufrj.br
Departamento de Qumica Inorgnica - Instituto de Qumica - UFRJ

Introduction
Ceria based oxides are highly refractory in nature, sintering of these compounds to obtain high density ceramics is a challenging task. The high sintering temperatures around 1400 1600 0C of these materials can cause the reduction of Ce 4+ to Ce3+ and Table 1: Variation of particle size (Scherrer formula) with thermal treatment. Sample S3 S3 S3 S3 S3 S3 Temperature (C) 50 500 600 700 900 1000 D (nm) 2 6 9 15 37 64

promote the formation of large grains and poor mechanical stability. In this work nanocrystalline samaria doped ceria (SDC) have been prepared by a soft chemical route for getting dense ceramics at lower sintering temperatures.

Experimental
Sm2O3 + HNO3 + (NH4)2Ce (NO3)6 +H2O
88

NH4OH + (NH4)2CO3
86

Tamanho de partcula x sinterizao

84

Aging and Isolation

sinterizao(%)

Sintering (%)

82

80

Thermal Treatment

78

Sintering

76

74 4 6 8 10 12 14 16

Results and Discussiona

Was observed a decrease in the width of the XRD peaks for the SDC samples thermal treated from 50 to 1000 0C (Figure 1). The results of relative density for the sintered bodies shows a increase with the decrease of the SDC particle size (Figure 2). For the samples sintered at 1250 0C was observed a increase in the relative density.
( u . a . )

Tamanho de partcula (nm)

Particle size (nm)

Figure 2: Particle size and sintering at 1200 oC

SDC Samples 600 C Sintering 1200 C SDC/NiO SDC/NiOC Figure 3: Sintering of SDC and Ni.

83,4 % 93,7 % 98,6%

1 0 0 0

s i d a d e n t e n (u.a.) I Intensity

2 4 0 0 2 0 0 0 1 6 0 0 1 2 0 0 8 0 0 4 0 0

Conclusion
7 0 0

i) The SDC crystallite size was dependent of the thermal treatment (Table 1). ii) It was observed an increase in the sintered degree with the decrease of the SDC crystallite size. iii) The presence of NiO or NiOC increases the sintered degree for the bodies prepared with the oxide mixture (Figure3).
7 0

2 0

3 0

4 0

5 0

6 0

7 0

5 0 0
8 0 0

7 0 0

6 0 0 2 0

3 0

4 0

5 0

6 0

5 0

Acknowledgement
IMA/UFRJ, CNPq/CT-Energ, CNPq/PIBIC, FAPERJ, CAPES.

5 0 0

4 0 0

3 0 0

2 0 0

2 0

3 0

4 0

5 0

6 0

7 0

References
1. Li, J.G.; Ikegami, T.; Mori, T., Acta Mater. 2004, 52, 2221.

T h e t a

2 Theta (degrees)

( g r a u s )

Figure 1: XRD of SDC phases obtained at different temperatures.

2. Amado, R.S.; Malta, L.F.B.; Garrido, F.M. S. e Medeiros, M. E., Qum. Nova 2007, 30, 189. 3. Banerjee,S.; Devi, P.S., Solid State Ionics 2008, 179, 661.

Conclusion From ours results we could conclude: i) the SDC crystallite size was dependent of the thermal treatment; ii) was observed an increase in the sintered degree with the decrease of the SDC crystallite size and iii) the presence of NiO or NiOC increases the sintered degree for the bodies prepared with the oxide mixture

References 1. Li, J.G.; Ikegami, T.; Mori, T., Acta Mater. 2004, 52, 2221. 2. Amado, R.S.; Malta, L.F.B.; Garrido, F.M. S. e Medeiros, M. E., Qum. Nova 2007, 30, 189. 3. Banerjee,S. ; Devi, P.S., Solid State Ionics 2008, 179, 661.