JP4589642B2 - Alumina / zirconia ceramics and process for producing the same - Google Patents
Alumina / zirconia ceramics and process for producing the same Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 87
- 239000000919 ceramic Substances 0.000 title claims description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 37
- 238000000034 method Methods 0.000 title claims 2
- 239000002245 particle Substances 0.000 claims description 59
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 34
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 238000010304 firing Methods 0.000 claims description 19
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 238000005452 bending Methods 0.000 claims description 6
- 238000001513 hot isostatic pressing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 description 13
- 230000007423 decrease Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000006104 solid solution Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 238000000280 densification Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 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 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、アルミナ・ジルコニア系セラミックスに関するものであって、特に種々の構造部材、切削工具、医療用器具、生体用材料に好適に使用されるアルミナ・ジルコニア系セラミックスおよびその製法に関する。 The present invention relates to alumina / zirconia ceramics, and particularly to alumina / zirconia ceramics suitably used for various structural members, cutting tools, medical instruments, and biomaterials, and a method for producing the same.
近年、アルミナ、ジルコニア系の酸化物セラミックスは、高強度、耐摩耗性及び耐食性が要求される構造部材として広く利用されている。特に、アルミナとジルコニアを一定の比率で含むアルミナ・ジルコニア系セラミックスは、結晶粒の微細化効果により、それぞれの単体セラミックスよりも高い強度が得られることが注目されている（非特許文献１参照）。 In recent years, alumina and zirconia-based oxide ceramics have been widely used as structural members that require high strength, wear resistance, and corrosion resistance. In particular, alumina / zirconia ceramics containing alumina and zirconia at a certain ratio are attracting attention because of the effect of refining crystal grains, higher strength than the individual ceramics can be obtained (see Non-Patent Document 1). .
しかし、上記のアルミナ・ジルコニア系セラミックスは、切削工具として用いた場合、靭性不足が原因で切刃に欠損やチッピングが生じ易く、実用に供する事ができないという欠点がある。このため、形状異方性粒子を生成させることによる靭性改善等が行なわれている。例えば、ＢａＯ、ＳｒO、ＣａＯの少なくとも１種とＳｉＯ２とを添加してアルミナ及びジルコニアの焼成を行うことにより、高靭性アルミナ−ジルコニア複合材料が得られることが知られている（例えば、特許文献１参照）。即ち、ＳｒＯ等を、アルミナ及びジルコニアの焼成時に共存させることにより、Ａｌ２Ｏ３結晶が細長く成長し、Ａｌ２Ｏ３粒子が細長成長結晶からなる組織を持つようになり、この細長成長Ａｌ２Ｏ３結晶によって優れた靭性を具備するようになるのである。 However, when the above-mentioned alumina / zirconia ceramics are used as a cutting tool, there is a drawback that the cutting edge is easily damaged or chipped due to insufficient toughness and cannot be put to practical use. For this reason, the toughness improvement etc. are performed by producing | generating a shape anisotropic particle. For example, it is known that a high toughness alumina-zirconia composite material can be obtained by adding at least one of BaO, SrO, CaO and SiO 2 and firing alumina and zirconia (for example, Patent Documents). 1). That is, by allowing SrO or the like to coexist at the time of firing alumina and zirconia, Al 2 O 3 crystals grow elongated and Al 2 O 3 particles have a structure composed of elongated growth crystals, and this elongated growth Al 2 The O 3 crystal has excellent toughness.
ところが、形状異方性粒子の生成によって破壊靭性が向上する一方で、強度と硬度が低下することが知られている。破壊靭性をより高くする為には形状異方性粒子をより細長く成長させる必要があるが、粒子が大きくなるほど強度と硬度が低下してしまう。即ち、前記特許文献１に開示されているようなアルミナ・ジルコニア系セラミックスでは、アルミナの異方性成長により靭性改善効果が見られるものの、曲げ強度が例えば１０５０ＭＰａ以下となり、形状異方性粒子の生成によって強度が低下してしまう。 However, it is known that the generation of shape anisotropic particles improves the fracture toughness while decreasing the strength and hardness. In order to further increase the fracture toughness, it is necessary to grow the shape anisotropic particles longer and longer, but the strength and the hardness decrease as the particles become larger. That is, in the alumina / zirconia ceramics disclosed in Patent Document 1, although the toughness improving effect is observed by the anisotropic growth of alumina, the bending strength becomes, for example, 1050 MPa or less, and the formation of shape anisotropic particles As a result, the strength decreases.
従って、本発明の目的は、粒成長を抑えながら、靭性が向上しており、高強度で且つ高靭性のアルミナ・ジルコニア系セラミックスを提供することにある。 Accordingly, an object of the present invention is to provide an alumina / zirconia ceramic having high toughness and high toughness while suppressing grain growth.
本発明者らは、アルミナ主体のアルミナ・ジルコニア系セラミックスにおいて、所定量のＳｒＯ、ＴｉＯ２、ＭｇＯ及びＳｉＯ２を配合して焼成を行い、形状異方性粒子の生成を抑えつつ、ＺｒＯ２粒子の微粒化により、正方晶ＺｒＯ２の準安定化を実現し、単斜晶への応力誘起相転移によって強度と破壊靭性とを向上できること、更にはＺｒＯ２へのＳｒＯ或いはＴｉＯ２の固溶が促進され、応力誘起相転移強化の効果が大きくできることを見出し、本発明に至った。 In the alumina-zirconia-based ceramic mainly composed of alumina, the present inventors blended a predetermined amount of SrO, TiO 2 , MgO and SiO 2 and fired to suppress the formation of shape anisotropic particles, while suppressing ZrO 2 particles of the atomization achieved metastable tetragonal ZrO 2, it can be improved and strength and fracture toughness by a stress-induced phase transformation to monoclinic, is more SrO or a TiO 2 solid solution to ZrO 2 As a result, the inventors have found that the effect of strengthening the stress-induced phase transition can be increased, and the present invention has been achieved.
すなわち、本発明によれば、Ａｌ２Ｏ３粒子及びＺｒＯ２粒子を含有するアルミナ・ジルコニア系セラミックスにおいて、
Ａｌ２Ｏ３含量が６５質量％以上であり、ＺｒＯ２含量が４〜３４質量％の範囲にあり、ＳｒＯを０．１〜４質量％の範囲で含み、さらにＴｉＯ２、ＭｇＯ及びＳｉＯ２を含有しているとともに、該ＴｉＯ ２ 含量、ＭｇＯ含量及びＳｉＯ ２ 含量が何れも０．１質量％以上であり、前記ＺｒＯ２粒子の一部には、ＳｒＯ或いはＴｉＯ２が固溶していることを特徴とするアルミナ・ジルコニア系セラミックスが提供される。
That is, according to the present invention, in the alumina / zirconia-based ceramics containing Al 2 O 3 particles and ZrO 2 particles,
Al 2 O 3 content is 65% by mass or more, ZrO 2 content is in the range of 4 to 34% by mass, SrO is included in the range of 0.1 to 4% by mass, and TiO 2 , MgO and SiO 2 are further contained. And the TiO 2 content, MgO content and SiO 2 content are all 0.1% by mass or more, and SrO or TiO 2 is dissolved in a part of the ZrO 2 particles. Alumina / zirconia ceramics are provided.
本発明のアルミナ・ジルコニア系セラミック焼結体においては、
（１）Ａｌ２Ｏ３粒子は、平均アスペクト比が２．５以下であり、且つ長軸平均粒径が１．５μｍ以下であり、ＺｒＯ２粒子の平均粒径が０．５μｍ以下であること、
（２）ＳｒＯ、ＴｉＯ２、ＭｇＯ及びＳｉＯ２の合計含量が１〜５質量％の範囲にあること、
（３）ＺｒＯ２当り、酸化物換算で０．４ｍｏｌ％以下の量でＹを必須成分として含有していること、
（４）ＺｒＯ２当り、酸化物換算で４ｍｏｌ％以下の量でＣｅを必須成分として含有していること、
（５）曲げ強度が１２００ＭＰａ以上であり、破壊靭性が４．２ＭＰａ・ｍ１／２以上であり、且つビッカース硬度が１７００以上であること、
が好適である。
In the alumina-zirconia ceramic sintered body of the present invention,
(1) Al 2 O 3 particles have an average aspect ratio of 2.5 or less, a major axis average particle size of 1.5 μm or less, and an average particle size of ZrO 2 particles of 0.5 μm or less. ,
(2) S rO, the total content of TiO 2, MgO and SiO 2 is in the range of 1 to 5 mass%,
(3) Y is contained as an essential component in an amount of 0.4 mol% or less in terms of oxide per ZrO 2 ;
(4) containing Ce as an essential component in an amount of 4 mol% or less in terms of oxide per ZrO 2 ;
(5) The bending strength is 1200 MPa or more, the fracture toughness is 4.2 MPa · m 1/2 or more, and the Vickers hardness is 1700 or more,
Is preferred.
さらに、本発明によれば、
Ａｌを酸化物換算で６５質量％以上、Ｚｒを酸化物換算で４〜３４質量％及びＳｒを酸化物換算で０．１〜４質量％の量で含有し、さらにＴｉ、Ｍｇ及びＳｉを酸化物換算で０．１質量％以上の量で含有し、且つＳｒ、Ｔｉ、Ｍｇ及びＳｉの酸化物換算での合計含量が１〜５質量％の範囲にある原料粉末を用意し、
前記原料粉末を所定形状に成形し、
得られた成形体を、１３００℃〜１５００℃の温度範囲で焼成し、
更に前記焼成温度より３０℃以上低い温度で熱間静水圧処理すること、
を特徴とするアルミナ・ジルコニア系セラミックスの製法が提供される。
Furthermore, according to the present invention,
Contains 65% by mass or more of Al in terms of oxide, 4 to 34% by mass of Zr in terms of oxide and 0.1 to 4% by mass of Sr in terms of oxide, and further oxidizes Ti, Mg and Si A raw material powder containing 0.1% by mass or more in terms of product and having a total content of 1 to 5% by mass in terms of oxides of Sr, Ti, Mg and Si is prepared,
The raw material powder is molded into a predetermined shape,
The obtained molded body was fired at a temperature range of 1300 ° C to 1500 ° C,
Furthermore, hot isostatic pressing at a temperature lower by 30 ° C. or more than the firing temperature,
A method for producing an alumina / zirconia ceramics is provided.
本発明のアルミナ・ジルコニアセラミックスでは、特にＺｒＯ２粒子の一部にＳｒＯ或いはＴｉＯ２が固溶していることにより、ＳｒＯ或いはＴｉＯ２による正方晶ＺｒＯ２の準安定化効果が発現し、応力誘起相転移の効果によって高強度化、高靭性化が達成されており、例えば１２００ＭＰａ以上の曲げ強度、４．２ＭＰａ・ｍ１／２以上の破壊靭性、及び１７００以上のビッカース硬度を有している。 In the alumina / zirconia ceramic of the present invention, particularly when SrO or TiO 2 is solid-solved in a part of ZrO 2 particles, the effect of metastabilization of tetragonal ZrO 2 by SrO or TiO 2 appears, and stress induction is caused. Higher strength and higher toughness have been achieved by the effect of the phase transition. For example, it has a bending strength of 1200 MPa or more, a fracture toughness of 4.2 MPa · m 1/2 or more, and a Vickers hardness of 1700 or more.
また、本発明の製法では、焼結助剤として機能するＳｉＯ２、ＴｉＯ２及びＭｇＯが一定の量割合で存在する条件下で焼成が行われるため、ＳｒＯやＴｉＯ２のＺｒＯ２への固溶が促進され、且つ形状異方性粒子の生成が有効に抑制され、且つ高緻密化、組織微細化が達成され、その結果、上述した高強度、高靭性、さらには高硬度のアルミナ・ジルコニア系セラミックスを得ることが可能となる。 Further, in the production method of the present invention, since firing is performed under the condition that SiO 2 , TiO 2 and MgO functioning as a sintering aid are present in a certain amount ratio, SrO or TiO 2 is dissolved in ZrO 2 . And the formation of anisotropically shaped particles is effectively suppressed, and high densification and microstructure refinement are achieved. As a result, the above-described high strength, high toughness and high hardness of alumina / zirconia system are achieved. Ceramics can be obtained.
（アルミナ・ジルコニアセラミックス）
本発明のセラミックスは、基本成分として、Ａｌ２Ｏ３粒子及びＺｒＯ２粒子を含有するものであるが、アルミナリッチの組成を有しており、Ａｌ２Ｏ３を６５質量％以上、好ましくは７０〜８５質量％、さらに好ましくは７５〜７９質量％の量で含有し、ＺｒＯ２を４〜３４質量％、好ましくは１５〜３０質量％、特に好ましくは１９〜２４質量％の量で含有している。即ち、Ａｌ２Ｏ３を６５質量％以上含有させることにより、高強度でかつ高硬度という効果を達成することが可能となり、ＺｒＯ２の含有量が４質量％未満ではＡｌ２Ｏ３結晶が大きく成長してしまい、特に強度の著しい低下を招き、一方、ＺｒＯ２の含有量が３４質量％を超えるとヤング率低下により硬度が低下してしまう。
(Alumina / zirconia ceramics)
The ceramic of the present invention contains Al 2 O 3 particles and ZrO 2 particles as basic components, but has an alumina-rich composition, and Al 2 O 3 is 65% by mass or more, preferably 70%. -85% by mass, more preferably 75-79% by mass, and ZrO 2 in an amount of 4-34% by mass, preferably 15-30% by mass, particularly preferably 19-24% by mass. Yes. That is, by containing 65% by mass or more of Al 2 O 3 , it is possible to achieve an effect of high strength and high hardness. When the content of ZrO 2 is less than 4% by mass, the Al 2 O 3 crystals are large. In particular, when the ZrO 2 content exceeds 34 mass%, the hardness decreases due to a decrease in Young's modulus.
また、本発明のセラミックスにおいては、ＺｒＯ２粒子の一部には、ＳｒＯ或いはＴｉＯ２が固溶していることが重要であり、これにより、破壊靭性を向上でき、同時に高強度化、高硬度化を実現できる。 In the ceramic of the present invention, it is important that SrO or TiO 2 is dissolved in a part of the ZrO 2 particles, thereby improving the fracture toughness and at the same time increasing the strength and hardness. Can be realized.
通常ＺｒＯ２は、Ｙ２Ｏ３やＣｅＯ２の安定化剤を適量固溶させることで機械的特性を向上させることができる。しかし、アルミナ・ジルコニア系セラミックスでは、Ｙ２Ｏ３やＣｒＯ２の固溶では、立方晶が多くなったり、正方晶の安定化度が高くなり、相変態の破壊靭性への寄与が小さくなる。また、Ａｌ２Ｏ３含量の多いアルミナ・ジルコニア系セラミックスでは、硬度は高いが、Ａｌ２Ｏ３含量の増大によって強度と靭性が低下している。これを補う目的で、ＳｒＯを添加し、形状異方性粒子を生成させて靭性を向上させるためには高温焼成を必要とし、この結果、粒成長や緻密化阻害等を生じてしまい、強度、硬度が大きく低下してしまい、やはり、破壊靭性、強度及び硬度を同時に向上させることができない。 Usually, ZrO 2 can improve mechanical properties by dissolving an appropriate amount of a stabilizer of Y 2 O 3 or CeO 2 . However, in alumina / zirconia ceramics, the solid solution of Y 2 O 3 or CrO 2 increases the number of cubic crystals or increases the degree of stabilization of tetragonal crystals, and the contribution of the phase transformation to fracture toughness decreases. Also, in many alumina-zirconia ceramics of Al 2 O 3 content, but the hardness is high, the strength and toughness by increasing the Al 2 O 3 content is reduced. In order to compensate for this, SrO is added to generate shape anisotropic particles and improve toughness, so that high temperature firing is required, resulting in grain growth, densification inhibition, etc. Hardness is greatly reduced, and again, fracture toughness, strength and hardness cannot be improved at the same time.
しかるに、本発明では、ＳｒＯ或いはＴｉＯ２のＺｒＯ２への固溶により正方晶ＺｒＯ２の準安定化が起こる。即ち、Ｓｒは、Ｚｒとのイオン半径差が大きいため、ＺｒＯ２への固溶量が少なく、立方晶は生成し難くなる。また、Ｔｉは、Ｚｒとイオン半径が近く、このため、多く固溶しても、過度の安定化は生じない。従って、何れの場合においても、応力誘起相転移効果が大きく、形状異方性粒子生成によらず破壊靭性を向上でき、従って、形状異方性粒子生成による強度や硬度の低下を回避することができ、破壊靭性、強度及び硬度を同時に向上させることができるわけである。 However, in the present invention, metastabilization of tetragonal ZrO 2 occurs due to solid solution of SrO or TiO 2 in ZrO 2 . That is, since Sr has a large ion radius difference from Zr, the amount of solid solution in ZrO 2 is small, and it is difficult to form cubic crystals. Ti has an ion radius close to that of Zr. Therefore, even if a large amount of Ti is dissolved, excessive stabilization does not occur. Therefore, in any case, the stress-induced phase transition effect is large, and the fracture toughness can be improved regardless of the formation of shape anisotropic particles. Therefore, the decrease in strength and hardness due to the formation of shape anisotropic particles can be avoided. The fracture toughness, strength and hardness can be improved at the same time.
本発明のセラミックスにおいては、ＳｒＯ含量は、０．１〜４質量％の範囲とする。ＳｒＯ含量が上記範囲よりも少量であると、ＺｒＯ２の単斜晶系が多くなり、強度が低下する。またＳｒＯ含量が上記範囲よりも多いものは、焼成温度を高くしなければ得ることができず、このため、形状異方性粒子による緻密化阻害や、ジルコニア粒成長による強度あるいは硬度の低下がおきる。 In the ceramic of the present invention, the SrO content is in the range of 0.1 to 4% by mass. When the SrO content is less than the above range, the monoclinic system of ZrO 2 increases and the strength decreases. In addition, when the SrO content is higher than the above range, it cannot be obtained unless the firing temperature is increased. For this reason, densification is inhibited by shape anisotropic particles, and strength or hardness decreases due to zirconia grain growth. .
また、上記のＳｒＯとともに、ＴｉＯ２、ＭｇＯ及びＳｉＯ２を含有していることも重要である。これらの酸化物成分は、ＳｒＯのＺｒＯ２粒子への固溶を促進する。即ち、Ｓｒは、通常、ＺｒＯ２結晶に殆ど固溶しないが、ＴｉＯ２、ＭｇＯ及びＳｉＯ２の存在下で、その固溶が促進され、準安定化ＺｒＯ２の相変態強化効果が向上する。さらに、酸化物成分は、焼結助剤としての機能も示し、Ａｌ２Ｏ３及びＺｒＯ２の結晶粒成長を抑制しながら、低い温度条件で焼結体を緻密化でき、微粒、高密度の組織形成により高強度化や高硬度化を実現させる。例えば、これらの酸化物成分の何れかを含有していないものは、高温での焼成が必要となり、形状異方性粒子による緻密化阻害や、ジルコニア粒成長による強度あるいは硬度の低下が生じてしまう。 It is also important that TiO 2 , MgO and SiO 2 are contained together with the above SrO. These oxide components promote solid solution of SrO in ZrO 2 particles. That is, Sr is usually hardly dissolved in the ZrO 2 crystal, but in the presence of TiO 2 , MgO, and SiO 2 , the solid solution is promoted, and the phase transformation strengthening effect of the metastabilized ZrO 2 is improved. Furthermore, the oxide component also exhibits a function as a sintering aid, and can suppress the growth of crystal grains of Al 2 O 3 and ZrO 2 while densifying the sintered body under low temperature conditions. Achieves higher strength and higher hardness by forming the structure. For example, those that do not contain any of these oxide components need to be fired at a high temperature, resulting in densification inhibition due to shape anisotropic particles and a decrease in strength or hardness due to zirconia grain growth. .
また、ＳｒＯと共存する酸化物成分の内、ＴｉＯ２は、既に述べたように、ＺｒＯ２結晶の準安定化効果を有している。従って、ＴｉＯ２は、ＳｒＯと共に、或いはＳｒＯの代わりにＺｒＯ２に固溶していてもよく、このようなＴｉＯ２のＺｒＯ２への固溶によっても、同様の準安定化効果を得ることができ、特にＳｒＯとＴｉＯ２との両方がＺｒＯ２に固溶しているものは、準安定化ＺｒＯ２の応力誘起相転移強化効果が高く、好適である。本発明において、ＴｉＯ２含量は、通常、０．１質量％以上、特に０．３乃至１質量％であることが好適である。ＴｉＯ２含量が増すにしたがい、ＺｒＯ２へのＴｉＯ２の固溶が生じる。また、ＳｒＯに比してＴｉＯ２を多量に含有するものでは、ＴｉＯ２のみがＺｒＯ２に固溶することもある。 Of the oxide components coexisting with SrO, TiO 2 has a quasi-stabilizing effect on the ZrO 2 crystal as described above. Therefore, TiO 2 may be dissolved in ZrO 2 together with SrO or in place of SrO, and the same metastabilizing effect can be obtained by such a solid solution of TiO 2 in ZrO 2 . can, in particular, both the SrO and TiO 2 are those dissolved in the ZrO 2, high metastable ZrO 2 stress induced phase transition reinforcing effect, which is preferable. In the present invention, the TiO 2 content is usually 0.1% by mass or more, and preferably 0.3 to 1% by mass. As the TiO 2 content increases, the solid solution of TiO 2 in ZrO 2 occurs. Further, in the case of containing a large amount of TiO 2 as compared with SrO, only TiO 2 may be dissolved in ZrO 2 .
さらに、セラミックス中のＭｇＯ含量及びＺｒＯ２含量は、それぞれ、０．１質量％以上、特に０．２乃至０．５質量％であることが好ましい。即ち、ＭｇＯ含量及びＺｒＯ２含量が、あまり少ないと、焼成時に液相が不足し、Ａｌ２Ｏ３が緻密化しにくくなり、高温での焼成が必要となってしまい、形状異方性粒子による緻密化阻害や、ジルコニア粒成長による強度あるいは硬度の低下を生じ易くなってしまう。 Furthermore, the MgO content and the ZrO 2 content in the ceramics are each preferably 0.1% by mass or more, and particularly preferably 0.2 to 0.5% by mass. That is, if the MgO content and the ZrO 2 content are too small, the liquid phase is insufficient at the time of firing, Al 2 O 3 becomes difficult to be densified, and firing at a high temperature is necessary, and the denseness due to shape anisotropic particles It becomes easy to cause deterioration of strength or hardness due to crystallization inhibition or zirconia grain growth.
また、上記のＳｒＯ、ＴｉＯ２、ＭｇＯ及びＳｉＯ２の含量は、合計で１〜５質量％の範囲とすることが好ましい。即ち、各成分の総量が、このような範囲にあるとき、ＳｒＯのＺｒＯ２への固溶が促進され、強度、靭性が向上すると共に、共晶点が１３００℃以下になり、焼結時に液相が生成して焼結が大きく促進される。この為、より低い温度での焼成により、高い緻密性の焼結体が得られるとともに、異方粒成長を抑制し、微細な組織となり、強度や硬度の低下を回避するのに有利となる。 The above-mentioned SrO, the content of TiO 2, MgO and SiO 2 is preferably in the range of 1 to 5 mass% in total. That is, when the total amount of each component is in such a range, the solid solution of SrO in ZrO 2 is promoted, the strength and toughness are improved, the eutectic point is 1300 ° C. or lower, and A phase is formed and sintering is greatly promoted. For this reason, by firing at a lower temperature, a highly dense sintered body can be obtained, an anisotropic grain growth is suppressed, a fine structure is obtained, and it is advantageous for avoiding a decrease in strength and hardness.
本発明のアルミナ・ジルコニアセラミックスでは、上述した各成分に加えて、Ｙ２Ｏ３やＣｅＯ２に代表されるＺｒＯ２の安定化剤を含有していてもよい。ただし、このような安定化剤が多量に配合されると、正方晶ＺｒＯ２の安定化度が高くなりすぎてしまい、ＺｒＯ２の応力誘起相転移強化効果を低下させてしまい、靭性の低下等をもたらすおそれがあるため、Ｙ２Ｏ３においては、その含有量を、ＺｒＯ２当り０．４モル％以下、特に０．２モル％以下とすることが好ましく、ＣｅＯ２においては、ＺｒＯ２当り４モル％以下、特に２．５モル％以下とすることが好ましい。 The alumina / zirconia ceramic of the present invention may contain a ZrO 2 stabilizer typified by Y 2 O 3 or CeO 2 in addition to the components described above. However, when such a stabilizer is blended in a large amount, the degree of stabilization of tetragonal ZrO 2 becomes too high, reducing the stress-induced phase transition strengthening effect of ZrO 2 , and reducing toughness. In Y 2 O 3 , the content is preferably 0.4 mol% or less per ZrO 2 , particularly preferably 0.2 mol% or less. In CeO 2 , the content per ZrO 2 It is preferably 4 mol% or less, particularly 2.5 mol% or less.
以上の説明から理解されるように、上記のような組成を有する本発明のアルミナ・ジルコニアセラミックスは、形状異方性粒子による緻密化阻害や、ジルコニア粒成長による強度あるいは硬度の低下が有効に回避されており、例えば、該セラミックス中のＡｌ２Ｏ３粒子は、平均アスペクト比が２．５以下であり、且つその長軸平均粒径が１．５μｍ以下、特に１μｍ以下であり、ＺｒＯ２粒子の平均粒径が０．５μｍ以下、特に０．３μｍ以下である。即ち、Ａｌ２Ｏ３粒子の平均アスペクト比が２．５を越えるとき或いはその長軸平均粒径が１．５μｍよりも大きいときには、形状異方性粒子による緻密化阻害を生じ、強度低下を生じてしまい。また、ＺｒＯ２粒子の平均粒径が０．５μｍよりも大きいと、正方晶の安定性が低下し、相変態によるミクロクラックが発生し、強度や靭性の低下を生じてしまう。 As can be understood from the above description, the alumina / zirconia ceramic of the present invention having the above composition effectively avoids densification inhibition due to shape anisotropic particles and reduction in strength or hardness due to zirconia grain growth. For example, the Al 2 O 3 particles in the ceramics have an average aspect ratio of 2.5 or less and a major axis average particle size of 1.5 μm or less, particularly 1 μm or less. ZrO 2 particles Has an average particle size of 0.5 μm or less, particularly 0.3 μm or less. That is, when the average aspect ratio of Al 2 O 3 particles exceeds 2.5, or when the major axis average particle size is larger than 1.5 μm, densification is inhibited by shape anisotropic particles, resulting in a decrease in strength. End. On the other hand, if the average particle diameter of the ZrO 2 particles is larger than 0.5 μm, the stability of the tetragonal crystal is lowered, microcracks are generated due to phase transformation, and the strength and toughness are lowered.
このように本発明のアルミナ・ジルコニア系セラミックスは、強度、靭性及び高度の何れの特性も優れており、後述する実施例から明らかな通り、１２００ＭＰａ以上、特に１４００ＭＰａ以上の曲げ強度、４．２ＭＰａ・ｍ１／２以上、特に５．０ＭＰａ・ｍ１／２以上の破壊靭性、及び１７００以上、特に１７５０以上のビッカース硬度を有しており、種々の構造部材、切削工具、医療用器具などの用途に適している。 As described above, the alumina / zirconia ceramics of the present invention are excellent in all of the properties of strength, toughness, and highness. As is apparent from Examples described later, bending strength of 1200 MPa or more, particularly 1400 MPa or more, 4.2 MPa · m 1/2 or more, particularly 5.0 MPa · m 1/2 or more fracture toughness, and 1700 or more, in particular has a 1750 or more Vickers hardness, various structural members, cutting tools, applications such as medical devices Suitable for
（アルミナ・ジルコニア系セラミックスの製法）
上述した本発明のアルミナ・ジルコニアセラミックスは、所定の組成の原料粉末を調製し、所定形状に成形し、焼成及び熱間静水圧処理することにより製造される。
(Alumina / zirconia ceramics manufacturing method)
The above-described alumina / zirconia ceramic of the present invention is produced by preparing a raw material powder having a predetermined composition, forming it into a predetermined shape, firing and hot isostatic pressing.
用いる原料粉末は、前述した組成の焼結体が得られるように、各種の金属分を含んでおり、例えばＡｌ２Ｏ３源となるＡｌ分、ＺｒＯ２源となるＺｒ分、及びＳｒＯ源となるＳｒ分を含み、且つ助剤成分としてのＴｉ分、Ｍｇ分及びＳｉ分を含有する。これら金属分は、一般的には酸化物の形で使用されるが、焼成により、前述した各種の酸化物を形成するものであれば酸化物に限定されるものではなく、金属単体、水酸化物、あるいは炭酸塩などの塩類の形で使用することもできる。即ち、原料粉末は、これらの金属分の原料を混合することにより調製され、原料粉末中の各種金属分の含有割合は、Ａｌ、Ｚｒ、Ｓｒ、Ｔｉ、Ｍｇ及びＳｉ量が、酸化物換算で、前述した焼結体の組成に対応するように設定される。また、原料粉末の平均粒径は、一般に、１．０μｍ以下が好ましい。 The raw material powder to be used contains various metal components so that a sintered body having the above-described composition can be obtained. For example, an Al component serving as an Al 2 O 3 source, a Zr component serving as a ZrO 2 source, and a SrO source Sr content and Ti content, Mg content and Si content as auxiliary components. These metal components are generally used in the form of oxides, but are not limited to oxides as long as they form the above-mentioned various oxides by firing. Or in the form of a salt such as carbonate. That is, the raw material powder is prepared by mixing the raw materials of these metals, and the content ratio of various metals in the raw material powder is such that the amounts of Al, Zr, Sr, Ti, Mg and Si are converted to oxides. , Is set to correspond to the composition of the sintered body described above. The average particle size of the raw material powder is generally preferably 1.0 μm or less.
原料粉末を用いての成形は、必要により、水や有機溶媒等の溶媒、有機バインダーなどを用いて原料粉末のスラリー乃至ペーストもしくはこれらを乾燥して得られる粉末を調製し、このようなスラリー乃至ペーストもしくは粉末を用いて行うことも可能である。また、成形手段としては、プレス成形、鋳込み、冷間静水圧成形、或いは冷間静水圧処理など、それ自体公知の手段を採用することができる。 The molding using the raw material powder is carried out by preparing a slurry or paste of the raw material powder or a powder obtained by drying these using a solvent such as water or an organic solvent, an organic binder, etc. It is also possible to use a paste or powder. Further, as the forming means, means known per se such as press molding, casting, cold isostatic pressing, or cold isostatic treatment can be employed.
上記成形体の焼成は、１３００〜１５００℃、特に１３００乃至１４９０℃の温度範囲で行われ、これにより、Ａｌ２Ｏ３やＺｒＯ２の粒成長を抑制しながら緻密化することができる。例えば、ＳｒＯが存在する条件下で１５００℃よりも高い温度で焼成を行うと、ＳｒＯとＡｌ２Ｏ３とが反応して異方粒成長し、焼結体の強度や硬度が低下してしまう。また、ＺｒＯ２の粒成長によって単斜晶ＺｒＯ２量が増加することによっても、強度や硬度の低下がもたらされる。また、１３００℃よりも低温での焼成では、緻密化が困難となってしまう。 The molded body is fired at a temperature in the range of 1300 to 1500 ° C., particularly 1300 to 1490 ° C., thereby enabling densification while suppressing grain growth of Al 2 O 3 and ZrO 2 . For example, if firing is performed at a temperature higher than 1500 ° C. in the presence of SrO, SrO and Al 2 O 3 react to grow anisotropically, reducing the strength and hardness of the sintered body. . Further, also by monoclinic ZrO 2 amount by grain growth of ZrO 2 is increased, decrease in strength and hardness is provided. Further, densification becomes difficult by firing at a temperature lower than 1300 ° C.
本発明においては、焼結助剤として、所定量のＳｉＯ２、ＴｉＯ２及びＭｇＯが使用されているため、ＳｒＯのＺｒＯ２への固溶が促進されると共に、共晶点が１３００℃以下になり、焼結時に液相が生成して材料の焼結が大きく促進される。この為、上記のような比較的低温領域での焼成により、緻密性の高い焼結体を得ることができる。また、このような比較的低温領域で焼結することによって、異方粒成長が抑制され、微細な組織となり、強度や硬度を低下させず、靭性を高めることができるのである。 In the present invention, since predetermined amounts of SiO 2 , TiO 2 and MgO are used as sintering aids, solid solution of SrO in ZrO 2 is promoted and the eutectic point is 1300 ° C. or lower. Thus, a liquid phase is generated during sintering, and the sintering of the material is greatly promoted. For this reason, a sintered compact with high density can be obtained by firing in a relatively low temperature region as described above. Further, by sintering in such a relatively low temperature region, anisotropic grain growth is suppressed, a fine structure is obtained, and the toughness can be increased without lowering the strength and hardness.
上記のような温度範囲での焼成時間は、例えばアルキメデス法による相対密度が９５％以上となる程度でよく、通常、１乃至５時間程度である。 The baking time in the above temperature range may be such that the relative density by the Archimedes method is 95% or more, and is usually about 1 to 5 hours.
上記の焼成に引き続いて行われる熱間静水圧処理は、前記焼成温度より３０℃以上低い温度、好ましくは５０℃以上低い温度、更に好ましくは１００℃以上低い温度で行われ、これによりアルミナ、ジルコニアが微粒で、アルミナの異方粒成長を抑えた緻密なアルミナ・ジルコニア系セラミックスを作製することができ、この焼結体は、既に述べたように、靭性が高く、しかも高強度、高硬度という特性を有している。 The hot isostatic pressure treatment performed following the firing is performed at a temperature that is 30 ° C. or more lower than the firing temperature, preferably 50 ° C. or more, and more preferably 100 ° C. or more, whereby alumina or zirconia. Can be used to produce dense alumina / zirconia ceramics that suppress the growth of anisotropic grains of alumina. As already mentioned, this sintered body has high toughness, high strength, and high hardness. It has characteristics.
尚、上記の熱間静水圧処理は、短時間でアルミナやジルコニアを微粒化させるため、通常、その下限温度は、１２００℃以上、特に１２５０℃以上とするのがよく、一般に、０．５乃至２時間程度行えばよい。 The hot isostatic pressure treatment atomizes alumina or zirconia in a short time, and therefore the lower limit temperature is usually 1200 ° C. or higher, particularly 1250 ° C. or higher. It may be performed for about 2 hours.
純度が９９．９５質量％で平均粒径０．２２μｍのＡｌ２Ｏ３粉末、純度が９９．９５質量％で平均粒径０．１μｍのジルコニア粉末、平均粒径０．４μｍのＴｉＯ２粉末、平均粒径０．６μｍのＭｇ（ＯＨ）２粉末、平均粒径０．５μmのＳｉＯ２粉末、及び平均粒径０．２μｍのＳｒＣＯ３粉末を、酸化物換算で、表１に示すような組成になるように秤量混合して、出発原料となる混合粉末を得た。（但し、試料No.6では、安定化剤として、ジルコニア当り０．３モル％のＹ２Ｏ３粉末を使用し、試料No.7では、安定化剤として、ジルコニア当り３モル％のＣｅＯ２粉末を、さらに使用した。 Al 2 O 3 powder having a purity of 99.95% by mass and an average particle size of 0.22 μm, zirconia powder having a purity of 99.95% by mass and an average particle size of 0.1 μm, TiO 2 powder having an average particle size of 0.4 μm, the average particle diameter 0.6μm of Mg (OH) 2 powder, SiO 2 powder having an average particle diameter of 0.5 [mu] m, and a SrCO 3 powder having an average particle diameter of 0.2 [mu] m, in terms of oxide, the composition shown in Table 1 Weighed and mixed to obtain a mixed powder as a starting material. (However, in sample No. 6, 0.3 mol% Y 2 O 3 powder per zirconia was used as a stabilizer, and in sample No. 7, 3 mol% CeO 2 per zirconia was used as a stabilizer. The powder was used further.
この混合粉末を、１ｔ／ｃｍ２の圧力で金型成形し、さらに３ｔ／ｃｍ２の圧力で静水圧処理を加えて成形体を作製し、表１に示す温度にて、本焼成及び熱間静水圧処理（表中にＨＩＰと表示）を行なった。尚、何れの場合も、本焼成は２時間、熱間静水圧処理は、１時間行った。 This mixed powder is molded at a pressure of 1 t / cm 2 and further subjected to hydrostatic pressure treatment at a pressure of 3 t / cm 2 to produce a molded body. Hydrostatic pressure treatment (indicated as HIP in the table) was performed. In each case, the main firing was performed for 2 hours and the hot isostatic pressure treatment was performed for 1 hour.
得られた各焼結体に対して、鏡面加工後、熱エッチングを行い、結晶粒径、アスペクト比、長軸平均粒径を電子顕微鏡で測定した。
また、Ｘ線回折（ＸＲＤ）によって単斜晶ＺｒＯ２の比率を測定し、準安定化度を測定した。さらに、透過型電子顕微鏡におけるエネルギー分散組成分析装置（ＥＤＳ）によりＺｒＯ２へのＳｒＯ或いはＴｉＯ２の固溶の確認を行った。
さらに、各焼結体の曲げ強度(JIS R 1601)、破壊靭性(JIS R 1607)、ビッカース硬度(JIS Z 2244)を測定し、表１に記載した。
Each obtained sintered body was subjected to thermal etching after mirror finishing, and the crystal grain size, aspect ratio, and long axis average grain size were measured with an electron microscope.
Further, the ratio of monoclinic ZrO 2 was measured by X-ray diffraction (XRD), and the degree of metastabilization was measured. Furthermore, the solid solution of SrO or TiO 2 in ZrO 2 was confirmed by an energy dispersive composition analyzer (EDS) in a transmission electron microscope.
Further, the bending strength (JIS R 1601), fracture toughness (JIS R 1607), and Vickers hardness (JIS Z 2244) of each sintered body were measured and listed in Table 1.
表１より、アルミナ粒子のアスペクト比や長軸平均粒径やジルコニアの平均粒子径が所定の範囲内にある本発明のセラミックス（試料Ｎｏ.１〜７）は、強度が１４２５〜１５５０ＭＰａ、破壊靭性４．５〜５．４ＭＰａ√ｍ、硬度１７３０〜１７９０Ｈｖの特性を示した。特に、試料Ｎｏ.４の材料では焼成温度が低く、微粒の組織が形成されたため、優れた強度、硬度、靭性を示した。 これに対して、本発明のセラミックスの中でも、アルミナ粒子のアスペクト比や長軸平均粒径等が所定の範囲外である試料Ｎｏ.８のセラミックスは、単斜晶ＺｒＯ２比率が高く、強度、硬度、靭性がともに、上記のセラミックスよりも低かった。 さらに、ＴｉＯ２、ＭｇＯ及びＳｉＯ２の何れをも含有していない比較例のセラミックス（試料Ｎｏ．９）は、試料Ｎｏ.８のセラミックスに比して、靭性がさらに劣っていた。 From Table 1, the ceramics according to the present invention (sample Nos. 1 to 7) in which the aspect ratio of the alumina particles, the long axis average particle diameter, and the average particle diameter of zirconia are within the predetermined ranges have a strength of 1425 to 1550 MPa and fracture toughness. The characteristics of 4.5 to 5.4 MPa√m and hardness of 1730 to 1790 Hv were exhibited. In particular, the material of Sample No. 4 exhibited excellent strength, hardness, and toughness because the firing temperature was low and a fine grain structure was formed. On the other hand, among the ceramics of the present invention, the ceramic of sample No. 8 in which the aspect ratio of the alumina particles, the long axis average particle diameter, etc. are outside the predetermined range has a high monoclinic ZrO 2 ratio, strength, Both hardness and toughness were lower than the above ceramics. Furthermore, the comparative ceramics (sample No. 9) that did not contain any of TiO 2 , MgO, and SiO 2 was further inferior in toughness compared to the ceramic of sample No. 8.
Claims (8)
Ａｌ２Ｏ３含量が６５質量％以上であり、ＺｒＯ２含量が４〜３４質量％の範囲にあり、ＳｒＯを０．１〜４質量％の範囲で含み、さらにＴｉＯ２、ＭｇＯ及びＳｉＯ２を含有しているとともに、該ＴｉＯ ２ 含量、ＭｇＯ含量及びＳｉＯ ２ 含量が何れも０．１質量％以上であり、前記ＺｒＯ２粒子の一部には、ＳｒＯが固溶していることを特徴とするアルミナ・ジルコニア系セラミックス。 In the alumina / zirconia ceramics containing Al 2 O 3 particles and ZrO 2 particles,
Al 2 O 3 content is 65% by mass or more, ZrO 2 content is in the range of 4 to 34% by mass, SrO is included in the range of 0.1 to 4% by mass, and TiO 2 , MgO and SiO 2 are further contained. And the TiO 2 content, MgO content and SiO 2 content are all 0.1% by mass or more, and SrO is dissolved in a part of the ZrO 2 particles. Alumina / zirconia ceramics.
Ａｌ２Ｏ３含量が６５質量％以上であり、ＺｒＯ２含量が４〜３４質量％の範囲にあり、ＳｒＯを０．１〜４質量％の範囲で含み、さらにＴｉＯ２、ＭｇＯ及びＳｉＯ２を含有しているとともに、該ＴｉＯ ２ 含量、ＭｇＯ含量及びＳｉＯ ２ 含量が何れも０．１質量％以上であり、前記ＺｒＯ２粒子の一部には、ＴｉＯ２が固溶していることを特徴とするアルミナ・ジルコニア系セラミックス。 In the alumina / zirconia ceramics containing Al 2 O 3 particles and ZrO 2 particles,
Al 2 O 3 content is 65% by mass or more, ZrO 2 content is in the range of 4 to 34% by mass, SrO is included in the range of 0.1 to 4% by mass, and TiO 2 , MgO and SiO 2 are further contained. And the TiO 2 content, MgO content and SiO 2 content are all 0.1% by mass or more, and TiO 2 is dissolved in a part of the ZrO 2 particles. Alumina-zirconia ceramics.
前記原料粉末を所定形状に成形し、
得られた成形体を、１３００℃〜１５００℃の温度範囲で焼成し、
更に前記焼成温度より３０℃以上低い温度で熱間静水圧処理すること、
を特徴とするアルミナ・ジルコニア系セラミックスの製法。 Contains 65% by mass or more of Al in terms of oxide, 4 to 34% by mass of Zr in terms of oxide and 0.1 to 4% by mass of Sr in terms of oxide, and further oxidizes Ti, Mg and Si A raw material powder containing 0.1% by mass or more in terms of product and having a total content of 1 to 5% by mass in terms of oxides of Sr, Ti, Mg and Si is prepared,
The raw material powder is molded into a predetermined shape,
The obtained molded body was fired at a temperature range of 1300 ° C to 1500 ° C,
Furthermore, hot isostatic pressing at a temperature lower by 30 ° C. or more than the firing temperature,
A process for producing alumina-zirconia ceramics.
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| DE602004014689T DE602004014689D1 (en) | 2003-08-28 | 2004-08-27 | Alumina-zirconia ceramic and process for its production |
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| FR2897612B1 (en) | 2006-02-17 | 2008-05-16 | Saint Gobain Ct Recherches | TITANIUM-ZIRCONIA ALUMINUM OXIDE FELT GRAIN |
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| JPH01320264A (en) * | 1988-06-21 | 1989-12-26 | Inax Corp | Production of alumina-series ceramic |
| JPH05262560A (en) * | 1992-03-17 | 1993-10-12 | Mitsubishi Materials Corp | Production of cutting tool made of aluminum oxide-zirconium oxide ceramic having excellent toughness |
| JPH06191937A (en) * | 1992-10-05 | 1994-07-12 | Shinagawa Refract Co Ltd | Sintered material of zro2 partially stabilized with mgo and its production |
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| JPH01320264A (en) * | 1988-06-21 | 1989-12-26 | Inax Corp | Production of alumina-series ceramic |
| JPH05262560A (en) * | 1992-03-17 | 1993-10-12 | Mitsubishi Materials Corp | Production of cutting tool made of aluminum oxide-zirconium oxide ceramic having excellent toughness |
| JPH06191937A (en) * | 1992-10-05 | 1994-07-12 | Shinagawa Refract Co Ltd | Sintered material of zro2 partially stabilized with mgo and its production |
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