JP2005075659A - Ceramic sintered compact, method for producing the same, and biomaterial - Google Patents
Ceramic sintered compact, method for producing the same, and biomaterial Download PDFInfo
- Publication number
- JP2005075659A JP2005075659A JP2003305233A JP2003305233A JP2005075659A JP 2005075659 A JP2005075659 A JP 2005075659A JP 2003305233 A JP2003305233 A JP 2003305233A JP 2003305233 A JP2003305233 A JP 2003305233A JP 2005075659 A JP2005075659 A JP 2005075659A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- sintered body
- ceramic sintered
- tio
- mgo
- 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.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
本発明は、抗折強度を向上させたセラミックス焼結体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セラミックス焼結体およびその製法を提供する。 The present invention relates to a ceramic sintered body with improved bending strength, and particularly a ceramic sintered body suitably used for various structural members, cutting tools, medical instruments, and biomaterials, and a method for producing the same. I will provide a.
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複合化する場合は、結晶粒の微細化効果によりそれぞれの単体よりも高い強度が得られることが注目されている（例えば非特許文献１参照）。
また、上記複合材の製造コスト低減若しくは特性改善の目的で、更に種々の添加物を少量に複合化する研究が行われている。例えば、アルミナが７０質量％以上の組成範囲でＳｉＯ２、ＭｇＯ、及びＣａＯを添加することにより低温での緻密化焼結を実現し、低い製造コストで耐摩耗性に優れた材料が開示されている（例えば特許文献１、特許文献２参照）。
更に、周期律表５Ａ族金属酸化物とＳｉＯ２を同時に添加して、異方性成長促進する効果による高靭性アルミナ、ジルコニア複合材料が開示されている（例えば特許文献３参照）。
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, when alumina and zirconia are compounded at a certain ratio, it has been noticed that a higher strength than each simple substance can be obtained due to the effect of crystal grain refinement (see, for example, Non-Patent Document 1).
In addition, for the purpose of reducing the manufacturing cost or improving the characteristics of the composite material, studies have been conducted to further compound various additives into small amounts. For example, a material that realizes densification and sintering at low temperature by adding SiO 2 , MgO, and CaO in a composition range of 70% by mass or more of alumina, and that is excellent in wear resistance at a low manufacturing cost is disclosed. (For example, refer to Patent Document 1 and Patent Document 2).
Furthermore, a high toughness alumina and zirconia composite material by the effect of simultaneously adding a group 5A metal oxide and SiO 2 in the periodic table to promote anisotropic growth is disclosed (for example, see Patent Document 3).
しかし、前記特許文献１では、アルミナの量が６０％以上になると強度が急激に低下し、高い硬度と耐摩耗性が要求される高アルミナ含有量の組成域では強度が低い問題があった。また、前記特許文献１及び特許文献２で開示した耐磨耗性アルミナ質セラミックスは液相焼結による焼結欠陥減少で耐摩耗性の改善が見られるが、強度と硬度が低いという問題があった。さらに、前記特許文献３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たものの、三点曲げ強度が１０００ＭＰａ以下で、特許文献１で開示されたセラミックスより低く、切削工具、産業機械、医療器具用の高特性が要求される部材には満足しうる曲げ強度ではない。 However, in Patent Document 1, when the amount of alumina is 60% or more, the strength sharply decreases, and there is a problem that the strength is low in a composition region having a high alumina content that requires high hardness and wear resistance. Further, the wear-resistant alumina ceramics disclosed in Patent Document 1 and Patent Document 2 show improved wear resistance due to a reduction in sintering defects due to liquid phase sintering, but there is a problem that strength and hardness are low. It was. Further, in Patent Document 3, although an effect of improving toughness was observed by the anisotropic growth of alumina, the three-point bending strength is 1000 MPa or less, which is lower than the ceramic disclosed in Patent Document 1, cutting tools, industrial machines, It is not a satisfactory bending strength for members requiring high properties for medical devices.
本発明者らは、アルミアを主体としたＡｌ２Ｏ３とＺｒＯ２からなる原料に一定量のＳｉＯ２、ＴｉＯ２およびＭｇＯを添加して、１３００℃〜１５００℃という比較的低い温度範囲で焼結させることにより、結晶粒成長を効果的に抑制でき、得られた焼結体は従来の材料を超える高強度材料を得られることを見出し、本発明に至った。 The present inventors added a certain amount of SiO 2 , TiO 2 and MgO to a raw material composed mainly of aluminum and consisting of Al 2 O 3 and ZrO 2 , and baked in a relatively low temperature range of 1300 ° C. to 1500 ° C. As a result, it has been found that crystal grain growth can be effectively suppressed, and that the obtained sintered body can obtain a high-strength material that exceeds conventional materials, and has led to the present invention.
すなわち、本発明は、Ａｌ２Ｏ３及びＺｒＯ２と、添加剤であるＳｉＯ２、ＴｉＯ２及びＭｇＯを含むセラミックス焼結体であって、Ａｌ２Ｏ３を６５〜９６質量％、ＺｒＯ２を４〜３４．４質量％含有して、ＳｉＯ２を０．２０質量％以上、ＴｉＯ２を０．２２質量％以上、及びＭｇＯを０．１２質量％以上含有し、かつＳｉＯ２、ＴｉＯ２及びＭｇＯの合計の含有割合が０．６〜４．５質量％であることを特徴とするセラミックス焼結体に関する発明である。 That is, the present invention is a ceramic sintered body containing Al 2 O 3 and ZrO 2 and additives SiO 2 , TiO 2, and MgO, wherein Al 2 O 3 is 65 to 96% by mass and ZrO 2 is ZrO 2 . 4 to 34.4% by mass, SiO 2 is 0.20% by mass or more, TiO 2 is 0.22% by mass or more, and MgO is 0.12% by mass or more, and SiO 2 , TiO 2 and It is an invention relating to a ceramic sintered body characterized in that the total content of MgO is 0.6 to 4.5% by mass.
本発明においては、更に
（１）前記Ａｌ２Ｏ３の平均粒径が３μｍ以下、及びＺｒＯ２の平均粒径が０．５μｍ以下であること、
（２）前記セラミックス焼結体におけるＺｒＯ２の２０％以上が正方晶であること、
（３）前記ＴｉＯ２とＭｇＯの原子比Ｔｉ／Ｍｇが０．５〜１．２の範囲であること、
（４）前記ＴｉＯ２とＭｇＯの少なくとも一部がＡｌ２Ｏ３結晶に溶解して固溶体結晶を形成しており、その溶解量が合わせて該Ａｌ２Ｏ３の０．１質量％以上に相当する量であること、
（５）前記Ａｌ２Ｏ３の少なく一部の結晶粒内にＴｉとＭｇの酸化物若しくはこれらを含む複合酸化物粒子が分散して存在すること
が望ましい。
In the present invention, (1) the average particle diameter of the Al 2 O 3 is 3 μm or less, and the average particle diameter of ZrO 2 is 0.5 μm or less.
(2) 20% or more of ZrO 2 in the ceramic sintered body is tetragonal,
(3) The atomic ratio Ti / Mg of TiO 2 and MgO is in the range of 0.5 to 1.2,
(4) At least a part of the TiO 2 and MgO is dissolved in an Al 2 O 3 crystal to form a solid solution crystal, and the combined amount corresponds to 0.1% by mass or more of the Al 2 O 3 The amount to be
(5) It is desirable that oxides of Ti and Mg or composite oxide particles containing these are present in a small part of the crystal grains of Al 2 O 3 .
また、本発明は、Ａｌ、Ｚｒ、Ｓｉ、Ｔｉ及びＭｇを金属として、又はこれらの金属化合物として含む原料を、これらの金属又は金属化合物を金属酸化物に換算して、セラミックス焼結体中でＡｌ２Ｏ３を６５〜９６質量％、ＺｒＯ２を４〜３４．４質量％含有し、更にＳｉＯ２、ＴｉＯ２及びＭｇＯの含有割合がそれぞれ０．２０質量％以上、０．２２質量％以上、及び０．１２質量％以上であって、かつＳｉＯ２、ＴｉＯ２及びＭｇＯの合計の含有割合が０．６〜４．５質量％となるように混合して、所定形状に成形後、１３００〜１５００℃で焼成することを特徴とするセラミックス焼結体の製法に関する発明である。
本発明においては、１３００〜１５００℃での焼成を酸化雰囲気で行い、更に前記焼成温度よりも６０℃以上低い温度で還元雰囲気において熱処理する工程を有することが望ましい。
Further, the present invention provides a raw material containing Al, Zr, Si, Ti and Mg as metals or these metal compounds, in a ceramic sintered body by converting these metals or metal compounds into metal oxides. Al 2 O 3 is contained in an amount of 65 to 96% by mass, ZrO 2 is contained in an amount of 4 to 34.4% by mass, and the content ratios of SiO 2 , TiO 2 and MgO are 0.20% by mass or more and 0.22% by mass or more, respectively. And 0.12% by mass or more, and the total content of SiO 2 , TiO 2, and MgO is mixed so as to be 0.6 to 4.5% by mass, and after forming into a predetermined shape, 1300 It is invention regarding the manufacturing method of the ceramic sintered compact characterized by baking at -1500 degreeC.
In the present invention, it is desirable to have a step of performing firing at 1300 to 1500 ° C. in an oxidizing atmosphere, and further heat-treating in a reducing atmosphere at a temperature lower than the firing temperature by 60 ° C. or more.
更に、本発明は、Ａｌ２Ｏ３及びＺｒＯ２と、添加剤であるＳｉＯ２、ＴｉＯ２及びＭｇＯからなるセラミックス焼結体であって、Ａｌ２Ｏ３を６５〜９６質量％、ＺｒＯ２を４〜３４．４質量％含有し、更にＳｉＯ２、ＴｉＯ２及びＭｇＯをそれぞれ０．２０質量％以上、０．２２質量％以上、及び０．１２質量％以上含有して、かつＳｉＯ２、ＴｉＯ２及びＭｇＯの合計の含有割合が０．６〜４．５質量％であるセラミックス焼結体より作製された生体用材料に関する発明である。 Furthermore, the present invention is a ceramic sintered body comprising Al 2 O 3 and ZrO 2 and additives SiO 2 , TiO 2 and MgO, wherein Al 2 O 3 is 65 to 96% by mass and ZrO 2 is ZrO 2 . 4 to 34.4% by mass, SiO 2 , TiO 2 and MgO are further contained by 0.20% by mass, 0.22% by mass and 0.12% by mass, respectively, and SiO 2 , TiO It is an invention relating to a biomaterial manufactured from a ceramic sintered body having a total content ratio of 2 and MgO of 0.6 to 4.5% by mass.
本発明のセラミックス焼結体は、Ａｌ２Ｏ３の含有割合が６５〜９６質量％、ＺｒＯ２の含有割合が４〜３４．４質量％であり、更にＳｉＯ２の含有割合が０．２０質量％以上、ＴｉＯ２の含有割合が０．２２質量％以上、及びＭｇＯの含有割合が０．１２質量％以上であって、かつＳｉＯ２、ＴｉＯ２及びＭｇＯの合計の含有割合が０．６〜４．５質量％であることを特徴とする。
本発明のセラミックス焼結体は、上記組成範囲のＡｌ２Ｏ３とＺｒＯ２に添加剤としてＳｉＯ２、ＴｉＯ２およびＭｇＯを一定割合含有させることにより、焼結の際にＡｌ２Ｏ３と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の実現が可能となる。
In the ceramic sintered body of the present invention, the content ratio of Al 2 O 3 is 65 to 96 mass%, the content ratio of ZrO 2 is 4 to 34.4 mass%, and the content ratio of SiO 2 is 0.20 mass%. %, The content ratio of TiO 2 is 0.22 mass% or more, and the content ratio of MgO is 0.12 mass% or more, and the total content ratio of SiO 2 , TiO 2 and MgO is 0.6 to It is 4.5 mass%.
Ceramics sintered body of the present invention, by the SiO 2, TiO 2 and MgO is constant percentage contained as an additive to Al 2 O 3 and ZrO 2 in the above composition range, Al 2 O 3 during sintering and ZrO The sintered body can be densified under a low temperature condition while suppressing the growth of crystal grains 2 and high strength can be realized by forming fine grains and a high-density structure.
本発明のセラミックス焼結体は、その焼結体におけるＡｌ２Ｏ３の平均粒径が３μｍ以下で、ＺｒＯ２の平均粒径が０．５μｍ以下であることが好ましい。また、ＺｒＯ２総量の少なくとも２０％以上が正方晶である焼結体であることが好ましい。これらにより相変態強化効果を有効に発現することができる。
また、前記添加剤の中でＴｉＯ２とＭｇＯの原子比（Ｔｉ／Ｍｇ）が０．５〜１．２の範囲のものが好ましい。これにより、強度低下の原因となる化合物の形成を抑制でき、より高強度化の焼結体を得ることが可能となる。
更に、前記ＴｉＯ２とＭｇＯの少なくとも一部がＡｌ２Ｏ３結晶に溶解して固溶体結晶を形成しており、その溶解量が合わせて該Ａｌ２Ｏ３の０．１質量％以上に相当する量とすることが望ましい。これによりＡｌ２Ｏ３結晶が固溶体形成により強化される。
更にまた、前記Ａｌ２Ｏ３の少なく一部の結晶粒内にＴｉあるいはＭｇの酸化物若しくは複合酸化物粒子が分散して存在することが望ましい。
ＴｉあるいはＭｇの酸化物若しくは複合酸化物粒子の分散強化効果によりセラミックス焼結体の強度と靭性を一層向上させることが可能となる。
The ceramic sintered body of the present invention preferably has an average particle diameter of Al 2 O 3 of 3 μm or less and an average particle diameter of ZrO 2 of 0.5 μm or less. Moreover, it is preferable that it is a sintered body in which at least 20% or more of the total amount of ZrO 2 is tetragonal. By these, the phase transformation strengthening effect can be expressed effectively.
Among the additives, those having an atomic ratio (Ti / Mg) of TiO 2 to MgO in the range of 0.5 to 1.2 are preferable. Thereby, formation of the compound causing the strength reduction can be suppressed, and a sintered body with higher strength can be obtained.
Furthermore, at least a part of the TiO 2 and MgO is dissolved in the Al 2 O 3 crystal to form a solid solution crystal, and the combined amount corresponds to 0.1% by mass or more of the Al 2 O 3. The amount is desirable. Thereby, the Al 2 O 3 crystal is strengthened by solid solution formation.
Furthermore, it is desirable that Ti or Mg oxide or composite oxide particles be dispersed in a small part of the crystal grains of Al 2 O 3 .
The strength and toughness of the ceramic sintered body can be further improved by the dispersion strengthening effect of Ti or Mg oxide or composite oxide particles.
本発明のセラミックス焼結体の製法は、Ａｌ、Ｚｒ、Ｓｉ、Ｔｉ及びＭｇを金属として、又はこれらの金属化合物として含む原料を、これらの金属又は金属化合物を金属酸化物に換算して、セラミックス焼結体中でＡｌ２Ｏ３を６５〜９６質量％、ＺｒＯ２を４〜３４．４質量％含有し、更にＳｉＯ２、ＴｉＯ２及びＭｇＯの含有割合がそれぞれ０．２０質量％以上、０．２２質量％以上、及び０．１２質量％以上であって、ＳｉＯ２、ＴｉＯ２及びＭｇＯの合計の含有割合が０．６〜４．５質量％となるように混合して、所定形状に成形後、１３００〜１５００℃で焼成することを特徴とする。
本発明においては特に、前記酸化雰囲気で得られた上記焼結体を、更に前記焼成温度よりも６０℃以上低い温度で還元雰囲気において熱処理する工程を有することが望ましい。このような条件で焼結することにより、ＴｉとＭｇの酸化物がＡｌ２Ｏ３でその溶解度が変化し、Ａｌ２Ｏ３とは異なる化合物粒子がＡｌ２Ｏ３の結晶粒内に析出することが可能となる。
本発明のセラミックス焼結体は、人工骨頭のような、高強度が要求される無毒で生体になじみやすく、拒否反応を起こさない人工材料として人工骨、人工歯根などの生体用材料に好適に使用される。
The method for producing a ceramic sintered body according to the present invention is obtained by converting a raw material containing Al, Zr, Si, Ti, and Mg as a metal or these metal compounds into a ceramic by converting these metals or metal compounds into metal oxides. The sintered body contains 65 to 96% by mass of Al 2 O 3 and 4 to 34.4% by mass of ZrO 2 , and the content ratio of SiO 2 , TiO 2 and MgO is 0.20% by mass or more, 0 .22 mass% or more, and 0.12 mass% or more, and the total content of SiO 2 , TiO 2 and MgO is mixed so as to be 0.6 to 4.5 mass% to obtain a predetermined shape It is characterized by firing at 1300-1500 ° C. after molding.
In the present invention, in particular, it is desirable to further include a step of heat-treating the sintered body obtained in the oxidizing atmosphere in a reducing atmosphere at a temperature lower than the firing temperature by 60 ° C. or more. By sintering under such conditions, oxides of Ti and Mg whose solubility is changed by Al 2 O 3, different compound particles are precipitated in the crystal grains of Al 2 O 3 is the Al 2 O 3 It becomes possible.
The ceramic sintered body of the present invention is suitably used as a biomaterial such as an artificial bone and an artificial tooth root as an artificial material such as an artificial bone head, which is non-toxic and easily adaptable to a living body, which does not cause a rejection reaction. Is done.
本発明により、組織微細化、高緻密化、相変態強化に加えて、固溶強化、粒子分散強化の効果をＡｌ２Ｏ３−ＺｒＯ２系複合材で発現でき、高硬度、高強度のセラミックス焼結体の提供が可能となる。 According to the present invention, the effect of solid solution strengthening and particle dispersion strengthening can be expressed by Al 2 O 3 —ZrO 2 composite material in addition to refinement of structure, densification, and phase transformation strengthening, and high hardness and high strength ceramics A sintered body can be provided.
通常Ａｌ２Ｏ３−ＺｒＯ２系複合系では、Ａｌ２Ｏ３の含有量が多いほどヤング率、硬度が高くなる反面、焼成温度が高いことによる粒成長が材料の強度を低下させる。しかし、Ａｌ２Ｏ３−ＺｒＯ２系原料粉末にＳｉＯ２、ＴｉＯ２及びＭｇＯ原料粉末を添加して焼成すると、共晶点が１３００℃以下になり、材料の焼結が大きく促進され、従来行われていた温度よりも低い温度でも組織が微細に保たれながら高い緻密性の焼結体が得られるようになる。
上記高強度を得る特徴は、Ａｌ２Ｏ３６５質量％以上の高ヤング率、高硬度の組成において効果的に発現される。
従って、本発明のセラミックス焼結体において、Ａｌ２Ｏ３の含有割合は６５質量％以上、好ましくは７０％質量以上であり、一方、Ａｌ２Ｏ３の含有割合は９６質量％以下、好ましくは９０質量％以下、特に好ましくは８５質量％以下である。上記６５〜９６質量％の範囲とすることにより、高強度かつ高硬度という効果が得られる。
また、ＺｒＯ２の含有割合は４質量％以上、好ましくは１０質量％以上、特に好ましくは１５質量％以上であり、一方、ＺｒＯ２の含有割合は３４．４質量％以下、好ましくは３０質量％以下、特に好ましくは２５質量％以下である。上記４〜３４．４質量％の範囲とすることにより、粒径微細化という効果が得られる。
Usually, in the Al 2 O 3 —ZrO 2 -based composite system, the higher the content of Al 2 O 3 , the higher the Young's modulus and hardness, but the grain growth due to the high firing temperature reduces the strength of the material. However, when SiO 2 , TiO 2 and MgO raw material powders are added to the Al 2 O 3 —ZrO 2 raw material powder and fired, the eutectic point becomes 1300 ° C. or less, and the sintering of the material is greatly promoted. A highly dense sintered body can be obtained while maintaining a fine structure even at a temperature lower than the known temperature.
The characteristics for obtaining the high strength are effectively expressed in a composition having a high Young's modulus and a high hardness of 65% by mass or more of Al 2 O 3 .
Therefore, in the ceramic sintered body of the present invention, the content ratio of Al 2 O 3 is 65% by mass or more, preferably 70% by mass or more, while the content ratio of Al 2 O 3 is 96% by mass or less, preferably It is 90 mass% or less, Most preferably, it is 85 mass% or less. By setting the content in the range of 65 to 96% by mass, the effects of high strength and high hardness can be obtained.
The content ratio of ZrO 2 is 4% by mass or more, preferably 10% by mass or more, particularly preferably 15% by mass or more, while the content ratio of ZrO 2 is 34.4% by mass or less, preferably 30% by mass. Hereinafter, it is particularly preferably 25% by mass or less. By setting the content in the range of 4 to 34.4% by mass, the effect of reducing the particle size can be obtained.
また、上記したように、例えばＡｌ２Ｏ３とＺｒＯ２原料にＳｉＯ２、ＴｉＯ２及びＭｇＯ原料を添加して焼成する際の共晶点を１３００℃以下とするには、前記ＳｉＯ２の含有割合は、０．２０質量％以上、好ましくは０・４質量％以上、ＴｉＯ２の含有割合は、０．２２質量％以上、好ましくは０．３質量％以上、及びＭｇＯの含有割合は、０．１２質量％以上、好ましくは０．２質量％以上である。
ＳｉＯ２、ＴｉＯ２及びＭｇＯの含有割合がそれぞれ前記０．２０質量％未満、０．２２質量％未満、及び０．１２質量％未満では、焼結温度で形成された液相の粘度が高くなる為焼結促進効果が小さくなる。
尚、ＳｉＯ２、ＴｉＯ２及びＭｇＯの合計の含有割合が０．６〜４．５質量％、好ましくは１．０〜３．０質量％である。
該範囲とすることにより、高緻密化と微粒組織形成という効果が得られる。
Further, as described above, for example, the eutectic point of time of firing by adding SiO 2, TiO 2 and MgO raw material Al 2 O 3 and ZrO 2 raw material 1300 ° C. or less, the content of the SiO 2 The ratio is 0.20 mass% or more, preferably 0.4 mass% or more, the content ratio of TiO 2 is 0.22 mass% or more, preferably 0.3 mass% or more, and the content ratio of MgO is 0 .12% by mass or more, preferably 0.2% by mass or more.
When the content ratio of SiO 2 , TiO 2 and MgO is less than 0.20% by mass, less than 0.22% by mass and less than 0.12% by mass, respectively, the viscosity of the liquid phase formed at the sintering temperature becomes high. Therefore, the sintering promotion effect is reduced.
Incidentally, SiO 2, total content ratio of the TiO 2 and MgO are 0.6 to 4.5 wt%, preferably from 1.0 to 3.0 wt%.
By setting it as this range, the effect of high densification and fine grain formation can be obtained.
本発明のセラミック焼結体は、上記組成中のＡｌ２Ｏ３の一部をＣｒ２Ｏ３によって置換して固溶体を形成するもしくはＺｒＯ２の一部をＨｆＯ２によって置換して固溶体を形成することにより硬度を改善することも可能である。また、粒成長抑制する目的、若しくは結晶の形状異方性成長を促進する目的で他の化合物を添加することも可能である。 Ceramic sintered body of the present invention forms a solid solution with part of that or ZrO 2 form a solid solution by substituting part of Al 2 O 3 by Cr 2 O 3 in the composition was replaced by HfO 2 Therefore, it is possible to improve the hardness. It is also possible to add other compounds for the purpose of suppressing grain growth or promoting the shape anisotropic growth of crystals.
次に、本発明のセラミックス焼結体の好ましい形態について説明する。
（１）セラミック焼結体の高強度特性を得るには、上記焼結体中のＡｌ２Ｏ３の平均粒径は好ましくは３μｍ以下、特に好ましくは２μｍ以下、ＺｒＯ２の平均粒径は好ましくは０．５μｍ以下、特に好ましくは０．３μｍ以下である。このような平均粒径とすることにより微粒化による強度向上だけでなく、ＺｒＯ２の微細、均一分散により相変態強化効果を大きくすることが可能となる。
（２）本発明のセラミックス焼結体中で、前記ＺｒＯ２粒子の２０％以上、好ましくは４０％以上を正方晶とすることが好ましい。ＺｒＯ２に、Ｙ、Ｃｅ、Ｍｇ、Ｃａなど種々の安定化剤を添加して、正方晶を室温においても準安定化の状態で存在させることは可能ではある。特にこれらの安定化剤を少量添加した場合、例えば、ＺｒＯ２に対して、２ｍｏｌ％以下のＹ２Ｏ３を添加すると、組織微粒化により単斜晶への相変態を抑制し、応力下での相変態発生のポテシャルが高く、相変態強化効果が大きくなる。
Next, the preferable form of the ceramic sintered compact of this invention is demonstrated.
(1) In order to obtain high strength characteristics of the ceramic sintered body, the average particle diameter of Al 2 O 3 in the sintered body is preferably 3 μm or less, particularly preferably 2 μm or less, and the average particle diameter of ZrO 2 is preferably Is 0.5 μm or less, particularly preferably 0.3 μm or less. By setting such an average particle size, not only the strength improvement by atomization but also the effect of strengthening the phase transformation can be increased by the fine and uniform dispersion of ZrO 2 .
(2) In the ceramic sintered body of the present invention, 20% or more, preferably 40% or more of the ZrO 2 particles are preferably tetragonal. Various stabilizers such as Y, Ce, Mg, and Ca can be added to ZrO 2 so that the tetragonal crystals can exist in a metastable state even at room temperature. In particular, when a small amount of these stabilizers are added, for example, when 2 mol% or less of Y 2 O 3 is added to ZrO 2 , the phase transformation to monoclinic crystals is suppressed by the atomization of the structure, and under stress The phase transformation occurrence potential is high, and the effect of strengthening the phase transformation is increased.
（３）本発明のセラミックス焼結体は、前記組成範囲で、ＴｉＯ２とＭｇＯの組成比は原子比（Ｔｉ／Ｍｇ）で０．５〜１．２の範囲とすることが好ましい。原子比（Ｔｉ／Ｍｇ）が前記０．５以上のときに焼成温度で液相の粘度が高くなるのをより効果的に抑制でき、良好な焼結促進効果が得られる。また、原子比（Ｔｉ／Ｍｇ）が前記１．２以下のときにＴｉＯ２とＡｌ２Ｏ３とが反応し熱膨張係数の異方性が大きいＡｌ２ＴｉＯ５相が生成するのを抑制し、強度低下を防止できる。材料の焼結性向上およびＡｌ２ＴｉＯ５相生成を抑える見地から、原子比（Ｔｉ／Ｍｇ）が０．７〜１．０の範囲であることが特に好ましい。
ＴｉとＭｇの原子比が前記範囲であるときに、同時にＡｌ２Ｏ３結晶により効果的に固溶するという効果も得られる。
（４）前記ＴｉＯ２とＭｇＯがＡｌ２Ｏ３結晶に溶解して固溶体結晶を形成することにより、焼結後の粒界相を減少して硬度を上げるとともに、Ａｌ２Ｏ３結晶を強化し、強度を向上することは本発明のセラミックス焼結体の好ましい形態の１つである。該Ａｌ２Ｏ３結晶へのＴｉＯ２とＭｇＯの溶解量が少なければ上記効果が小さいので、前記組成中ＴｉＯ２とＭｇＯが合わせて該Ａｌ２Ｏ３の０．１質量％以上に相当する量がＡｌ２Ｏ３結晶に溶解していることが好ましい。この場合、該Ａｌ２Ｏ３の０．５質量％以上に相当する量が該Ａｌ２Ｏ３結晶に溶解していることが特に好ましい。
(3) In the ceramic sintered body of the present invention, the composition ratio of TiO 2 and MgO is preferably in the range of 0.5 to 1.2 in terms of atomic ratio (Ti / Mg). When the atomic ratio (Ti / Mg) is 0.5 or more, an increase in the viscosity of the liquid phase at the firing temperature can be more effectively suppressed, and a good sintering acceleration effect can be obtained. Further, when the atomic ratio (Ti / Mg) is 1.2 or less, TiO 2 and Al 2 O 3 react with each other to suppress the formation of an Al 2 TiO 5 phase having a large thermal expansion coefficient anisotropy. , Strength reduction can be prevented. From the viewpoint of suppressing the sinterability of the material and suppressing the generation of Al 2 TiO 5 phase, the atomic ratio (Ti / Mg) is particularly preferably in the range of 0.7 to 1.0.
When the atomic ratio of Ti and Mg is within the above range, the effect of effective solid solution with the Al 2 O 3 crystal is also obtained.
(4) The TiO 2 and MgO dissolve in the Al 2 O 3 crystal to form a solid solution crystal, thereby reducing the grain boundary phase after sintering and increasing the hardness, and strengthening the Al 2 O 3 crystal. Improving the strength is one of the preferred forms of the ceramic sintered body of the present invention. Since the Al 2 O 3 TiO 2 and the dissolved amount is less if the effect of MgO on the crystal is small, the amount of said TiO 2 and MgO in the composition is combined equivalent to more than 0.1% by weight of the Al 2 O 3 Is preferably dissolved in the Al 2 O 3 crystal. In this case, it is particularly preferred that an amount equivalent to more than 0.5% by weight of the Al 2 O 3 is dissolved in the Al 2 O 3 crystal.
（５）本発明の好ましい他の態様は、前記Ａｌ２Ｏ３の少なく一部の結晶粒内にＴｉとＭｇの酸化物若しくはこれらを含む複合酸化物粒子を分散させることである。前記ＴｉとＭｇの酸化物若しくはこれらを含む複合酸化物がＡｌ２Ｏ３結晶に溶解して形成した固溶体を、溶解量が少ない条件下では析出し、例えば、ＴｉＯ２、ＭｇＡｌ２Ｏ４の微粒子がＡｌ２Ｏ３の結晶粒内に分散した組織を形成する。これにより、微粒子分散の強化効果で材料の強度を大幅に向上できる。上記微粒子のサイズについては、長軸０．２μｍ以下が好ましく、０．１μｍ以下が特に好ましい。 (5) Another preferable aspect of the present invention is to disperse oxides of Ti and Mg or composite oxide particles containing these in a small part of the crystal grains of Al 2 O 3 . The solid solution formed by dissolving the oxide of Ti and Mg or a composite oxide containing these in an Al 2 O 3 crystal is precipitated under a condition where the amount of dissolution is small. For example, fine particles of TiO 2 and MgAl 2 O 4 Forms a structure dispersed in the crystal grains of Al 2 O 3 . Thereby, the intensity | strength of material can be improved significantly by the reinforcement effect of microparticle dispersion | distribution. The size of the fine particles is preferably 0.2 [mu] m or less, and particularly preferably 0.1 [mu] m or less.
本発明のセラミックス焼結体は、種々の公知のセラミックス原料を用いて作製することができる。本発明のセラミックス焼結体の製法は、先ず、原料を所定の割合で混合し、所定形状に成形する。ここでいう原料とは、酸化物、金属、炭酸塩、水酸化物などの塩類等を粉末あるは水溶液等して使用することが可能である。
粉末として使用する場合その平均粒径は、１．０μｍ以下が好ましい。
また、成形には、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の成形法を使用可能である。次に、本発明によれば、１３００〜１５００の温度範囲で焼成することが重要である。上記焼結温度が１３００℃未満であると緻密な焼結体が得られず、また１５００℃を超えると、結晶粒成長が発生するため、いずれの場合も高強度の焼結体は得られにくい。上記の見地から、本発明の焼結体は特に１３５０〜１４５０℃で焼成されることが望ましい。また、本発明では、この焼成後に、上記焼成温度（１３５０〜１４５０℃）よりも６０℃以上低い温度で熱間静水圧焼成を行うことが望ましい。更には、この熱間静水圧焼成後に、更に前記焼成温度（１３５０〜１４５０℃）よりも６０℃以上低い温度で還元雰囲気において熱処理することが好ましい。
The ceramic sintered body of the present invention can be produced using various known ceramic raw materials. In the method for producing a ceramic sintered body of the present invention, first, raw materials are mixed at a predetermined ratio and formed into a predetermined shape. The raw material here can be used as a powder or an aqueous solution of salts such as oxides, metals, carbonates and hydroxides.
When used as a powder, the average particle size is preferably 1.0 μm or less.
For the molding, a molding method such as press molding, casting, cold isostatic pressing, or cold isostatic pressing can be used. Next, according to the present invention, it is important to bake in a temperature range of 1300 to 1500. If the sintering temperature is less than 1300 ° C., a dense sintered body cannot be obtained, and if it exceeds 1500 ° C., crystal grain growth occurs, and in either case, a high-strength sintered body is difficult to obtain. . From the above viewpoint, the sintered body of the present invention is particularly preferably fired at 1350 to 1450 ° C. Moreover, in this invention, after this baking, it is desirable to perform hot isostatic baking at the temperature lower 60 degreeC or more than the said baking temperature (1350-1450 degreeC). Furthermore, after this hot isostatic firing, it is preferable to perform heat treatment in a reducing atmosphere at a temperature lower by 60 ° C. or more than the firing temperature (1350 to 1450 ° C.).
上記の焼成は酸化性雰囲気、例えば大気中、或いは一定の酸素分圧を有する混合ガス雰囲気で行うと、ＴｉＯ２とＭｇがＡｌ２Ｏ３結晶粒内に溶解する。
本発明によれば、このようにして得られた焼結体を、好ましくは前記焼成温度よりも６０℃以上低い温度、特に好ましくは１１００〜１３５０℃で還元雰囲気において熱処理することにより、Ｔｉの原子価が４価から３価に変化してＴｉＯ２の溶解度が増加し、その結果Ｍｇの溶解度が減少するため、Ａｌ２Ｏ３の結晶粒内にＭｇが含まれた化合物、ＭｇＡｌ２Ｏ４が析出する。これにより本発明の微粒子分散強化のセラミックス焼結体が得られる。
本発明のセラミックス焼結体は、高硬度及び高強度という特性を有するので、種々の構造部材、摺動部材、切削工具に使用できる。特に、人工骨頭のような、安定性、高強度、耐磨耗性が要求される生体用材料に好適に使用される。
When the above baking is performed in an oxidizing atmosphere, for example, the air or a mixed gas atmosphere having a constant oxygen partial pressure, TiO 2 and Mg are dissolved in the Al 2 O 3 crystal grains.
According to the present invention, the thus obtained sintered body is preferably heat-treated in a reducing atmosphere at a temperature lower than the firing temperature by 60 ° C. or more, particularly preferably 1100 to 1350 ° C. Since the solubility of TiO 2 increases and the solubility of Mg decreases as a result of the change from tetravalent to trivalent, the MgAl 2 O 4 compound, MgAl 2 O 4 , is included in the Al 2 O 3 crystal grains. Precipitate. As a result, the ceramic sintered body with enhanced dispersion of fine particles of the present invention can be obtained.
Since the ceramic sintered body of the present invention has characteristics of high hardness and high strength, it can be used for various structural members, sliding members, and cutting tools. In particular, it is suitably used for biomaterials that require stability, high strength, and wear resistance, such as artificial bone heads.
純度が９９．９質量％で平均結晶粒径０．５μｍのＡｌ２Ｏ３粉末と、純度が９９．９質量％で平均粒径０．２μｍのＺｒＯ２粉末、Ｙ２Ｏ３の含有割合がそれぞれ０、１．５、２、３ｍｏｌ％の準安定化ＺｒＯ２、および純度９９．５質量％以上で、平均粒径０．５〜１．０μｍのＳｉＯ２、ＴｉＯ２およびＭｇ（ＯＨ）２を表１に示す割合でイソプロピルアルコールの溶媒混合後、圧力１００ＭＰａで成形し、その後３００ＭＰａで冷間静水圧処理した。これを表１に示す温度で大気中5時間焼成し、一部の試料については更に表１に示す温度（ＨＩＰ温度）でＡｒ−Ｏ２（Ｏ２濃度：２０容積％）混合ガス雰囲気中で２００ＭＰａの熱間静水圧処理を行った。更に、１部の試料については表１に示す温度（水素処理温度）下に水素雰囲気中で５時間熱処理した。 Al 2 O 3 powder having a purity of 99.9% by mass and an average crystal grain size of 0.5 μm, a ZrO 2 powder having a purity of 99.9% by mass and an average grain size of 0.2 μm, and a content ratio of Y 2 O 3 Metastable ZrO 2 of 0 , 1.5, 2 and 3 mol%, respectively, and SiO 2 , TiO 2 and Mg (OH) 2 having a purity of 99.5% by mass or more and an average particle size of 0.5 to 1.0 μm. After mixing the solvent of isopropyl alcohol at the ratio shown in Table 1, it was molded at a pressure of 100 MPa, and then cold isostatically treated at 300 MPa. This was baked in the air at the temperature shown in Table 1 for 5 hours, and some samples were further heated at the temperature shown in Table 1 (HIP temperature) in an Ar—O 2 (O 2 concentration: 20% by volume) mixed gas atmosphere. A hot isostatic pressure treatment of 200 MPa was performed. Further, one part of the sample was heat-treated for 5 hours in a hydrogen atmosphere at the temperature shown in Table 1 (hydrogen treatment temperature).
得られた焼結体の破断面の走査型電子顕微鏡写真よりＡｌ２Ｏ３とＺｒＯ２の結晶粒径を測定した。
また、Ｘ線回折強度より全ＺｒＯ２中の正方晶ＺｒＯ２の比率を計算した。計算方法を以下に示す。
正方晶比率（％）＝Ｉｔ／（Ｉｍ１＋Ｉｍ２＋Ｉｔ）
ここで、Ｉｔ：正方晶（１１１）面のＸ線回折強度
Ｉｍ１：単斜晶（１１１）面のＸ線回折強度
Ｉｍ２：単斜晶（−１１−１）面のＸ線回折強度
なお、一部の試料に対し、Ａｌ２Ｏ３の格子定数測定によりＴｉＯ２とＭｇＯの溶解量を推定した。また、水素雰囲気で熱処理した試料を透過型電子顕微鏡でＭｇＡｌ２Ｏ４微粒子が結晶粒内に析出分散していることを確認した。
上記の試料を三点曲げ試験およびビッカース硬度を測定し、上記組織構造解析の結果と合わせて表２に示した。
The crystal grain sizes of Al 2 O 3 and ZrO 2 were measured from scanning electron micrographs of the fracture surface of the obtained sintered body.
Moreover, to calculate the tetragonal ZrO 2 in the ratio of the total ZrO 2 from X-ray diffraction intensity. The calculation method is shown below.
Tetragonal ratio (%) = I t / (I m1 + I m2 + I t )
Here, I t : X-ray diffraction intensity of tetragonal (111) plane I m1 : X-ray diffraction intensity of monoclinic (111) plane I m2 : X-ray diffraction intensity of monoclinic (-11-1) plane For some samples, the dissolved amounts of TiO 2 and MgO were estimated by measuring the lattice constant of Al 2 O 3 . Moreover, it was confirmed that the MgAl 2 O 4 fine particles were precipitated and dispersed in the crystal grains of the sample heat-treated in a hydrogen atmosphere using a transmission electron microscope.
The sample was measured for a three-point bending test and Vickers hardness, and the results are shown in Table 2 together with the results of the structure analysis.
表１，２から分かるように、本発明に基いたセラミックス焼結体は、抗折強度が１３００ＭＰａ以上、ビッカース硬度が１７００Ｈｖ以上の高強度、高硬度を示した。特に、試料Ｎｏ．２０〜２３は、微粒子分散強化の効果が加わり、抗折強度が１７００ＭＰａ以上、ビッカース硬度が１８００Ｈｖ以上の優れた特性を示した。
これに対して試料Ｎｏ．６は、ＳｉＯ２、ＴｉＯ２およびＭｇＯを添加せず、試料Ｎｏ．７は上記添加量が本発明より少なく、試料Ｎｏ．８はＳｉＯの量が少ないため、何れも焼成温度が高くなり、結晶粒成長により強度と硬度が低下した。また、試料Ｎｏ．１３は上記添加量が多すぎたため、粒界相が多く形成することにより低強度、低硬度であった。
As can be seen from Tables 1 and 2, the ceramic sintered body based on the present invention exhibited a high strength and a high hardness with a bending strength of 1300 MPa or more and a Vickers hardness of 1700 Hv or more. In particular, sample no. Nos. 20 to 23 exhibited an excellent characteristic that the effect of strengthening the fine particle dispersion was added, the bending strength was 1700 MPa or more, and the Vickers hardness was 1800 Hv or more.
In contrast, sample no. No. 6 does not add SiO 2 , TiO 2, and MgO. No. 7 has a smaller amount of addition than the present invention. In No. 8, since the amount of SiO was small, the firing temperature was high, and the strength and hardness were lowered due to crystal grain growth. Sample No. No. 13 had a low strength and a low hardness due to the formation of a large number of grain boundary phases because the addition amount was too large.
表１示すＮｏ．６、１６と２１の材料を用い、人工骨頭を作製した。６０回転／ｍｉｎ、荷重５０ｋｇの条件で同材質の臼との１０００ｈ摩耗試験の結果を表３に示す。本発明以外の試料Ｎｏ．６に比べ、本発明の試料Ｎｏ．１６と２１は摩耗量が小さく、摩耗後の表面状態良好であることが分かる。 No. shown in Table 1. Artificial bone heads were prepared using materials 6, 16, and 21. Table 3 shows the result of a 1000 h wear test with a mortar made of the same material under the conditions of 60 rotations / min and a load of 50 kg. Sample No. other than the present invention. Compared to sample No. 6, sample No. 16 and 21 show that the amount of wear is small and the surface condition after wear is good.
本発明で得られるセラミックス焼結体は、種々の構造部材、切削工具、生体用材料に好適に使用される。 The ceramic sintered body obtained by the present invention is suitably used for various structural members, cutting tools, and biomaterials.
Claims (9)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003305233A JP2005075659A (en) | 2003-08-28 | 2003-08-28 | Ceramic sintered compact, method for producing the same, and biomaterial |
| US10/927,266 US7148167B2 (en) | 2003-08-28 | 2004-08-26 | Alumina/zirconia ceramics and method of producing the same |
| EP04255176A EP1510509B1 (en) | 2003-08-28 | 2004-08-27 | Alumina/zirconia ceramics and method of producing the same |
| DE602004014689T DE602004014689D1 (en) | 2003-08-28 | 2004-08-27 | Alumina-zirconia ceramic and process for its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003305233A JP2005075659A (en) | 2003-08-28 | 2003-08-28 | Ceramic sintered compact, method for producing the same, and biomaterial |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2005075659A true JP2005075659A (en) | 2005-03-24 |
Family
ID=34408707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003305233A Pending JP2005075659A (en) | 2003-08-28 | 2003-08-28 | Ceramic sintered compact, method for producing the same, and biomaterial |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2005075659A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006095018A (en) * | 2004-09-29 | 2006-04-13 | Kyocera Corp | Biological member and joint prosthesis using the same |
| JP2006122634A (en) * | 2003-12-25 | 2006-05-18 | Kyocera Corp | Biological member, artificial joint employing the same, and method for manufacture the member |
| JP2007209912A (en) * | 2006-02-10 | 2007-08-23 | Sage Corporation | Manufacturing method of ceramics particles for improving quality of chlorine treated water and quality improving method of chlorine treated water |
| JP2009056458A (en) * | 2007-08-06 | 2009-03-19 | Sage Corporation | Washing water making apparatus, washing water, water making apparatus and water making method |
| JP2010229570A (en) * | 2009-03-26 | 2010-10-14 | Kyocera Corp | Fiber guide |
| JP2013501121A (en) * | 2009-08-05 | 2013-01-10 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Melted alumina-zirconia grit |
| JP2013199415A (en) * | 2012-03-26 | 2013-10-03 | Kyocera Corp | Ceramic sintered compact, electronic component mounting substrate using the same, and electronic device |
| KR101322442B1 (en) | 2006-02-17 | 2013-10-25 | 생-고뱅 생트레 드 레체르체 에 데투드 유로삐엔 | Alumina - titanium oxide - zirconia fused grain |
| US9550169B2 (en) | 2014-09-08 | 2017-01-24 | Denso Corporation | Honeycomb structure body and method of producing the same |
| WO2020022425A1 (en) * | 2018-07-27 | 2020-01-30 | 京セラ株式会社 | Aluminous porcelain and ceramic heater |
| JP2020147822A (en) * | 2019-03-15 | 2020-09-17 | 株式会社高純度化学研究所 | MANUFACTURING METHOD OF MgO-TiO-BASED SPUTTERING TARGET |
-
2003
- 2003-08-28 JP JP2003305233A patent/JP2005075659A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006122634A (en) * | 2003-12-25 | 2006-05-18 | Kyocera Corp | Biological member, artificial joint employing the same, and method for manufacture the member |
| JP2006095018A (en) * | 2004-09-29 | 2006-04-13 | Kyocera Corp | Biological member and joint prosthesis using the same |
| JP2007209912A (en) * | 2006-02-10 | 2007-08-23 | Sage Corporation | Manufacturing method of ceramics particles for improving quality of chlorine treated water and quality improving method of chlorine treated water |
| KR101322442B1 (en) | 2006-02-17 | 2013-10-25 | 생-고뱅 생트레 드 레체르체 에 데투드 유로삐엔 | Alumina - titanium oxide - zirconia fused grain |
| JP2009056458A (en) * | 2007-08-06 | 2009-03-19 | Sage Corporation | Washing water making apparatus, washing water, water making apparatus and water making method |
| JP2010229570A (en) * | 2009-03-26 | 2010-10-14 | Kyocera Corp | Fiber guide |
| JP2013501121A (en) * | 2009-08-05 | 2013-01-10 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Melted alumina-zirconia grit |
| JP2013199415A (en) * | 2012-03-26 | 2013-10-03 | Kyocera Corp | Ceramic sintered compact, electronic component mounting substrate using the same, and electronic device |
| US9550169B2 (en) | 2014-09-08 | 2017-01-24 | Denso Corporation | Honeycomb structure body and method of producing the same |
| WO2020022425A1 (en) * | 2018-07-27 | 2020-01-30 | 京セラ株式会社 | Aluminous porcelain and ceramic heater |
| CN112739661A (en) * | 2018-07-27 | 2021-04-30 | 京瓷株式会社 | Alumina ceramic and ceramic heater |
| JPWO2020022425A1 (en) * | 2018-07-27 | 2021-08-12 | 京セラ株式会社 | Alumina porcelain and ceramic heaters |
| JP7148613B2 (en) | 2018-07-27 | 2022-10-05 | 京セラ株式会社 | Alumina porcelain and ceramic heater |
| JP2020147822A (en) * | 2019-03-15 | 2020-09-17 | 株式会社高純度化学研究所 | MANUFACTURING METHOD OF MgO-TiO-BASED SPUTTERING TARGET |
| JP7178707B2 (en) | 2019-03-15 | 2022-11-28 | 株式会社高純度化学研究所 | Method for manufacturing MgO-TiO-based sputtering target |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5366398B2 (en) | Composite ceramics and manufacturing method thereof | |
| EP1510509B1 (en) | Alumina/zirconia ceramics and method of producing the same | |
| JP4428267B2 (en) | Zirconia-alumina composite ceramic material and method for producing the same | |
| JP6637956B2 (en) | Sintered ceramic material, powder composition for obtaining sintered ceramic material, method for producing the same, and ceramic component | |
| EP1514856B1 (en) | Alumina/zirconia ceramics and method of producing the same | |
| WO2005042047A1 (en) | Biological member and method for manufacture thereof | |
| JP2005075659A (en) | Ceramic sintered compact, method for producing the same, and biomaterial | |
| JP4589642B2 (en) | Alumina / zirconia ceramics and process for producing the same | |
| JP4883885B2 (en) | Biomaterial, method for manufacturing the same, and artificial joint | |
| CN100435860C (en) | Biological member and method for manufacture thereof | |
| JP4761749B2 (en) | Biomaterial and artificial joint using the same | |
| JP4831945B2 (en) | Zirconia-alumina ceramics and process for producing the same | |
| JP4601304B2 (en) | Alumina / zirconia ceramics and process for producing the same | |
| JP4601303B2 (en) | Alumina / zirconia ceramics and process for producing the same | |
| JP3488350B2 (en) | Alumina sintered body and method for producing the same | |
| JP3559413B2 (en) | Alumina sintered body and method for producing the same | |
| JP3145597B2 (en) | Alumina sintered body and method for producing the same | |
| JP3121996B2 (en) | Alumina sintered body | |
| JP4514563B2 (en) | Alumina / zirconia ceramics and process for producing the same | |
| JP2005008435A (en) | Composite ceramic and method for preparing the same | |
| JP2010248051A (en) | Alumina-zirconia composite sintered compact | |
| JP4612358B2 (en) | Alumina / zirconia ceramics and production method thereof | |
| JP4460918B2 (en) | Alumina / zirconia ceramics and process for producing the same | |
| JP4243514B2 (en) | Composite ceramics and manufacturing method thereof | |
| JP2005211253A (en) | Biological member, method for manufacture thereof and artificial joint |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060518 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081215 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081224 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090220 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090714 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20091201 |