Ceramic Engineering and Science Proceedings Ersan Ustundag & Gary Fischman

1999 The American Ceramic Society

GAS PRESSURE SINTERING SILICON NITRIDE CERAMICS USING RARE EARTH AND TRANSITION METAL AS SINTERING AIDS

A.J.N.Dias'; J.Duailibi Fh';C. A.Vilardo', T.C.Silva', M.C.S.Nobrega2

1 - Instituto Nacional de Tecnologia Av. Venezula 821603 - Rio de Janeiro RJ - Brazil CEP 2008 1-310

2 - COPPE/UFRJ Cidade Universithia, bl F-204 Rio de Janeiro - RJ - Brazil

ABSTRACT

Silicon nitride ceramics with additions of 3wt.% of yttria together with 2wt% of rare earth and transition metals oxides, were gas pressure sintered using multiple steps of temperature and pressure. Compositions containing La~03, Nd203 and Sm203, and the transition metals oxides, Cr203, Cd203 and TiO2, were tested. The results showed that gas pressure sintering (GPS) is a possible way to process these ceramics to high density. Also, the final density and aspect ratio of p-Si3N4 grains are strongly dependent of soaking time in the last step of temperature and pressure.
INTRODUCTION

High temperature mechanical properties of silicon nitride ceramics are mainly governed by the amorphous grain-boundary phase remaining fiom liquid phase sintering.('*2) Attempts to improve the mechanical properties have been directed to modifL the constitution and reduce this grain-boundary phase.'3' G a s pressure sintering (GPS) enables densification of this ceramics employing lower quantities of sintering additives or more refractaries ones, because the high pressure nitrogen gas depresses thermal decomposition of silicon nitride even at temperatures higher than 1850C. The high nitrogen pressure is also beneficial to the formation of silicon nitride ceramics with high aspect ratio of p-Si3N4grains and nitrogen enriched phases at grain boundaries which improve the high temperature mechanical properties of this material.(475) Previous works have been showed that it is possible to dens@ silicon nitride ceramics employing quantities of sintering additives as low as 5 wt.% (6) and using more refractaries systems using rare earth oxides"-9' and transition metal oxides'") that leads to grain boundary phase with high softening temperature. The aim of this work was to study the densification, fracture toughness and microstructure of silicon nitride ceramics employing 3 wt.% of yttria together with 2wt% of rare earth oxides, La203, Nd203
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and Sm203, and 2wt% of transition metals oxides, Cr203, Cd203 and Ti&, sintered by GPS using multiple steps of temperature and pressure.

MATERIALS AND METHODS

High purity Si3N4, Y203, Nd203, SmzO3, Cr203, TiO2, and CdO were used for the preparation of compositions, as shown in Table I.
Table 1. Compositions and Theoretical Density (dt)

CODE 3Y IT 3Y2T 3Y2Cr 3Y2Cd 3Y2N 3Y2S 3Y2L

COMPOSITION 96%Si3N4 - 3%Y203 - 1%Ti02 95%Si3N4 - 3%Y203 2%Ti02 95%Si3N4 - 3%Y203 2%Cr203 95%Si3N4 - 3%Y203- 2%CdO 95% Si3N4 - 3% Y2O3 2% Nd2O3 95%Si3N4 3%Y203 2%Sm~03 95% Si3N4 3% Y2O3 - 2% La203

dt (g/cm3) 3,219 3,225 3,239 3,253 3,250 3,254 3,247

All compositions were milled during 6 hours in an attrition mill using ethyl alcohol P.A. as a fluid. After drying, the mixtures were sieved through a 65 mesh screen to eliminate large agglomerates and, then, uniaxialy pressed at 60 MPa. Samples were initially heated at 600C for 2 hours to eliminate the binder added during the milling (PEG).After that, they were placed in a graphite crucible coated with boron nitride and gas pressure sintered in a high pure nitrogen atmosphere, according to two sintering conditions, as follows:

1 - Multiple step sintering, with the first step similar to the normal sintering at 1750"C, with soaking time of 40 min. At the end of this step the pressure w a s increased to 40 bar and temperature simultaneously i n c r d to 1950C w i t ha heating rate of lO"C/min. Mer 15 min. at 1950"C, the pressure was raised to 100 bar, with a 15 min. soalung time at 1950C.
2 - The same condition of cycle 1 except for the soaking time of the last step, which were 4h.

Using a ddatometer coupled in the GPS furnace, it was determined the densification curve and the densification rate along the process of some compositions. The samples density were determined by Archimedes method and compared with theoretical density of each composition investigated and calculated

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from the density values of each component according to the phase rule. Fracture toughness was measured by Vickers indentation method using a load of 10 N.

RESULTS AND DISCUSSION

The Table I1 shows the final densities for each composition sintered according to the cycles 1 and 2. Table 11. Relative density in percentage of theoretical density (%dt)

COMPOSITION 3Y IT 3Y2T 3Y2Cr 3Y2Cd 3Y2N 3Y2S 3Y2L

1750"C/40 min. 1950 "C/30 min. 91.5 92.9 90.3 90.7 90.8 89.9 99.4

1750" a 4 0 min. 1950 "C/4 h. 95.9 97.7 93.5 96.3 96.5 97.2 99.7

Although the conditions employed in cycle 1 were enough to promote densification closed to theoretical density in silicon nitride ceramics doped with yttria and alumina'6', those conditions were unsuitable to achieve high density values, except for the composition 3Y2L, with lanthanum oxide. The results also showed that 5 wt.% of these additive systems are insufficient to achieve density greater than 99 % even in this condition. The four hour soaking time employed in cycle 2, shows that to obtain silicon nitride ceramics with high density it is necessary longer soaking times at high temperatures. The reason to the lowest density values of composition 3Y2Cr is due to the high melting point of chromium silicides formed during the sintering. Analysis of densification rate curve for the composition 3Y2T show that the increase of pressure in the last stage of sintering doesn't have a perceptive effect on densification. It could explain the lower density of composition with titanium oxide than ones obtained when more refractory oxides were used. The Table I11 shows the fracture toughness of composition 3Y2L sintered according cycles 1 and 2 and compositions 3Y2N, 3Y2S and 3S2A sintered according cycle 2.

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Table III - Fracture Toughness I(Ic ( MPa.m"n)

COMPOSITION 3Y2L 3 Y2N 3Y2S

1750 "C/40min. 1950 "C/30min. 2.0 rt 0.4

1750 "C/40&. 1950 "C/4h 6.3 A 0.4 3.6 f 0.3 5.1+ 0.4

As it can be seen in Table 11, the better value of fracture toughness was achieved by the composition 3Y2L, reflecting its density and aspect ratio of pSi3N4 grain dependence. In spite of good densification obtained for the composition 3Y2L sintered according cycle 1 (30 min. Soaking time at 1950 "C), the fracture toughness was very low. The increase of soaking time in cycle 2 led to a better aspect ratio and, consequently, improved the fracture toughness, although some abnormal pain growth were observed. Figure 1 and 2 show, respectively, the microstructure of composition 3Y2L and 3Y2Cr after the end of cycle 1 and cycle 2, where the effect of soaking time on grain growth can be observed.

(b) 3Y2L - 1950 "C/4 h. (a) 3Y2L - 1950 "C/30 min. Figure 1: Effect of 4h soaking time over aspect ratio of p-Si3N4 grains in composition with 3wt.% of Yz03 and 2wt.% of La203

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(a) 3Y2Cr - 1950 "C/30 min.

(b) 3Y2Cr - 1950 "C/4 h.

Figure 2: Effect of 4h soaking time over aspect ratio of p-Si3N4 grains in composition with 3wt.% of YzO~ and 2wt.% of CrzO3

CONCLUSIONS
Density around 9 9 3 % of the theoretical density and KICof 6,3 MPa.m-ln for the composition containing 3wt% of yttria and 2wtY0 of lanthanum oxide as sintering adds, shows that gas pressure sintering is a feasible way to obtain high density silicon nitride ceramics with low quantities of sintering adds and more refractory grain boundary phase. The substitution of lanthanum oxide by the same amount of neodymium, samarium, chromium, cadmium and titanium oxides, has shown to be insufficient to obtain silicon nitride ceramics with densities closed to theoretical density, using the same gas pressure sintering conditions. However, the results obtained allow us to suppose that a small increase in the total amount of sintering adds w i l l lead high density bodies.

REFERENCES
(1)P.Arato and F. Weber, 'Development of Microstructure of Silicon Nitride During Pressure Sintering"; pp 1917 - 24 in Ceramics : Changing the Future, Edited by P. Vincenzine, Techna Srl, 1995.

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(2)G.S.Blugaq S.Mello Castanho, J.S.Moya and M.J.Reece, Mcrostructural Analysis of Si3N,-~~O3/Si3N,-Y,O3Couples to Investigate the Muence of Sinterhg Additives Microstructure; pp 199-204 in Fourth Euroceramics Vol. 9, Edited by B.S.Tmchina and A.Bellosi, Grmpo Editoriale Faenza Editrice, Italy,
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