JP3214048B2 - Zirconia sintered body and its manufacturing method - Google Patents
Zirconia sintered body and its manufacturing methodInfo
- Publication number
- JP3214048B2 JP3214048B2 JP08496592A JP8496592A JP3214048B2 JP 3214048 B2 JP3214048 B2 JP 3214048B2 JP 08496592 A JP08496592 A JP 08496592A JP 8496592 A JP8496592 A JP 8496592A JP 3214048 B2 JP3214048 B2 JP 3214048B2
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- Japan
- Prior art keywords
- sintered body
- mol
- oxide
- zirconia sintered
- cerium oxide
- Prior art date
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- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は熱耐久性に優れた高い機
械的強度を有するジルコニア焼結体に関するものであ
る。本発明のセラミックスは、切削または切断用工具
類、各種ダイス、ノルズ、などの構成材料としての用途
に好適である。しかし、このセラミックスはこの用途に
制限されるものではない。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zirconia sintered body having excellent heat durability and high mechanical strength. The ceramic of the present invention is suitable for use as a constituent material for cutting or cutting tools, various dies, knurls, and the like. However, this ceramic is not limited to this application.
【０００２】[0002]
【従来の技術】高強度・高靭性ジルコニア焼結体とし
て、ジルコニアに酸化マグネシウム、酸化カルシウム、
酸化イットリウム又は酸化セリウムを添加した部分安定
化ジルコニア焼結体がすでに知られている。このうち、
主流である酸化イットリウムを３モル％含む部分安定化
ジルコニア焼結体は、強度が強いが熱安定性に劣るとい
う欠点を有する。一方、酸化セリウムを１２モル％含む
ジルコニア焼結体は熱安定性に優れているが、三点曲げ
強度が約５０ｋｇ／ｍｍ２であり、強度的に劣ってい
る。この原因は、焼結体の粒径が１μｍ以上と大きいこ
とであると考えられる。 特開平３−１５９９６０公報
に酸化セリウムと少量のアルカリ土類金属酸化物を添加
したジルコニア焼結体の機械的特性が報告されている。
このジルコニア焼結体の機械的特性は酸化イットリウム
を３モル％含むジルコニア焼結体に比較し靱性が高いの
が特徴であるが、一方、強度に関しては約８０ｋｇ／ｍ
ｍ２と、従来の酸化セリウム系ジルコニア焼結体より
は、改善されているが、依然として、酸化イットリウム
を３モル％含む部分安定化ジルコニア焼結体の強度より
は劣る。2. Description of the Related Art Magnesium oxide, calcium oxide, and zirconia are used as zirconia sintered bodies with high strength and toughness.
A partially stabilized zirconia sintered body to which yttrium oxide or cerium oxide is added is already known. this house,
A partially stabilized zirconia sintered body containing 3 mol% of yttrium oxide, which is a mainstream, has a disadvantage that it has high strength but is inferior in thermal stability. On the other hand, a zirconia sintered body containing 12 mol% of cerium oxide has excellent thermal stability, but has a three-point bending strength of about 50 kg / mm 2 and is inferior in strength. It is considered that the cause is that the particle size of the sintered body is as large as 1 μm or more. JP-A-3-159960 reports the mechanical properties of a zirconia sintered body to which cerium oxide and a small amount of alkaline earth metal oxide are added.
The mechanical properties of this zirconia sintered body are characterized by a higher toughness than that of a zirconia sintered body containing 3 mol% of yttrium oxide, while the strength is about 80 kg / m2.
m 2, which is an improvement over a conventional cerium oxide-based zirconia sintered body, but still inferior to the strength of a partially stabilized zirconia sintered body containing 3 mol% of yttrium oxide.
【０００３】[0003]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、現在、部分安定化ジルコニア焼結体として
主流である酸化イットリウムを３モル％含むジルコニア
焼結体と同等の強度を有し、熱安定性に優れた酸化セリ
ウムを添加したジルコニア焼結体を提供することにあ
る。An object of the present invention is to provide a partially stabilized zirconia sintered body which has the same strength as a zirconia sintered body containing 3 mol% of yttrium oxide which is the mainstream. Another object of the present invention is to provide a zirconia sintered body to which cerium oxide having excellent thermal stability is added.
【０００４】[0004]
【課題を解決するための手段】ジルコニア焼結体の強度
に対する焼結体の粒子径の影響については、以前から検
討されており、例えば特公昭６１−２１１８４におい
て、酸化イットリウムを添加したジルコニア焼結体の粒
子径が２μｍ以下がよいと規定している。The effect of the particle size of the sintered body on the strength of the zirconia sintered body has been studied for a long time. For example, Japanese Patent Publication No. 61-21184 discloses a zirconia sintered body containing yttrium oxide. It is specified that the particle diameter of the body is preferably 2 μm or less.
【０００５】特開平３−１５９９６０公報における酸化
セリウム系ジルコニウム焼結体においては、焼結体の粒
子径は１．３〜１．５μｍであり、この粒子径をもっと
小さく出来れば、酸化イットリウムを３モル％含むジル
コニア焼結体と同等以上の強度を有し、熱安定性に優れ
た酸化セリウムを添加したジルコニア焼結体が製造でき
ると考えた。従って、鋭意検討した結果、高強度を有
し、熱安定性に優れた酸化セリウム系ジルコニア焼結体
及びその製造方法を検討した結果、焼結体の粒子径を
０．５μｍ以下に制御した酸化セリウム系ジルコニア焼
結体を初めて得た。In the cerium oxide-based zirconium sintered body disclosed in JP-A-3-159960, the particle size of the sintered body is 1.3 to 1.5 μm. It was considered that a zirconia sintered body to which cerium oxide was added, which had a strength equal to or higher than that of a zirconia sintered body containing mol% and had excellent thermal stability, could be produced. Thus, a result of intensive studies, have high strength, thermal stability superior ceria zirconia sintered body and the results of studying the production method, the particle size of the sintered body
A cerium oxide-based zirconia sintered body controlled to 0.5 μm or less was obtained for the first time.
【０００６】さらに、酸化セリウム添加量を９〜１１モ
ル％とし、酸化カルシウムの添加量を０．７〜１．２モ
ル％にして、添加量を最適化することにより、結晶相が
完全に正方晶となり、三点曲げ強度が、従来の酸化セリ
ウム系ジルコニア焼結体では得られなかった１００ｋｇ
／ｍｍ２以上のジルコニア焼結体が得られることも明ら
かにし、本発明を完成するに至った。Further, the amount of cerium oxide is set to 9 to 11 mol%, and the amount of calcium oxide is set to 0.7 to 1.2 mol%, and the crystal phase is completely squared by optimizing the addition amount. 100 kg, which cannot be obtained with a conventional cerium oxide-based zirconia sintered body
/ Mm 2 or more, a zirconia sintered body was obtained, and the present invention was completed.
【０００７】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【０００８】本発明に用いた安定化剤添加量は、通常
は、酸化セリウムが７〜１４％、酸化カルシウムが０．
２〜２モル％であり、好ましくは、酸化セリウムが８〜
１４モル％、酸化カルシウムが０．２〜１．５モル％で
ある。さらに、酸化セリウムが９〜１１モル％、酸化カ
ルシウムが０．７〜１．２モル％であると、さらに好ま
しい。The amount of the stabilizer used in the present invention is usually 7-14% for cerium oxide and 0.1% for calcium oxide.
2 to 2 mol%, preferably, cerium oxide is 8 to 2 mol%.
14 mol%, and 0.2 to 1.5 mol% of calcium oxide. Further, it is more preferable that cerium oxide is 9 to 11 mol% and calcium oxide is 0.7 to 1.2 mol%.
【０００９】酸化カルシウムは安定化剤としての寄与と
焼結体の粒成長を抑制する効果があることが知られてい
る（例えば、J.Am.Ceramics Soc., Vol. 73, P.3269-32
77(1990))。しかしながら、この文献中の酸化セリウム
−酸化カルシウム系ジルコニア焼結体でも平均粒子径は
１．０４μｍであり、平均粒子径が１μｍ以下の酸化セ
リウム−酸化カルシウム系ジルコニア焼結体は得られて
いない。It is known that calcium oxide has a contribution as a stabilizer and an effect of suppressing grain growth of a sintered body (for example, J. Am. Ceramics Soc., Vol. 73, P. 3269-). 32
77 (1990)). However, even the cerium oxide-calcium oxide zirconia sintered body in this document has an average particle diameter of 1.04 μm, and a cerium oxide-calcium oxide zirconia sintered body having an average particle diameter of 1 μm or less has not been obtained.
【００１０】酸化カルシウムの添加量が１．５モル％を
越えると、酸化カルシウムは正方晶よりも立方晶を作り
やすい為に、正方晶の割合が減少し、期待されるほどの
高い靭性と強度は得られない。If the amount of calcium oxide exceeds 1.5 mol%, calcium oxide tends to form a cubic crystal rather than a tetragonal crystal, so that the proportion of the tetragonal crystal decreases, and the toughness and strength as expected are high. Cannot be obtained.
【００１１】又、酸化カルシウムが０．２モル％未満の
場合には、粒成長抑制効果が小さい為に、期待されるほ
どの高い靭性と強度は得られない。When the content of calcium oxide is less than 0.2 mol%, the toughness and strength as expected cannot be obtained because the effect of suppressing the grain growth is small.
【００１２】従って、酸化カルシウムの添加量として
は、ジルコニア結晶相が主として正方晶となる、０．２
〜１．５モル％であることが好ましい。Therefore, the amount of calcium oxide to be added should be such that the zirconia crystal phase is mainly tetragonal.
It is preferably about 1.5 mol%.
【００１３】又、酸化カルシウムを添加すると靱性を下
げる方向にあるので、この効果を考慮に入れて酸化セリ
ウム含有量を低める必要がある。靱性値があまりに低す
ぎると強度がばらつき、かえって平均強度を下げ、信頼
性に欠ける焼結体になってしまう。この様なことから酸
化セリウム含有量としては、１４モル％以下でなければ
ならない。また酸化セリウムが７モル％未満では結晶相
が単斜晶であり、高強度が得られない。Since the addition of calcium oxide tends to lower the toughness, it is necessary to reduce the cerium oxide content in consideration of this effect. If the toughness value is too low, the strength varies, and on the contrary, the average strength decreases, resulting in a sintered body lacking reliability. Therefore, the content of cerium oxide must be 14 mol% or less. If the content of cerium oxide is less than 7 mol%, the crystal phase is monoclinic and high strength cannot be obtained.
【００１４】さらに酸化セリウムの添加量を９〜１１モ
ル％、酸化カルシウム０．７〜１．２モル％に範囲を絞
ることにより、焼結体の強度がさらに強くなり、三点曲
げ強度が１００ｋｇ／ｍｍ２以上となる。Further, by narrowing the addition amount of cerium oxide to 9 to 11 mol% and calcium oxide to 0.7 to 1.2 mol%, the strength of the sintered body is further increased, and the three-point bending strength is 100 kg. / Mm 2 or more.
【００１５】これらの焼結体は酸化セリウム系ジルコニ
ア焼結体の特徴である熱安定性に優れている。酸化イッ
トリウムを３モル％含むジルコニア焼結体は、１００〜
３００℃程度の比較的低温度のアニ−ルで正方晶が単斜
晶に転移し、強度低下してしまい、さらに劣化が進むと
焼結体が崩壊さえしてしまう。These sintered bodies are excellent in thermal stability which is a characteristic of the cerium oxide based zirconia sintered body. A zirconia sintered body containing 3 mol% of yttrium oxide is 100 to 100%.
At a relatively low temperature of about 300 ° C., the tetragonal crystal is transformed into a monoclinic crystal and the strength is reduced, and if the deterioration proceeds further, the sintered body may even collapse.
【００１６】例えば、鏡面研磨した焼結体試料を１７０
℃、水熱下に２４時間保持した後、生成単斜晶量をＸ線
回折試験で測定し熱安定性を評価した場合、従来の酸化
イットリウムを３モル％含むジルコニア焼結体は、５０
％以上単斜晶に転移してしまうのに対して、本発明のセ
リウム系ジルコニア焼結体は、正方晶から単斜晶に全く
転移しないか、或いはわずか５％以下しか単斜晶に転移
せず、熱安定性に優れているジルコニア焼結体である。For example, a mirror-polished sintered body sample is
C. for 24 hours under hydrothermal conditions, and the amount of monoclinic crystals formed was measured by an X-ray diffraction test to evaluate the thermal stability. The conventional zirconia sintered body containing 3 mol% of yttrium oxide was 50%.
% Or more, while the cerium-based zirconia sintered body of the present invention does not transform from tetragonal to monoclinic at all, or only 5% or less transforms to monoclinic. And a zirconia sintered body having excellent thermal stability.
【００１７】このようなジルコニア焼結体を作製するた
め原料粉末は、ジルコニウム塩、セリウム塩及びカルシ
ウム塩を用い、加水分解によって沈殿を得たのち、６０
０℃以上で焼成して得られる平均粒子径が０．５μｍ以
下の微粉末であることが必須である。これを越えると緻
密な機械的強度の高い焼結体を得られない。The raw material powder for producing such a zirconia sintered body is obtained by using a zirconium salt, a cerium salt and a calcium salt, and obtaining a precipitate by hydrolysis.
Average particle size obtained by firing at 0 ° C or more is 0.5 μm or less
It is essential that it be the fine powder below . If it exceeds this, a dense sintered body having high mechanical strength cannot be obtained.
【００１８】このことは、原料粉末を微粉化することに
より、酸化カルシウムが焼結体の粒成長を抑制する効果
がより発揮されることによると考えられる。このことに
より、本発明により初めて、焼結体の粒子径を０．５μ
ｍ以下に制御した酸化セリウム系ジルコニア焼結体得る
ことが出来、従来の酸化セリウム系ジルコニア焼結体で
は得られなかった１００ｋｇ／ｍｍ2以上のジルコニア
焼結体が得られた。This is considered to be due to the fact that, by pulverizing the raw material powder, calcium oxide exerts an effect of suppressing grain growth of the sintered body. As a result, for the first time according to the present invention , the particle size of the sintered body is reduced to 0.5 μm.
m was obtained, and a zirconia sintered body of 100 kg / mm 2 or more, which could not be obtained with a conventional cerium oxide-based zirconia sintered body, was obtained.
【００１９】尚、原料粉末の製造方法として、一度にセ
リウム塩及びカルシウム塩を添加する方法でも良いし、
或いは、最初にセリウムを添加して、セリウム系ジルコ
ニア粉末を製造した後、カルシウム塩を添加しても良
い。The raw material powder may be produced by adding cerium salt and calcium salt at once,
Alternatively, the calcium salt may be added after cerium is added first to produce the cerium-based zirconia powder.
【００２０】本発明によるジルコニア焼結体は、上記の
様にして製造された粉末を、例えばプレス成形で成形
し、大気又は酸素中１３５０〜１５５０℃で焼結して得
られる。焼結温度が１３５０℃未満では焼結体密度が低
く、また１５５０℃を越えると粒成長するため不適であ
る。The zirconia sintered body according to the present invention is obtained by molding the powder produced as described above, for example, by press molding, and sintering it at 1350 to 1550 ° C. in air or oxygen. If the sintering temperature is lower than 1350 ° C., the density of the sintered body is low, and if it exceeds 1550 ° C., the grains grow unfavorably.
【００２１】なお本発明のジルコニア焼結体は、焼結体
の特性を阻害しない範囲で、酸化アルミニウム等の不可
避的不純物を含んでいても良い。The zirconia sintered body of the present invention may contain unavoidable impurities such as aluminum oxide as long as the characteristics of the sintered body are not impaired.
【００２２】以下の実施例により、本発明を具体的に説
明するが、この実施例により、本発明は何等限定される
ものでない。The present invention will be described in detail with reference to the following examples, but the present invention is not limited by these examples.
【００２３】[0023]
【実施例】実施例中における三点曲げ強度と破壊靱性の
測定は以下の方法による。EXAMPLES In the examples, the three-point bending strength and the fracture toughness were measured by the following methods.
【００２４】三点曲げ強度測定は、板状焼結体を切断、
研削して３ｍｍ×４ｍｍ×４０ｍｍの角棒状試験片と
し、ＪＩＳ Ｒ １６０１に定められたスパン長さ３０
ｍｍ、荷重印加速度０．５ｍｍ／分の条件によって行
う。The three-point bending strength is measured by cutting a plate-like sintered body,
Grinding into a 3 mm x 4 mm x 40 mm square bar-shaped test piece, with a span length of 30 specified in JIS R 1601
mm and a load application speed of 0.5 mm / min.
【００２５】破壊靱性の測定は、鏡面研磨した焼結体試
料面にビッカ−ス圧子を打ち込み、圧痕長さと圧痕から
発生した亀裂長さとの比から値を算出するインデンテ−
ション法によって行う。圧子の打ち込み荷重は５０ｋｇ
とする。算出に用いる計算式はＪＩＳ Ｒ １６０７に
従う。The fracture toughness is measured by injecting a Vickers indenter into a mirror-polished sintered sample surface and calculating the value from the ratio of the length of the indentation to the length of the crack generated from the indentation.
It is performed by the method. The driving load of the indenter is 50kg
And The calculation formula used for the calculation conforms to JIS R1607.
【００２６】焼結体の粒子径の測定は、鏡面研磨した焼
結体を１３５０℃、１時間サ−マルエッチングを行った
後、走査型電子顕微鏡で観察し測定した。The particle size of the sintered body was measured by subjecting a mirror-polished sintered body to thermal etching at 1350 ° C. for 1 hour and then observing the same with a scanning electron microscope.
【００２７】焼結体の熱安定性は、１７０℃、水熱下、
２４時間の条件で劣化試験を行い、鏡面研磨した焼結体
試料面をＸ線回折試験し、その単斜晶量を測定した。単
斜晶率Ｘｍは以下の式により求めた。単斜晶の〈１１
１〉面、〈１１−１〉面、正方晶の〈２００〉面、立方
晶の〈２００〉面のＸ線回折強度をそれぞれＭ〈１１
１〉、Ｍ〈１１−１〉、Ｔ〈２００〉、Ｃ〈２００〉と
したとき、 Ｘｍ＝（Ｍ〈１１１〉＋Ｍ〈１１−１〉）／（Ｍ〈１１
１〉＋Ｍ〈１１−１〉＋Ｔ〈２００〉＋Ｃ〈２００〉） 又、平均粒子径は、遠心沈降光透過方式により測定し、
装置としては、堀場製作所製ＣＡＰＡ−７００型を使用
した。The thermal stability of the sintered body is as follows: 170 ° C., under hydrothermal conditions.
The deterioration test was performed under the condition of 24 hours, and the mirror-polished sintered body sample surface was subjected to an X-ray diffraction test to measure the amount of monoclinic crystal. The monoclinic fraction Xm was determined by the following equation. Monoclinic <11
The X-ray diffraction intensities of the <1> plane, the <11-1> plane, the tetragonal <200> plane, and the cubic <200> plane were respectively determined by M <11
1m, M <11-1>, T <200>, and C <200>, Xm = (M <111> + M <11-1>) / (M <11
1> + M <11-1> + T <200> + C <200>) The average particle diameter is measured by a centrifugal sedimentation light transmission method.
As a device, model CAPA-700 manufactured by Horiba, Ltd. was used.
【００２８】実施例１ 原料粉末は、以下の方法により調製した。Example 1 A raw material powder was prepared by the following method.
【００２９】オキシ塩化ジルコニウムの水溶液と塩化セ
リウム水溶液及び塩化カルシウムを所望の組成（酸化セ
リウム＝１２．４モル％、酸化カルシウム＝１．０モル
％）となるように混合し１００℃で１００時間、加熱を
続けて加水分解生成ゾルを得た。An aqueous solution of zirconium oxychloride, an aqueous cerium chloride solution and calcium chloride are mixed so as to have a desired composition (cerium oxide = 12.4 mol%, calcium oxide = 1.0 mol%), and the mixture is heated at 100 ° C. for 100 hours. Heating was continued to obtain a hydrolysis sol.
【００３０】これを蒸発乾固して得た粉末を９００℃で
仮焼し、次に分散媒にエタノ−ルを用いたボ−ルミルで
２０時間粉砕し、酸化セリウム−酸化カルシウム系ジル
コニア粉末を得た。The powder obtained by evaporating this to dryness was calcined at 900 ° C., and then ground with a ball mill using ethanol as a dispersion medium for 20 hours to obtain a cerium oxide-calcium oxide zirconia powder. Obtained.
【００３１】この酸化セリウム−酸化カルシウム系ジル
コニア粉末の平均粒子径は、０．４μｍであった。The average particle diameter of the cerium oxide-calcium oxide zirconia powder was 0.4 μm.
【００３２】次いで、前記原料粉末をラバ−プレス法に
よって、厚さ、幅、長さがそれぞれ４ｍｍ、３７ｍｍ、
５４ｍｍである板状成形体とした。この成形体を１５０
０℃の温度で１時間焼成し、本発明の酸化セリウム−酸
化カルシウム系ジルコニア焼結体を得た。Next, the raw material powder was subjected to a rubber press method to have a thickness, a width and a length of 4 mm, 37 mm, respectively.
A plate-shaped molded body having a size of 54 mm was obtained. This molded body is
It was calcined at a temperature of 0 ° C. for 1 hour to obtain a cerium oxide-calcium oxide-based zirconia sintered body of the present invention.
【００３３】三点曲げ強度は９３ｋｇ／ｍｍ２、破壊靱
性は３．５ＭＰａｍ1/2 、結晶相は１００％正方晶であ
り、焼結体の粒子径は０．５μｍであり、又、１７０
℃、水熱下、２４時間の条件での劣化試験後の単斜晶の
増加は観測されなかった。The three-point bending strength is 93 kg / mm 2 , the fracture toughness is 3.5 MPam 1/2 , the crystal phase is 100% tetragonal, the particle size of the sintered body is 0.5 μm, and 170
No increase in monoclinic crystal was observed after the degradation test under the conditions of ° C and hydrothermal conditions for 24 hours.
【００３４】実施例２ 原料粉末は、以下の方法により調製した。Example 2 A raw material powder was prepared by the following method.
【００３５】オキシ塩化ジルコニウムの水溶液と塩化セ
リウム水溶液を所望の組成（１２．４モル％）となるよ
うに混合し１００℃で１００時間、加熱を続けて加水分
解生成ゾルを得た。An aqueous solution of zirconium oxychloride and an aqueous cerium chloride solution were mixed so as to have a desired composition (12.4 mol%), and heating was continued at 100 ° C. for 100 hours to obtain a hydrolysis-formed sol.
【００３６】これを蒸発乾固して得た粉末を９００℃で
仮焼し、次に分散媒にエタノ−ルを用いたボ−ルミルで
２０時間粉砕し、酸化セリウム系ジルコニア粉末を得
た。The powder was evaporated to dryness, and the obtained powder was calcined at 900 ° C., and then pulverized with a ball mill using ethanol as a dispersion medium for 20 hours to obtain a cerium oxide-based zirconia powder.
【００３７】次にこの粉末と炭酸カルシウムを所望の組
成（１．０モル％）なるように分散媒にエタノ−ルを用
いたボ−ルミルで２０時間混合した後、９３０℃で仮焼
し、同様の方法で粉砕して酸化セリウム−酸化カルシウ
ム系ジルコニア粉末を調製した。Next, this powder and calcium carbonate were mixed in a ball mill using ethanol as a dispersion medium for a desired composition (1.0 mol%) for 20 hours, and calcined at 930 ° C. Pulverization was performed in the same manner to prepare cerium oxide-calcium oxide-based zirconia powder.
【００３８】この酸化セリウム−酸化カルシウム系ジル
コニア粉末の平均粒子径は、０．４μｍであった。The average particle diameter of the cerium oxide-calcium oxide zirconia powder was 0.4 μm.
【００３９】次いで、前記原料粉末をラバ−プレス法に
よって、厚さ、幅、長さがそれぞれ４ｍｍ、３７ｍｍ、
５４ｍｍである板状成形体とした。この成形体を１５０
０℃の温度で１時間焼成し、本発明の酸化セリウム−酸
化カルシウム系ジルコニア焼結体を得た。Next, the raw material powder was subjected to a rubber press method to have a thickness, width and length of 4 mm, 37 mm, respectively.
A plate-shaped molded body having a size of 54 mm was obtained. This molded body is
It was calcined at a temperature of 0 ° C. for 1 hour to obtain a cerium oxide-calcium oxide-based zirconia sintered body of the present invention.
【００４０】三点曲げ強度は９４ｋｇ／ｍｍ２、破壊靱
性は３．８ＭＰａｍ1/2 、結晶相は１００％正方晶であ
り、焼結体の粒子径は０．５μｍであり、又、１７０
℃、水熱下、２４時間の条件での劣化試験後の単斜晶の
増加は観測されなかった。The three-point bending strength is 94 kg / mm 2 , the fracture toughness is 3.8 MPam 1/2 , the crystal phase is 100% tetragonal, the particle size of the sintered body is 0.5 μm, and 170
No increase in monoclinic crystal was observed after the degradation test under the conditions of ° C and hydrothermal conditions for 24 hours.
【００４１】実施例３ 酸化セリウムの添加量を１０．０モル％とする以外は、
実施例２と同様の条件で、酸化セリウム−酸化カルシウ
ム系ジルコニア焼結体を得た。Example 3 Except that the amount of cerium oxide added was 10.0 mol%,
Under the same conditions as in Example 2, a cerium oxide-calcium oxide-based zirconia sintered body was obtained.
【００４２】三点曲げ強度は１２６ｋｇ／ｍｍ２、破壊
靱性は８．０ＭＰａｍ1/2 、結晶相は１００％正方晶で
あり、焼結体の粒子径は０．５μｍであり、又、１７０
℃、水熱下、２４時間の条件での劣化試験後の単斜晶の
増加は観測されなかった。The three-point bending strength is 126 kg / mm 2 , the fracture toughness is 8.0 MPam 1/2 , the crystal phase is 100% tetragonal, the particle size of the sintered body is 0.5 μm, and
No increase in monoclinic crystal was observed after the degradation test under the conditions of ° C and hydrothermal conditions for 24 hours.
【００４３】実施例４ 酸化セリウムの添加量を１０．０モル％、焼結温度が１
４５０℃である以外は、実施例２と同様の条件で、酸化
セリウム−酸化カルシウム系ジルコニア焼結体を得た。Example 4 The amount of cerium oxide added was 10.0 mol% and the sintering temperature was 1
A cerium oxide-calcium oxide-based zirconia sintered body was obtained under the same conditions as in Example 2 except that the temperature was 450 ° C.
【００４４】三点曲げ強度は１３３ｋｇ／ｍｍ２、破壊
靱性は７．０ＭＰａｍ1/2 、結晶相は１００％正方晶で
あり、焼結体の粒子径は０．４μｍであり、又、１７０
℃、水熱下、２４時間の条件での劣化試験後の単斜晶の
増加は観測されなかった。The three-point bending strength is 133 kg / mm 2 , the fracture toughness is 7.0 MPam 1/2 , the crystal phase is 100% tetragonal, the particle size of the sintered body is 0.4 μm, and
No increase in monoclinic crystal was observed after the degradation test under the conditions of ° C and hydrothermal conditions for 24 hours.
【００４５】実施例５ 酸化セリウムの添加量を１０．０モル％、酸化カルシウ
ムの添加量を０．５モル％とし、焼結温度が１４５０℃
である以外は、実施例２と同様の条件で、酸化セリウム
−酸化カルシウム系ジルコニア焼結体を得た。Example 5 The addition amount of cerium oxide was 10.0 mol%, the addition amount of calcium oxide was 0.5 mol%, and the sintering temperature was 1450 ° C.
A cerium oxide-calcium oxide-based zirconia sintered body was obtained under the same conditions as in Example 2 except that
【００４６】三点曲げ強度は９７ｋｇ／ｍｍ２、破壊靱
性は１７．５ＭＰａｍ1/2 、結晶相は１００％正方晶で
あり、焼結体の粒子径は０．４μｍであり、又、１７０
℃、水熱下、２４時間の条件での劣化試験後の単斜晶の
増加は観測されなかった。The three-point bending strength is 97 kg / mm 2 , the fracture toughness is 17.5 MPam 1/2 , the crystal phase is 100% tetragonal, the particle size of the sintered body is 0.4 μm, and
No increase in monoclinic crystal was observed after the degradation test under the conditions of ° C and hydrothermal conditions for 24 hours.
【００４７】実施例６ 酸化セリウムの添加量を８．０モル％、焼結温度が１４
５０℃である以外は、実施例２と同様の条件で、酸化セ
リウム−酸化カルシウム系ジルコニア焼結体を得た。Example 6 The amount of cerium oxide added was 8.0 mol% and the sintering temperature was 14
A cerium oxide-calcium oxide-based zirconia sintered body was obtained under the same conditions as in Example 2 except that the temperature was 50 ° C.
【００４８】三点曲げ強度は９５ｋｇ／ｍｍ２、破壊靱
性は１８．０ＭＰａｍ1/2 、結晶相は１００％正方晶で
あり、焼結体の粒子径は０．４μｍであり、又、１７０
℃、水熱下、２４時間の条件での劣化試験後の単斜晶は
１％しか増加しなかった。The three-point bending strength is 95 kg / mm 2 , the fracture toughness is 18.0 MPam 1/2 , the crystal phase is 100% tetragonal, the particle size of the sintered body is 0.4 μm, and
The monoclinic crystal increased by only 1% after the deterioration test under the conditions of 24 ° C. and hydrothermal condition for 24 hours.
【００４９】実施例７ 酸化セリウムの添加量を７．０モル％、酸化カルシウム
の添加量を２．０モル％、焼結温度が１４５０℃である
以外は、実施例２と同様の条件で、酸化セリウム−酸化
カルシウム系ジルコニア焼結体を得た。Example 7 The same conditions as in Example 2 were used except that the addition amount of cerium oxide was 7.0 mol%, the addition amount of calcium oxide was 2.0 mol%, and the sintering temperature was 1450 ° C. A cerium oxide-calcium oxide-based zirconia sintered body was obtained.
【００５０】三点曲げ強度は８０ｋｇ／ｍｍ２、破壊靱
性は１６．０ＭＰａｍ1/2 、結晶相は９０％正方晶、残
り１０％が立方晶であり、焼結体の粒子径は０．５μｍ
であった。又、１７０℃、水熱下、２４時間の条件での
劣化試験後の単斜晶は２％しか増加しなかった。The three-point bending strength is 80 kg / mm 2 , the fracture toughness is 16.0 MPam 1/2 , the crystal phase is 90% tetragonal, the remaining 10% is cubic, and the particle size of the sintered body is 0.5 μm
Met. Further, the monoclinic crystal after the deterioration test under the condition of 170 ° C. and hydrothermal condition for 24 hours increased only 2%.
【００５１】実施例１〜７の測定結果を表１に示した。Table 1 shows the measurement results of Examples 1 to 7.
【００５２】[0052]
【表１】 [Table 1]
【００５３】[0053]
【発明の効果】以上の結果から明らかなとおり、本発明
のジルコニア焼結体は、焼結体の粒子径を制御すること
で高強度、高靱性を有し、熱安定性に優れた焼結体を得
ることができる。特に、さらに酸化セリウムの添加量を
９〜１１モル％、酸化カルシウム０．７〜１．２モル％
に範囲を絞ることにより、焼結体の強度がさらに強くな
り、三点曲げ強度が１００ｋｇ／ｍｍ２以上となる。As is clear from the above results, the zirconia sintered body of the present invention has high strength and high toughness by controlling the particle size of the sintered body, and has excellent heat stability. You can get the body. Particularly, the addition amount of cerium oxide is 9 to 11 mol%, and calcium oxide is 0.7 to 1.2 mol%.
By narrowing the range, the strength of the sintered body is further increased, and the three-point bending strength is 100 kg / mm 2 or more.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−30663（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/42 - 35/49 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-30663 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C04B 35/42-35/49 CA (STN ) REGISTRY (STN)
Claims (5)
剤として使用するジルコニア焼結体において、焼結体の
粒子径が０．５μｍ以下であることを特徴とするジルコ
ニア焼結体。1. A zirconia sintered body using cerium oxide and calcium oxide as a stabilizer, wherein the sintered body has a particle diameter of 0.5 μm or less .
ルシウムを０．２〜１．５モル％を含み、結晶相が主と
して正方晶であることを特徴とする請求項１に記載のジ
ルコニア焼結体。2. The zirconia sintering composition according to claim 1, comprising 8 to 14 mol% of cerium oxide and 0.2 to 1.5 mol% of calcium oxide, and wherein the crystal phase is mainly tetragonal. Union.
ルシウムを０．７〜１．２モル％含み、結晶相が主とし
て正方晶であり、さらに三点曲げ強度が１００ｋｇ／ｍ
ｍ2以上であることを特徴とする請求項１に記載のジル
コニア焼結体。3. The composition contains 9 to 11 mol% of cerium oxide and 0.7 to 1.2 mol% of calcium oxide, has a mainly tetragonal crystal phase, and has a three-point bending strength of 100 kg / m.
zirconia sintered body according to claim 1, characterized in that m 2 or more.
ム塩を用い、加水分解によって沈殿を得たのち、６００
℃以上で焼成して得られる粉末を粉砕して、平均粒子径
を０．５μｍ以下とした微粉末を成形し、その成形体を
大気又は酸素中において、１３５０〜１５５０℃の温度
で焼結することを特徴とする請求項１に記載のジルコニ
ア焼結体の製造方法。4. A precipitate is obtained by hydrolysis using a zirconium salt, a cerium salt and a calcium salt.
The powder obtained by sintering at a temperature of at least 0 ° C. is pulverized to form a fine powder having an average particle diameter of 0.5 μm or less, and the formed body is sintered at a temperature of 1350 to 1550 ° C. in air or oxygen. The method for producing a zirconia sintered body according to claim 1, wherein:
水分解によって沈殿を得たのち、６００℃以上で焼成し
て得られる粉末にカルシウム塩を混合したのち、６００
℃以上で焼成して得られる粉末を粉砕して、平均粒子径
を０．５μｍ以下とした微粉末を成形し、その成形体を
大気又は酸素中において、１３５０〜１５５０℃の温度
で焼結することを特徴とする請求項１に記載のジルコニ
ア焼結体の製造方法。5. Using a zirconium salt and a cerium salt, pressurized
After a precipitate is obtained by hydrolysis , the powder obtained by calcining at 600 ° C. or higher is mixed with a calcium salt,
The powder obtained by sintering at a temperature of at least 100 ° C. is pulverized to form a fine powder having an average particle size of 0.5 μm or less, and the compact is sintered at 1350 to 1550 ° C. in air or oxygen. The method for producing a zirconia sintered body according to claim 1, wherein:
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|---|---|---|---|
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| Publication Number | Publication Date |
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