JPH0469105B2 - - Google Patents
Info
- Publication number
- JPH0469105B2 JPH0469105B2 JP59097572A JP9757284A JPH0469105B2 JP H0469105 B2 JPH0469105 B2 JP H0469105B2 JP 59097572 A JP59097572 A JP 59097572A JP 9757284 A JP9757284 A JP 9757284A JP H0469105 B2 JPH0469105 B2 JP H0469105B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- zirconia
- powder
- oxide
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 40
- 239000013078 crystal Substances 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 10
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 230000006866 deterioration Effects 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 7
- 238000003878 thermal aging Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は、熱耐久性に優れた高い機械的強度を
有するジルコニア系焼結体に関するものである。
安定化剤としてCeO2を添加した、主として正
方晶の結晶相からなるジルコニア焼結体（以下、
Ce−PSZ焼結体と略記する）は、高い強度と破
壊靭性を発現する。しかし、この焼結体は室温で
は、熱力学的に不安定な結晶相である正方晶系の
粒子を含有している。従つて、500℃以下の低い
温度環境下に長時間保持された場合、正方晶粒子
が安定相である単斜晶に徐々に転移し、この転移
に伴う体積膨脹のために、焼結体に亀裂が発生す
るという、いわゆる熱経時劣化現象を生じる。従
つて、これらの欠点を解消することにより、焼結
体の用途を大きく拡大できるので、その為の焼結
体が求められている。
Y2O3−ZrO2系焼結体に於いては、この熱経時
劣化を抑制する方法として、正方晶粒子の粒径を
小さくする方法、並びに安定化剤であるY2O3の
添加量を多くする方法が知られている。
このような方法はCe−PSZ焼結体にも適用で
きる。すなわち、Ce−PSZ焼結体の粒子径を小
さくすることによつて、またCeO2含量を多くす
ることによつて、熱経時劣化の少い、比較的安定
な焼結体を得ることができる。
本発明者等は、このような熱経時劣化をおこさ
ないジルコニア径焼結体及び熱経時劣化の抑制方
法について研究を行い、熱経時劣化が焼結体粒子
の大きさと安定化剤の量だけに依存するのではな
く、焼結体中に共存する第２相の存在に著しく依
存するということを見出した。すなわち、Ce−
PSZの第１相の他に、第２相としてアルミナ、ア
ルミナ系複酸化物、La、Nd等を含むジルコニア
系複酸化物などを存在させることによつて、従来
のCe−PSZ焼結体に比べて、より一層の熱耐久
性を保証できることを見出し、本発明を完成させ
るに至つた。
本発明の焼結体は熱耐久性ばかりでなく、機械
的強度においても高い強度を有するものである。
すなわち、本発明はCeO2を主体とした安定化
剤を５〜30モル％含有するZrO260〜99重量％と
Al2O3、Al2O3−MgO系酸化物、Al2O3−SiO2系
酸化物およびLa、Pr、Nd又はPmとZrの複酸化
物のうちの少くとも１種以上からなる酸化物１〜
40重量％よりなるジルコニア系焼結体を提供する
ものである。
以下、本発明をさらに詳細に説明する。
本発明で使用されるCeO2を主体とした安定化
剤とは、安定化剤としてCeO2が主成分になつて
いるという意味で、これ以外にMgO、CaO、
Y2O3及びCe、Pr、Nd、Pm以外のランタン系希
土類元素の酸化物などが例示されるが、これらが
少量含まれることは何らさしつかえない。
該安定化剤の量は、ジルコニアに対してして５
〜30モル％の範囲でなければならない。この範囲
であれば、ジルコニアは主として正方晶又は正方
晶と立方晶の混合相からなり好ましい。しかし、
この他の30重量％以下の単斜晶が共存していても
さしつかえない。５モル％より少なく、又は30モ
ル％をこえる範囲において、正方晶ジルコニアが
生成されなかつたり、機械的強度が充分得られな
くなつたりするので好ましくない。
本発明焼結体で共存する酸化物は、アルミナ系
又はジルコニア系酸化物であり、これらの割合と
しては、１〜40重量％である。40重量％をこえる
と、正方晶よりなるジルコニアに基因する強化機
構が減少し、強度低下をおこし好ましくない。ま
た、１重量％よりも少ないと、熱耐久性が充分で
なくなる。
共存する酸化物としては、アルミナ系では、
Al2O3、Al2O3−MgO系酸化物又はAl2O3−SiO2
系酸化物があげられ、Al2O3−MgO系酸化物では
スピネル型結晶相が、Al2O3−SiO2系酸化物では
ムライト型結晶相が主体となる。一方、ジルコニ
ア系では、La、Pr、Nd又はPmとZrの複酸化物
があげられ、これらはパイロクロア型の立方晶結
晶相が主体となる。
さらに、本発明の焼結体の結晶の平均粒子径は
5μｍ以下であることが好ましい。5μｍをこえる
と結晶の粒成長による強度低下が著しくなり好ま
しくない。
以上説明した熱耐久性に優れた焼結体とは、焼
結体を200〜300℃の温度、４〜20mmHgの水蒸気
分圧を有する空気環境下で1000時間のエージング
後、焼結体表面の単斜晶が全体の30重量％以下で
あり、かつ曲げ強度値がエージング前の値の20％
以上の減少を示さないような焼結であることを意
味する。
以下、本発明の焼結体の製造方法について説明
する。
CeO2を主体とした安定化剤を含むZrO2として
は、安定化剤酸化物粉末とZrO2粉末を混合する
方法、安定化剤元素とZrを含む水溶液を用いて
湿式合成法によつて粉末を得る方法などいずれの
方法でもさしつかえない。
共存させる酸化物の添加方法は、Al2O3粉末、
Al2O3−MgO系酸化物ではスピネル粉末、Al2O3
−CiO2系酸化物ではムライト粉末として、ジル
コニア粉末に混合する方法、アルミナ、マグネシ
ア、シリカの各粉末を所定量ジルコニア粉末に添
加混合する方法、或いはジルコニウム、アルミニ
ウム、マグネシウム、ケイ素などのイオンを含む
水溶液を用いて、湿式合成法によつて粉末を得る
方法、いずれの方法も適用できる。
La、Pr、Nd又はPmとZrからなる複酸化物で
は、パイロクロア型の酸化物粉末として、添加混
合物する方法も勿論可能であるが、上記ランタン
系希土類金属酸化物をジルコニアに混合すれば、
焼結過程でこれら酸化物とジルコニアの自発的な
反応がおこり、パイロクロア型で立方晶の化合物
が形成される。また、ジルコウムと上記ランタン
系希土類金属を含む溶液から湿式合成法によつて
粉末を得ることもよい方法である。
これら、各成分を含有した粉末をラバープレス
法などにより成形した後、1400〜1650℃の温度で
焼成することにより、本発明焼結体が得られる。
以上、説明した様に、本発明焼結は、熱経時劣
化に対いて強い、つまり熱耐久性の良い特性を有
するものであるが、その効果を明確にするために
熱経時劣化をおこさない焼結体晶の平均粒子径と
安定化剤の量の関係について第１図に示す。Cd
−PSZのみからなる焼結体では、点線ａより右の
の領域が熱耐久性を示す組成範囲であつたが、
本発明の焼結体の一例であるLa2O3とNd2O3を２
モル％含むZrO2を添加した例では、実線ｂと点
線ａに囲まれた斜線部の部分にまで熱耐久性の
範囲が顕著に拡大されたことがわかる。さらに従
来の焼結体よりも、より長時間にわたつて熱経時
劣化をおこさない焼結体でもある。
この様に、本発明焼結体は、機械的強度ばかり
でなく、熱耐久性も優れているため、工業材料と
して、ダイス、ノズル、粉砕、メデイア、ベアリ
ング等の用途ばかりでなく、熱のかかる部分での
使用例えばエンジン部品など広い用途に好適であ
る。
以下、さらに本発明を実施例により説明する
が、本発明はこれらにより限定されるものではな
い。
実施例 １
オキシ塩化ジルコニウムと塩化セリウム及び塩
化ランタン又は塩化ネオジウムを所定量混合した
溶液にPH＝９となるようにアンモニア水を添加
し、沈澱を得た。この沈澱をロ過分離後、乾杯し
た後温度950℃で２時間焼成して、焼結体用原料
微粉末を得た。また、比較のために、CeO2と
ZrO2だけからなる粉末も同様の操作によつて合
成した。得られた粉末をラバープレス法によつて
成形体とし、1400〜1650℃の温度で２時間焼成し
て、焼結体を得た。
焼結体の曲げ強度をJIS R1601−1981に規定さ
れた方法に準じて測定した。また、エージングに
よる熱劣化テストは、焼結体を温度200℃の電気
炉で、露点20℃の空気を流通しながら、1000時間
保持したのち、その曲げ強度を測定することによ
つて行つた。
得られた結果を表１に示す。
The present invention relates to a zirconia-based sintered body having excellent thermal durability and high mechanical strength. A zirconia sintered body ( hereinafter referred to as
Ce-PSZ sintered body) exhibits high strength and fracture toughness. However, this sintered body contains tetragonal particles, which is a thermodynamically unstable crystal phase at room temperature. Therefore, when kept in a low temperature environment of 500℃ or less for a long time, the tetragonal particles gradually transform into monoclinic, which is a stable phase, and due to the volume expansion accompanying this transition, the sintered body This causes a so-called thermal aging phenomenon in which cracks occur. Therefore, by eliminating these drawbacks, the uses of the sintered body can be greatly expanded, and a sintered body for this purpose is desired. In Y 2 O 3 -ZrO 2 based sintered bodies, methods of suppressing this thermal aging deterioration include reducing the grain size of the tetragonal grains and adding the amount of Y 2 O 3 as a stabilizer. There are known methods to increase the number of Such a method can also be applied to Ce-PSZ sintered bodies. In other words, by reducing the particle size of the Ce-PSZ sintered body and by increasing the CeO 2 content, a relatively stable sintered body with less thermal aging deterioration can be obtained. . The present inventors have conducted research on a zirconia diameter sintered body that does not cause such thermal aging deterioration and a method for suppressing thermal aging deterioration. It has been found that, rather than depending on the sintered body, it significantly depends on the presence of a second phase coexisting in the sintered body. That is, Ce−
In addition to the first phase of PSZ, by making alumina, alumina-based double oxide, zirconia-based double oxide containing La, Nd, etc. exist as a second phase, it is possible to improve the conventional Ce-PSZ sintered body. In comparison, the inventors discovered that it is possible to guarantee even higher thermal durability, leading to the completion of the present invention. The sintered body of the present invention has not only high thermal durability but also high mechanical strength. That is, the present invention uses 60 to 99% by weight of ZrO2 containing 5 to 30 mol% of a stabilizer mainly composed of CeO2 .
Oxidation consisting of at least one of Al 2 O 3 , Al 2 O 3 -MgO oxide, Al 2 O 3 -SiO 2 oxide, and multiple oxides of La, Pr, Nd, or Pm and Zr. Object 1~
A zirconia-based sintered body consisting of 40% by weight is provided. The present invention will be explained in more detail below. The stabilizer mainly composed of CeO 2 used in the present invention means that CeO 2 is the main component as a stabilizer, and it also contains MgO, CaO,
Examples include Y 2 O 3 and oxides of lanthanum-based rare earth elements other than Ce, Pr, Nd, and Pm, but there is nothing wrong with including a small amount of these. The amount of the stabilizer is 5% relative to zirconia.
Must be in the range ~30 mol%. Within this range, zirconia is preferably composed mainly of tetragonal crystals or a mixed phase of tetragonal crystals and cubic crystals. but,
There is no problem even if other monoclinic crystals coexist in an amount of 30% by weight or less. If it is less than 5 mol% or exceeds 30 mol%, it is not preferable because tetragonal zirconia may not be produced or sufficient mechanical strength may not be obtained. The oxides coexisting in the sintered body of the present invention are alumina-based or zirconia-based oxides, and the proportion thereof is 1 to 40% by weight. If it exceeds 40% by weight, the strengthening mechanism based on the tetragonal zirconia decreases, resulting in a decrease in strength, which is not preferable. Moreover, if it is less than 1% by weight, thermal durability will not be sufficient. In alumina type, coexisting oxides include:
Al 2 O 3 , Al 2 O 3 −MgO-based oxide or Al 2 O 3 −SiO 2
Al2O3 - MgO-based oxides mainly have a spinel-type crystal phase, while Al2O3 - SiO2 -based oxides mainly have a mullite-type crystalline phase. On the other hand, zirconia-based materials include La, Pr, Nd, or Pm and Zr double oxides, which mainly have a pyrochlore cubic crystal phase. Furthermore, the average grain size of the crystals of the sintered body of the present invention is
It is preferably 5 μm or less. If it exceeds 5 μm, the strength decreases significantly due to crystal grain growth, which is not preferable. The sintered body with excellent thermal durability described above is obtained by aging the sintered body for 1000 hours in an air environment with a temperature of 200 to 300°C and a partial pressure of water vapor of 4 to 20 mmHg. Monoclinic crystals account for 30% or less of the total weight, and the bending strength value is 20% of the value before aging.
This means sintering that does not show a decrease in Hereinafter, the method for manufacturing a sintered body of the present invention will be explained. ZrO 2 containing a stabilizer mainly composed of CeO 2 can be produced by mixing stabilizer oxide powder and ZrO 2 powder, or by wet synthesis using an aqueous solution containing the stabilizer element and Zr. Any method is acceptable, including the method of obtaining . The method of adding oxides to coexist is Al 2 O 3 powder,
Al 2 O 3 −MgO-based oxides include spinel powder, Al 2 O 3
-CiO2 -based oxides can be mixed with zirconia powder as mullite powder, mixed with a predetermined amount of each powder of alumina, magnesia, and silica into zirconia powder, or contain ions of zirconium, aluminum, magnesium, silicon, etc. Any method of obtaining a powder by a wet synthesis method using an aqueous solution can be applied. For double oxides consisting of La, Pr, Nd, or Pm and Zr, it is of course possible to mix them together as pyrochlore-type oxide powder, but if the above-mentioned lanthanum-based rare earth metal oxide is mixed with zirconia,
During the sintering process, a spontaneous reaction between these oxides and zirconia occurs, forming a pyrochlore-type cubic compound. It is also a good method to obtain a powder from a solution containing zirconium and the above-mentioned lanthanum-based rare earth metal by a wet synthesis method. The sintered body of the present invention can be obtained by molding the powder containing each of these components by a rubber press method or the like and then firing it at a temperature of 1400 to 1650°C. As explained above, the sintered material of the present invention is resistant to thermal deterioration over time, that is, has good thermal durability. The relationship between the average particle diameter of the crystalline crystals and the amount of stabilizer is shown in FIG. Cd
-For the sintered body made only of PSZ, the region to the right of dotted line a was the composition range that showed thermal durability;
La 2 O 3 and Nd 2 O 3 , which are an example of the sintered body of the present invention, are
It can be seen that in the example in which ZrO 2 containing mol % was added, the range of thermal durability was significantly expanded to the shaded area surrounded by solid line b and dotted line a. Furthermore, it is a sintered body that does not deteriorate over a longer period of time than conventional sintered bodies. As described above, the sintered body of the present invention has excellent not only mechanical strength but also thermal durability, so it can be used as an industrial material not only for dies, nozzles, crushers, media, bearings, etc. It is suitable for a wide range of applications such as engine parts. EXAMPLES Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto. Example 1 Aqueous ammonia was added to a solution in which a predetermined amount of zirconium oxychloride, cerium chloride, and lanthanum chloride or neodymium chloride were mixed to give a pH of 9 to obtain a precipitate. This precipitate was separated by filtration, toasted, and then fired at a temperature of 950° C. for 2 hours to obtain a fine raw material powder for a sintered body. Also, for comparison, CeO 2 and
A powder consisting only of ZrO 2 was also synthesized by the same procedure. The obtained powder was molded into a molded body by a rubber press method and fired at a temperature of 1400 to 1650°C for 2 hours to obtain a sintered body. The bending strength of the sintered body was measured according to the method specified in JIS R1601-1981. The thermal deterioration test due to aging was carried out by holding the sintered body in an electric furnace at a temperature of 200°C for 1000 hours while circulating air with a dew point of 20°C, and then measuring its bending strength. The results obtained are shown in Table 1.
【表】【table】
【表】
実施例 ２
平均一次粒子径が300ÅのCe−PSZ粉末に、高
純度アルミナ粉末を所定量添加し、ボールミルで
湿式混合粉砕して、得られた粉末をラバープレス
法によつて成形した後、1400〜1650℃の温度で２
時間焼結して焼結体を作成した。この焼結体につ
いて、実施例１に記載した方法に従つて、熱劣化
の有無を判定した。結果を表２に示す。また、ア
ルミナ粉末の換わりに平均一次粒子径が0.2μｍの
Al2O3−MgO系酸化物（スピネル粉末）又は
Al2O3−SiO2系酸化物（ムライト粉末）を用い
て、上記と同様の焼結体作製及び熱劣化テストを
行い、表２に記載した結果を得た。[Table] Example 2 A predetermined amount of high-purity alumina powder was added to Ce-PSZ powder with an average primary particle size of 300 Å, wet-mixed and pulverized in a ball mill, and the resulting powder was molded by a rubber press method. After that, 2 at a temperature of 1400-1650℃
A sintered body was created by sintering for a period of time. The presence or absence of thermal deterioration of this sintered body was determined according to the method described in Example 1. The results are shown in Table 2. In addition, instead of alumina powder, we can use powder with an average primary particle size of 0.2μm.
Al 2 O 3 −MgO-based oxide (spinel powder) or
Using Al2O3 - SiO2 -based oxide (mullite powder), the same sintered body preparation and thermal deterioration test as above were performed, and the results shown in Table 2 were obtained.
【表】【table】
第１図は、熱耐久性についてCe−PSZ焼結体
と本発明焼結体のそれぞれの効果を発現する範囲
を示すものである。
……Ce−PSZ焼結体の効果範囲、……本
発明焼結体により拡大された効果範囲、ａ……
Ce−PSZ焼結体の効果の境界線、ｂ……本発明
焼結体の効果の境界線。
FIG. 1 shows the range in which the Ce-PSZ sintered body and the sintered body of the present invention exhibit their respective effects regarding thermal durability. ...Effective range of Ce-PSZ sintered body,...Effective range expanded by the sintered body of the present invention, a...
Boundary line of effect of Ce-PSZ sintered body, b... Boundary line of effect of sintered body of the present invention.
Claims (1)
含むZrO2の60〜99重量％と下記Ａ成分の１〜40
重量％よりなることを特徴とするジルコニア系焼
結体。 Ａ成分：Al2O3、Al2O3−MgO系酸化物、
Al2O3−SiO2系酸化物およびLa、Pr、Nd又は
PmとZrの複酸化物のうちの少くとも１種以上か
らなる酸化物。 ２ 焼結体中のジルコニア結晶相が、主として正
方晶又は正方晶と立方晶からなる特許請求の範囲
第１項記載のジルコニア系焼結体。 ３ 焼結体中の結晶の平均粒子径が5μｍ以下で
ある特許請求の範囲第１項又は第２項記載のジル
コニア系焼結体。[Claims] 1. 5 to 30 mol% of a stabilizer mainly composed of CeO 2
60 to 99% by weight of ZrO 2 and 1 to 40% of the following A component
% by weight of a zirconia-based sintered body. A component: Al2O3 , Al2O3 - MgO-based oxide,
Al 2 O 3 −SiO 2 oxide and La, Pr, Nd or
An oxide consisting of at least one type of double oxide of Pm and Zr. 2. The zirconia-based sintered body according to claim 1, wherein the zirconia crystal phase in the sintered body mainly consists of tetragonal crystals or tetragonal and cubic crystals. 3. The zirconia-based sintered body according to claim 1 or 2, wherein the average particle size of crystals in the sintered body is 5 μm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59097572A JPS60246261A (en) | 1984-05-17 | 1984-05-17 | Zirconia sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59097572A JPS60246261A (en) | 1984-05-17 | 1984-05-17 | Zirconia sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60246261A JPS60246261A (en) | 1985-12-05 |
| JPH0469105B2 true JPH0469105B2 (en) | 1992-11-05 |
Family
ID=14195949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59097572A Granted JPS60246261A (en) | 1984-05-17 | 1984-05-17 | Zirconia sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60246261A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06102574B2 (en) * | 1985-08-20 | 1994-12-14 | 株式会社ノリタケカンパニーリミテド | High toughness ceramic sintered body excellent in heat resistance stability and method for producing the same |
| GB2206111B (en) * | 1987-06-24 | 1991-08-14 | Council Scient Ind Res | Sintered ceramic product |
| WO1996009263A1 (en) * | 1994-09-23 | 1996-03-28 | Alsimag Technical Ceramics, Inc. | Improved stabilized zirconia |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090870A (en) * | 1983-10-20 | 1985-05-22 | 日立化成工業株式会社 | Manufacture of high strength zirconia ceramic |
| JPS60108367A (en) * | 1983-11-16 | 1985-06-13 | 日立化成工業株式会社 | Zirconia sintered body |
| JPS60141671A (en) * | 1983-12-27 | 1985-07-26 | 日立化成工業株式会社 | Manufacture of zirconia sintered body |
-
1984
- 1984-05-17 JP JP59097572A patent/JPS60246261A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090870A (en) * | 1983-10-20 | 1985-05-22 | 日立化成工業株式会社 | Manufacture of high strength zirconia ceramic |
| JPS60108367A (en) * | 1983-11-16 | 1985-06-13 | 日立化成工業株式会社 | Zirconia sintered body |
| JPS60141671A (en) * | 1983-12-27 | 1985-07-26 | 日立化成工業株式会社 | Manufacture of zirconia sintered body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60246261A (en) | 1985-12-05 |
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