Ceramio letter

Journal of the Ceramic Society of Japan 107 [1] 92-95 (1999)

Differences in the Tetragonal to Monoclinic Phase Transformation Rate in

Hot Water of 3mol% Y2O3-ZrO2 Ceramics under Different
Surface Conditions
Shietaka WADA and Kazushige YOKOYAMA*
Toyota Central R & D Labs., Inc., Nagakute, Aichi 480-1192
*Toyota Technological Institute
, Hisakata, Tenpaku-ku, Nagoya-shi 468-8511

表 面 状 態 の 異 な る3mol% Y2O3-ZrO2セ ラ ミ ッ ク スの 熱 水 中 に お け る 正 方 晶 か ら
単 斜 晶 へ の 転移 速 度 の 違 い

和 田重 孝 ・横 山和 成*
(株)豊田中央研究所, 480-1192愛 知郡長久手町
*豊田工業大学, 468-8511名 古屋市天白区久方

Hot-isostatic-pressed (HIP'd) tetragonal zirconia ceramic containing 3mol% Y2O3 was soaked in hot water
at 95-100•Ž to evaluate the transformation rate from the tetragonal (T) to the monoclinic (M) phase. The
transformation rate differed considerably between the polished surface and the surface cut by a diamond
wheel. After about 1000h of soaking in hot water, the volume of the M-phase was 50% in the cut surface and
less than 20% in the polished surface. Tetragonal ZrO2 with polished and cut surfaces were annealed at
1000•Ž for 2h in air. When the annealed specimens were soaked in hot water, the transformation rate in the
cut surface was the same as that before annealing; on the other hand, the M-phase volume in the polished sur
face increased to 70% after 1000h of soaking. Surface roughness, a rhombohedral phase generated by cut
ting or machining and orientation of the T-phase crystal due to machining, are thought to be causes of the
transformation rate change. However, not one of them on its own could explain all the phenomena without
contradiction. [Received September 8, 1998; Accepted November 6, 1998]

Key-words: Zirconia, Tetragonal, Monoclinic, Transformation, Surface

1. Introduction 3. Results and discussion

The fact that tetragonal zirconia transforms to the The relationships between the M-phase content and soak
monoclinic phase and that the ceramic decreases its ing time in hot water for both polished and cut surfaces are
mechanical strength dramatically upon low-temperature an shown in Fig. 1. In cut surfaces, the M-phase content ob
nealing (200-300•Ž in air) have been well known for 17 viously increased faster than those in polished surfaces.

years.1)-3) The transformation also occurs in water at less One of the factors which affected the transformation rate
than 100•Ž, although the transformation rate is slow.2),4) was assumed to be the surface roughness. That is, a surface
The tetragonal to monoclinic (T•¨M) transformation with high roughness has a large specific surface area. Conse
rate is accelerated by the absorbed water,5),6) as well as quently, the area exposed to water is larger. The surface
affected by the content of yttrium oxide, content of Al2O3 roughness of the two surfaces were measured by Surf
and the grain size of the ceramics.7),8) However, the effect corder (SEF-3400, Kosaka Labs., Ltd.). The mean
of the surface conditions on the T•¨M transformation rate roughness of the cut surface, 0.2-0.3ƒÊm, was about ten to
has not been reported. twenty times greater than that of the polished surface,
In the present study, the T•¨M transformation rate in hot 0.015ƒÊm.
water was observed, using HIP'd zirconia ceramics under It is well known that the rhombohedral (R) phase is
different surface conditions, i.e., roughness, machining
and/or annealing.

2. Experimental procedure
HIP'd, commercially available 3mol% Y2O3-ZrO2
ceramic was used as the specimen. The bulk density of the
specimen was 6.05g/cm3 and the average grain size was
0.4ƒÊm. The size of the specimen was 15•~15•~5mm3. A
15•~15mm2 surface was polished, while a 15•~5mm2 sur
face was cut by a diamond wheel.
The specimens were set on the bottom of a triangular
beaker having a capacity of 500cm3, which was filled with
distilled water. The beaker was then soaked in a water bath
at 95-100•Ž.
The phase contents of the tested surfaces were determin
ed by X-ray diffraction (XRD) analysis (Cu-target) after
different dipping periods. The volume ratio of M/T was Fig. 1. Relationship between monoclinic content and soaking
calculated from the peak height, M(111)+M(111)/ time in hot water for cut surfaces and polished surfaces: upper and
M(111)+M(111)+T(111).9) lower surfaces refer to the position of the surface in hot water.

92
 Shigetaka WADA et al. Journal of the Ceramic SocietyofJapan 107 [1] 1999 93

Fig. 2. X-ray diffraction profiles of (A) polished surface, (B) cut surface, (C) annealed surface of (A), (D) annealed surface of (B), and
(E) 500h-soaked surface of (D).

generated by the machining of T-phase ceramics, and the fi nding that the cut surface followed by annealing did not
peak corresponds to T (111) tails in the lower angle become stable, is comprehensible. Although the data in Fig.
side.10),11) As seen in Fig. 2, the T (111) peak of cut surface 3 (B) exhibit a large fluctuation and were taken from only
(B) shows a larger tail than that of polished surface (A). two specimens, other data, which are not shown here, for
Stress caused by the generated R-phase was also surfaces ground with a diamond wheel showed a similar
hypothesized to affect the transformation rate. tendency.
To eliminate the generated R-phase, specimens were In Fig. 1, the M-phase content in the upper side of the
heat-treated at 1000•Ž for 2h in air.10) The annealed polished surface increased rapidly after about 1500h. On
specimens were quenched in air at room temperature to the other hand, that of the lower surface increased gradual
avoid the T•¨M transformation. The surface roughness ly until 2700h. The lower surface came into contact with
showed no change after the heat treatment. As seen in Figs. the beaker bottom. There was no temperature difference
2 (C) and (D), the tails of the T (111) peak vanished entire between the upper and lower surfaces, because the beaker
ly, that is, the R-phase vanished upon annealing. was soaked in a water bath. After 1000h of soaking, many
Annealed and non annealed specimens were soaked in small white precipitates, which floats in the water with a
hot water. Figure 3 shows the M-phase content of four slight shake, were observed. The precipitates were analyz
kinds of surfaces as a function of the soaking time. The ed by fluorescence X-ray diffraction. The ratios of Zr ions to
polished surface before annealing showed a similar M Y ions were 1:0.064 for the precipitates and 1:0.068 for
- phase content vs time relation as that in Fig. 1. The polish the original ceramics. The precipitates were considered to
ed and annealed surface showed a very fast transformation be a hydrate of Zr and Y ions dissolved in water, from the
rate. The X-ray profile of the specimen after 500h of soak zirconia ceramic. Water around the upper surface is cir
ing is shown in Fig. 2 (E). On the other hand, cut surfaces culated freely by convection. However, water in the gap bet
did not show distinct differences. We expected the T-phase ween the lower surface and the bottom of the beaker might
of the polished surface followed by annealing to be more not move easily. Then, the concentration of Zr and Y ion in
stable than that of the just-polished surface and the T-phase water in the gap might be higher than that around the upper
of the cut surface followed by annealing to become more surface. Based on these discussions, it is speculated that the
stable than that of the just-cut surface. Results shown in T•¨M transformation rate is suppressed by the high concen
Fig. 3 were contrary to our predictions. tration of Zr and Y ions in water.
The third factor which may affect the transformation rate Figure 4 shows the relation between the M-phase content
is the ferroelectric domain switching of the T-phase and the and the distance from the surface of the specimen in Fig. 1
resultant stress.12) The peak height of T (200) is higher after 2700h of soaking. The surfaces were ground manual
than that of T (002) in the polished surface, as seen in Fig. ly with abrasive paper. The layer of M-phase could be
2 (A) . For the as-fired surface, the relations are the same. ground very easily, like chalk. Although the T•¨M transfor
However, the peak height of T (002) becomes higher than mation rate is faster in the cut surfaces than that in polished
that of T (200) when the T-phase zirconia ceramic was surface, as seen in Fig. 1, the depth of the layer including
machined.12) Also, in this experiment, T (002)>T(200) in the M-phase is greater in polished surface than in the cut
the cut surface (Fig. 2 (B)). The relation did not change surfaces. The reason for this discord cannot be explained
after annealing, as seen in Fig. 2 (D). If the stress induced here.
by ferroelectric domain switching is the cause of the in The scanning electron microscope (SEM) micrographs
stability of the T-phase, the result in Fig. 3 (B), that is, the of a fractured section normal to the polished surface is
 Differences in the Tetragonal to Monoclinic Phase Transformation Rate in Hot water
94 of 3mol% Y2O3-ZrO2 Ceramics under Different Surface Conditions

Fig. 3. Relationship between monoclinic content and soaking

time in hot water before and after annealing for (A) polished sur
face and (B) cut surface. One circle corresponds to one specimen.

Fig. 5. SEM micrographs of (A) broken surface, (B) monoclinic

phase region and (C) tetragonal-phase region.

shown in Fig. 5. The surface warped at about 20ƒÊm from

the surface, as seen in Fig. 5 (A). This corresponds to the
distance at which the M-phase diminishes to almost zero in
Fig. 4. The microstructure in the surface layer and the in
ner bulk are shown in Figs. 5 (B) and (C). Some of the frac
tured faces of the inner bulk are at intra-grains. On the
other hand, fracture occurred only at grain boundaries in
the surface layer. Grain boundary fracture results from the
stress generated by the T•¨M transformation.
Experiments similar to those described above were car
ried out for the specimens sintered and HIP'd by us using
TZP-3Y (Y2O3 3mol%-ZrO2, Tosoh Co.) powder. The as
fi red surface of a normally sintered specimen (mean

Fig. 4. Monoclinic content for polished surface and cut surfaces roughness: 0.6ƒÊm) showed a rather fast transformation
as a function of the distance from the surface. rate similar to that of the cut surface in Fig. 1. On the other
 Shigetaka WADA et al. Journal of the Ceramic SocietyofJapan 107 [1] 1999 95

hand, the T•¨M transformation rate of surface ground us of the transformation rate change. However, not one of
ing a# 400 diamond wheel (mean roughness: 0.07ƒÊm) was them on its own could explain all the phenomena without
almost the same as that of the polished surface in Fig . 1. In contradictions.
HIP'd specimens, the T•¨M transformation rates of as
HIP'd and ground surfaces were similar to that of normally Acknowledgments We would like to acknowledge valuable
sintered specimens. discussions with Jing-Feng Li from Tohoku Univ., and H.
As mentioned above, the T•¨M transformation rates of Hasegawa and T. Okamoto from Toyota CRDL.
TZP were strongly affected by the surface conditions . In
practical applications, this fact should be considered in the
design stage. In particular, the surface of ceramic com References
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