JP2004075532A - High strength / high toughness zirconia sintered material and biomaterial using the same - Google Patents
High strength / high toughness zirconia sintered material and biomaterial using the same Download PDFInfo
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Abstract
Description
本発明は、摺動部材、刃物、医療器材、食器具、機械部品など構造用材料、並びに特に人工骨、人工関節、人工歯根などの生体材料として好適なジルコニア焼結材に関する。 The present invention relates to a zirconia sintered material that is suitable as a structural material such as a sliding member, a knife, a medical instrument, a tableware, and a mechanical component, and particularly a biomaterial such as an artificial bone, an artificial joint, or an artificial tooth root.
純粋なジルコニア（ＺｒＯ2）は、高温から順に、立方晶（cubic）、正方晶（tetragonal）、単斜晶（monoclinic）の三つの結晶相を示す。平衡論上は、１１７０℃以下の低温では単斜晶、１１７０℃から２３７０℃の間では正方晶、２３７０℃から融点（２７１５℃）までが立方晶とされている。単斜晶と正方晶との相転位はマルテンサイト型であり、約４．６％の体積変化を伴う。純粋なジルコニアはこの体積変化のため、転移温度を通過すると破壊するため、安定して使用することができない。そこで、一般的にはＹ2Ｏ3、ＣａＯ、ＭｇＯなどの酸化物を１．５〜１５ mol％程度添加し、蛍石型の立方晶とし、加熱によっても転移の生じない安定化ＺｒＯ2 として広く使用されてきた。 Pure zirconia (ZrO 2 ) exhibits three crystal phases, cubic, tetragonal, and monoclinic, in order from high temperature. According to the equilibrium theory, at a low temperature of 1170 ° C. or lower, monoclinic crystal is used, 1170 ° C. to 2370 ° C. is tetragonal, and 2370 ° C. to melting point (2715 ° C.) is cubic. The phase transition between monoclinic and tetragonal is martensitic, with a volume change of about 4.6%. Pure zirconia cannot be used stably because of its volume change, it breaks when it passes the transition temperature. Therefore, generally, about 1.5 to 15 mol% of an oxide such as Y 2 O 3 , CaO, or MgO is added to form a fluorite-type cubic crystal, and as stabilized ZrO 2 which does not undergo transition even by heating. Widely used.
これに対し、準安定な正方晶を一部残した部分安定化ジルコニアは高強度・高靱性を持つことが明らかとなり注目されている。 に 対 し On the other hand, partially stabilized zirconia partially leaving a metastable tetragonal crystal has been clearly noted and has high strength and high toughness.
例えば、正方晶ジルコニア多結晶体（Tetragonal Zirconia Polycrystal:ＴＺＰ）、特にＹ2Ｏ3を固溶し、正方晶ジルコニア（ｔ−ＺｒＯ2 ）の安定領域１３００℃〜１５５０℃の温度で焼結して正方晶または正方晶と立方晶とからなるＹ−ＴＺＰは高強度・高靱性であり、構造用部材として用いられている。この高強度・高靱性の発現は応力誘起変態によってもたらされる。つまり、応力場における亀裂先端で準安定相である正方晶から単斜晶への相変態による破壊エネルギーの緩和によって生じている。しかしながら、このようなＴＺＰはｔ−ＺｒＯ2 が単斜晶ジルコニアに変化すると同時に体積膨張を生じるため、変態しすぎると表面性状の荒れを引き起こしたり、かえって強度が低下するなどの問題があった。特に水分存在下の１００〜３００℃付近の温度域では相変態しやすくなる。 For example, tetragonal zirconia polycrystal (Tetragonal Zirconia Polycrystal: TZP), in particular, Y 2 O 3 is dissolved and sintered in a stable region of tetragonal zirconia (t-ZrO 2 ) at a temperature of 1300 ° C. to 1550 ° C. Y-TZP comprising tetragonal or tetragonal and cubic has high strength and high toughness and is used as a structural member. The development of high strength and high toughness is brought about by stress-induced transformation. That is, it is caused by relaxation of fracture energy due to phase transformation from tetragonal, which is a metastable phase, to monoclinic at a crack tip in a stress field. However, such TZP has a problem that, when t-ZrO 2 is changed to monoclinic zirconia and at the same time, volume expansion occurs, so that too much transformation causes rough surface properties or lowers strength. In particular, in a temperature range around 100 to 300 ° C. in the presence of moisture, phase transformation is likely to occur.
また、ＣｅＯ2 を固溶し、正方晶または正方晶と立方晶とからなるＣｅ−ＴＺＰは、相変態を起こすしきい値が低いため比較的低応力で相変態が誘起され、Ｙ2Ｏ3で安定化する場合よりも広い相変態ゾーンがクラック先端で得られる。そのため、Ｙ2Ｏ3で安定化したＺｒＯ2 と比べ、ＣｅＯ2 で安定化したＺｒＯ2 であるＣｅ−ＴＺＰは１０ＭＰａ・ｍ1/2 以上の高い破壊靱性を示す。また、Ｃｅ−ＴＺＰは水分存在下の１００〜３００℃付近の温度域でもほとんど相変態せず、さらに広い固溶範囲を持つなど優れた特性を有した材料として知られている。しかし、この応力誘起相変態のしきい応力の低さのため、逆に強度の低下を招きやすく、Ｙ−ＴＺＰと比べ強度が不十分である。最近ではＣｅ−ＴＺＰにＡｌ2Ｏ3等を分散させて複合化することによりＣｅ−ＴＺＰの強度を向上させることも試みられている。 In addition, Ce-TZP, which is a solid solution of CeO 2 and composed of tetragonal or tetragonal and cubic, has a low threshold value for causing phase transformation, so that phase transformation is induced with relatively low stress and Y 2 O 3 A wider phase transformation zone is obtained at the crack tip than when stabilized at Therefore, Ce-TZP, which is ZrO 2 stabilized with CeO 2 , exhibits higher fracture toughness of 10 MPa · m 1/2 or more than ZrO 2 stabilized with Y 2 O 3 . Also, Ce-TZP is known as a material having almost no phase transformation even in a temperature range of about 100 to 300 ° C. in the presence of moisture and having excellent properties such as having a wider solid solution range. However, due to the low threshold stress of this stress-induced phase transformation, the strength tends to be reduced, and the strength is insufficient compared with Y-TZP. Recently, attempts have been made to improve the strength of Ce-TZP by dispersing Al 2 O 3 or the like in Ce-TZP and forming a composite.
本発明は、上記Ｙ−ＴＺＰおよびＣｅ−ＴＺＰの欠陥を解消し、湿潤環境下においても特性劣化せず、高強度で高靱性なジルコニア焼結材を提供することを目的とする。 An object of the present invention is to provide a high strength and high toughness zirconia sintered material that eliminates the above-described defects of Y-TZP and Ce-TZP, does not deteriorate its properties even in a wet environment, and has a high strength.
Ｃｅ−ＴＺＰレベルの靱性と水分存在下での相の安定性を持ちながら、Ｙ−ＴＺＰレベルの強度を併せ持つジルコニア焼結材について鋭意検討した結果、単にジルコニア焼結材中に安定化剤であるＹ2Ｏ3およびＣｅＯ2 を含有させるだけでは高強度・高靱性を発現させるには不十分であり、Ｙ−ＴＺＰとＣｅ−ＴＺＰとを特定比で含ませることによって、相乗作用によって優れた熱的安定性と高強度・高靭性を発現することを知見し、本発明を完成するに至った。 As a result of diligent studies on a zirconia sintered material having a Y-TZP level strength while having a Ce-TZP level toughness and a phase stability in the presence of moisture, the zirconia sintered material is simply a stabilizer. Including Y 2 O 3 and CeO 2 alone is not enough to develop high strength and high toughness. By including Y-TZP and Ce-TZP at a specific ratio, excellent heat is obtained by synergistic action. The present inventors have found that they exhibit high mechanical stability and high strength and high toughness, and have completed the present invention.
本発明のジルコニア焼結材は、ＣｅＯ2 を８ mol％〜１５ mol％含んだジルコニアと、Ｙ2Ｏ3を２ mol％〜５ mol％含んだジルコニアとが分散したジルコニア焼結材であって、前記ＣｅＯ2 を含んだジルコニアと、前記Ｙ2Ｏ3を含んだジルコニアとの体積比が９：１〜６：４としたものである。
上記ジルコニア焼結材は、ジルコニア中にＹ2Ｏ3およびＣｅＯ2 を均一に分散させたものではなく、意図的に不均一に分散させたものでり、焼結材を微小領域で観察すればＹおよびＣｅが不均一に分布している。この状態に着目して上記ジルコニア焼結材を表現し直すと以下のように表現される。
すなわち、本発明のジルコニア焼結材は、ジルコニアを主成分とし、ＣｅＯ2 を４．７ mol％〜１３．４ mol％およびＹ2Ｏ3を０．２ mol％〜２．１ mol％含むジルコニア焼結材であって、直径５ｎｍ以下の微小領域での観察において、Ｚｒ原子数ＮＺｒに対するＹ原子数ＮＹの割合ＮＹ／ＮＺｒをＹ2Ｏ3の含有量ＭＹ2Ｏ3（ mol％）で除したＮＹ／（ＮＺｒ・ＭＹ2Ｏ3）の標準偏差をσＹとし、前記ＮＺｒに対するＣｅ原子数ＮＣｅの割合ＮＣｅ／ＮＺｒをＣｅＯ2の含有量ＭＣｅＯ2（ mol％）で除したＮＣｅ／（ＮＺｒ・ＭＣｅＯ2 ）の標準偏差をσＣｅとしたとき、前記σＹが０．００１５以上、０．１以下であり、前記σＣｅが０．０００１以上、０．０１以下とされたものである。
上記ジルコニア焼結材には、さらに３０ vol％以下のＡｌ2Ｏ3および／またはＭｇＯあるいはＣａＯを０．０１ vol％〜３．０ vol％含有させることができる。なお、Ａｌ2Ｏ3、ＭｇＯ、ＣａＯなどを含有させる場合におけるＣｅＯ2 、Ｙ2Ｏ3の含有量（ mol％）は、ジルコニア、ＣｅＯ2 およびＹ2Ｏ3の合計を１００としたときのＣｅＯ2 、Ｙ2Ｏ3の構成比を意味するものである。
The zirconia sintered material of the present invention is a zirconia sintered material in which zirconia containing 8 mol% to 15 mol% of CeO 2 and zirconia containing 2 mol% to 5 mol% of Y 2 O 3 are dispersed. The volume ratio between the zirconia containing CeO 2 and the zirconia containing Y 2 O 3 is 9: 1 to 6: 4.
The zirconia sintered material is not a material in which Y 2 O 3 and CeO 2 are uniformly dispersed in zirconia, but is intentionally non-uniformly dispersed. Y and Ce are unevenly distributed. Focusing on this state, the above-mentioned zirconia sintered material can be expressed as follows.
In other words, the zirconia zirconia sintered material of the present invention, the zirconia as a main component, containing CeO 2 4.7 mol% ~13.4 mol% and a Y 2 O 3 0.2 mol% ~2.1 mol% In observation of a sintered material in a minute region having a diameter of 5 nm or less, the ratio NY / NZr of the number of Y atoms NY to the number of Zr atoms NZr is divided by the Y 2 O 3 content MY 2 O 3 (mol%). the NY / and σY standard deviation (NZr · MY 2 O 3) , NCe / (NZr · the percentage NCE / NZr of Ce atoms NCE for said NZr divided by the content MCEO 2 of CeO 2 (mol%) When the standard deviation of MCeO 2 ) is σCe, the σY is 0.0015 or more and 0.1 or less, and the σCe is 0.0001 or more and 0.01 or less.
The zirconia sintered material may further contain 0.01 vol% to 3.0 vol% of Al 2 O 3 and / or MgO or CaO of 30 vol% or less. The content of CeO 2, Y 2 O 3 in the case of containing Al 2 O 3, MgO, CaO or the like (mol%) is, CeO when zirconia, a total of CeO 2 and Y 2 O 3 and 100 2 and Y 2 O 3 .
熱的安定性と高強度・高靱性を併せ持つという相反する課題を克服する鍵は正方晶をどのように存在させるかに有る。安定化剤の添加量が過多となれば、強度・靱性が低下し、過少であれば相変態を生じる。そのため、高強度を発現できるＹ2Ｏ3と相の安定・高靱性を発現できるＣｅＯ2 の同時添加が考えられるが、この場合、強度、靭性は十分に向上しない。一方、Ｙ2Ｏ3を含んだジルコニアとＣｅＯ2 を含んだジルコニアとを分散させて複合化することにより、安定化剤がジルコニア粒子内で不均一に分散した粒子となるため、異種のジルコニア粒子間で相互作用して、マトリックスの拘束力が大きくなり、正方晶が安定する。このため相変態が抑制されるばかりでなく、強度も向上し、靱性はＣｅ−ＴＺＰにより高いレベルを発現するようになる。 The key to overcoming the conflicting issues of having both thermal stability and high strength and high toughness lies in how the tetragonal crystal is present. If the amount of the stabilizer is too large, the strength and toughness decrease, and if the amount is too small, phase transformation occurs. Therefore, simultaneous addition of Y 2 O 3 capable of expressing high strength and CeO 2 capable of exhibiting phase stability and high toughness can be considered, but in this case, strength and toughness are not sufficiently improved. On the other hand, by dispersing and complexing zirconia containing Y 2 O 3 and zirconia containing CeO 2 , the stabilizer becomes non-uniformly dispersed particles in the zirconia particles. Interact with each other to increase the binding force of the matrix and stabilize the tetragonal crystal. For this reason, not only the phase transformation is suppressed, but also the strength is improved, and the toughness is expressed by Ce-TZP at a higher level.
前記ジルコニア焼結材は、水分存在下においても熱的安定性に優れ、高強度・高靭性であるため生体材料、特に摺動部を有する関節部材や人工骨等の骨代替材料として好適である。生体材料として使用する場合、前記ジルコニア焼結材の表面部に厚さ０．１mm〜３mm、気孔率２５％〜７５％の多孔質層を形成することが好ましく、さらに前記多孔質層の表面に生体親和性材料、例えばハイドロキシアパタイトなどのリン酸カルシウム系材料の薄膜によってコーティング層を形成することが好ましい。 The zirconia sintered material is excellent in thermal stability even in the presence of moisture, and has high strength and high toughness. Therefore, the zirconia sintered material is suitable as a biomaterial, particularly as a bone substitute material such as a joint member having a sliding portion or an artificial bone. . When used as a biomaterial, a porous layer having a thickness of 0.1 mm to 3 mm and a porosity of 25% to 75% is preferably formed on the surface of the zirconia sintered material. The coating layer is preferably formed by a thin film of a biocompatible material, for example, a calcium phosphate-based material such as hydroxyapatite.
本発明のジルコニア焼結材は、特定量のＣｅＯ2 を含むジルコニアと特定量のＹ2Ｏ3を含んだジルコニアとが分散し、それらの体積比が９：１〜６：４とされたものであり、前記ＣｅＯ2 およびＹ2Ｏ3の不均一分散状態に着目して言い換えると、Ｚｒ原子数ＮＺｒに対するＹ原子数ＮＹの割合ＮＹ／ＮＺｒをＹ2Ｏ3の含有量ＭＹ2Ｏ3（ mol％）で除したＮＹ／（ＮＺｒ・ＭＹ2Ｏ3）の標準偏差σＹを０．００１５以上、０．１以下とし、および前記ＮＺｒに対するＣｅ原子数ＮＣｅの割合ＮＣｅ／ＮＺｒをＣｅＯ2 の含有量ＭＣｅＯ2 （ mol％）で除したＮＣｅ／（ＮＺｒ・ＭＣｅＯ2 ）の標準偏差σＣｅを０．０００１以上、０．０１以下としたので、湿潤環境下においても表面性状の荒れや、強度、靭性の低下を抑制することができ、特に生体材料として好適なジルコニア焼結材を提供することができる。 The zirconia sintered material of the present invention is one in which zirconia containing a specific amount of CeO 2 and zirconia containing a specific amount of Y 2 O 3 are dispersed, and their volume ratio is 9: 1 to 6: 4. In other words, paying attention to the non-uniform dispersion state of CeO 2 and Y 2 O 3 , in other words, the ratio of the number of Y atoms NY to the number of Zr atoms NZr, NY / NZr, is defined as the Y 2 O 3 content MY 2 O 3 ( mol%) in dividing the NY / (NZr · MY 2 O 3) standard deviations σY 0.0015 or more, and 0.1 or less, and containing a proportion NCE / NZr of Ce atoms NCE for said NZr of CeO 2 Since the standard deviation σCe of NCe / (NZr · MCeO 2 ) divided by the amount MCeO 2 (mol%) was set to 0.0001 or more and 0.01 or less, even in a wet environment, the roughness of the surface properties, the strength, and the toughness were increased. Can be suppressed, It is possible to provide a suitable zirconia sintered material as a biological material.
本発明のジルコニア焼結材は、ＣｅＯ2 を８ mol％〜１５ mol％含んだジルコニア（Ｃｅ−ＴＺＰ）と、Ｙ2Ｏ3を２ mol％〜５ mol％含んだジルコニア（Ｙ−ＴＺＰ）とが分散してなるジルコニア焼結材であり、前記所定量のＣｅＯ2 を含むジルコニア粉末および前記所定量のＹ2Ｏ3を含むジルコニア粉末とを均一に混合して焼結一体化したものである。なお、所定量のＣｅＯ2 、Ｙ2Ｏ3を含有するジルコニア原料粉末のジルコニアは結晶構造がＴＺＰである必要はない。 The zirconia sintered material of the present invention is composed of zirconia (Ce-TZP) containing 8 mol% to 15 mol% of CeO 2 and zirconia (Y-TZP) containing 2 mol% to 5 mol% of Y 2 O 3. Is a zirconia sintered material in which the zirconia powder containing the predetermined amount of CeO 2 and the zirconia powder containing the predetermined amount of Y 2 O 3 are uniformly mixed and sintered and integrated. . The zirconia of the zirconia raw material powder containing predetermined amounts of CeO 2 and Y 2 O 3 does not need to have a crystal structure of TZP.
Ｃｅ−ＴＺＰに固溶しているＣｅＯ2 は正方晶ジルコニアの安定化剤として作用する。安定化剤は熱力学的に正方晶の化学的自由エネルギーを小さくするから、多くしすぎると安定になりすぎて靱性強化に有効な変態を生じず、少なすぎると焼結後の冷却時に単斜晶へ変態する。そのため、ＣｅＯ2 を８〜１５ mol％とするのが好ましく、より好ましくは１０〜１２ mol％である。原料粉末のサイズには特に制限はないが、比表面積（Ｂ．Ｅ．Ｔ．値）５ｍ2/ｇ以上、好ましくは１０ｍ2/ｇ以上の粉末が好ましい。 CeO 2 dissolved in Ce-TZP acts as a stabilizer for tetragonal zirconia. Stabilizers thermodynamically reduce the chemical free energy of the tetragonal crystal.If too large, the stabilizer will be too stable and will not produce a transformation effective for strengthening toughness, and if too small, it will be monoclinic during cooling after sintering. Transforms into crystals. Therefore, the content of CeO 2 is preferably set to 8 to 15 mol%, more preferably 10 to 12 mol%. The size of the raw material powder is not particularly limited, but a powder having a specific surface area (BET value) of 5 m 2 / g or more, preferably 10 m 2 / g or more is preferable.
Ｙ−ＴＺＰに固溶しているＹ2Ｏ3 は正方晶ジルコニアの安定化剤として作用する。Ｙ2Ｏ3もＣｅＯ2同様に、多くしすぎると安定になりすぎて靱性強化に有効な変態を生じず、少なすぎると焼結後の冷却時に単斜晶へ変態する。そのため、Ｙ2Ｏ3を２〜５ mol％とするのが好ましく、より好ましくは２．５〜３．５ mol％である。原料粉末のサイズには特に制限はないが、比表面積（Ｂ．Ｅ．Ｔ．値）５ｍ2/ｇ以上、好ましくは１０ｍ2/ｇ以上の粉末が好ましい。 Y 2 O 3 dissolved in Y-TZP acts as a stabilizer for tetragonal zirconia. As with CeO 2, if Y 2 O 3 is too large, it becomes too stable and does not undergo transformation effective for strengthening toughness. If it is too small, it transforms to monoclinic upon cooling after sintering. Therefore, the content of Y 2 O 3 is preferably 2 to 5 mol%, and more preferably 2.5 to 3.5 mol%. The size of the raw material powder is not particularly limited, but a powder having a specific surface area (BET value) of 5 m 2 / g or more, preferably 10 m 2 / g or more is preferable.
前記ＣｅＯ2 を含んだＣｅ−ＴＺＰと、前記Ｙ2Ｏ3を含んだＹ−ＴＺＰとの体積比は９：１〜６：４とされる。
Ｃｅ−ＴＺＰは主に靱性と相変態抑制に、Ｙ−ＴＺＰは主に強度に寄与する。そのため、ＣｅＯ2 含有ジルコニアが多すぎると強度低下を招き、Ｙ2Ｏ3含有のジルコニアが多すぎると靱性低下や相変態を招く。そのため、ＣｅＯ2 含有のジルコニアとＹ2Ｏ3含有のジルコニアとの体積比は９：１〜６：４、好ましくは８：２〜７：３とするのがよい。
The volume ratio between the Ce-TZP containing CeO 2 and the Y-TZP containing Y 2 O 3 is 9: 1 to 6: 4.
Ce-TZP mainly contributes to toughness and suppression of phase transformation, and Y-TZP mainly contributes to strength. Therefore, if the amount of zirconia containing CeO 2 is too large, the strength is reduced, and if the amount of zirconia containing Y 2 O 3 is too large, the toughness is reduced and phase transformation is caused. Therefore, the volume ratio of zirconia containing CeO 2 to zirconia containing Y 2 O 3 is preferably 9: 1 to 6: 4, and more preferably 8: 2 to 7: 3.
ジルコニアに含まれるＹ2Ｏ3とＣｅＯ2 はジルコニア粒子内で不均一に分散しているほうが、粒子間で相互作用して、マトリックスの拘束力が大きくなり、正方晶が安定する。このため、上記のように８ mol％〜１５ mol％のＣｅＯ2 を含有するジルコニア粉末と２ mol％〜５ mol％のＹ2Ｏ3を含有するジルコニア粉末とを体積比で９：１〜６：４で混合、分散して焼結したものが好適である。この様な焼結材はＹ2Ｏ3とＣｅＯ2 とが不均一な状態で分散しており、Ｙ、Ｃｅ原子の不均一分散状態を統計的に表現すると以下のように表現される。すなわち、前記ジルコニア焼結材は、ジルコニアを主成分とし、焼結材の全体においてＣｅＯ2 を４．７ ｍｏｌ％〜１３．４ ｍｏｌ％、Ｙ2Ｏ3を０．２ ｍｏｌ％〜２．１ ｍｏｌ％含み、直径５ｎｍ以下の微小領域での観察において、Ｚｒ原子数ＮＺｒに対するＹ原子数ＮＹの割合ＮＹ／ＮＺｒをＹ2Ｏ3の含有量ＭＹ2Ｏ3（ｍｏｌ％）で除したＮＹ／（ＮＺｒ・ＭＹ2Ｏ3）の標準偏差をσＹ、前記ＮＺｒに対するＣｅ原子数ＮＣｅの割合ＮＣｅ／ＮＺｒをＣｅＯ2の含有量ＭＣｅＯ2（ mol％）で除したＮＣｅ／（ＮＺｒ・ＭＣｅＯ2 ）の標準偏差をσＣｅとしたとき、０．００１５≦σＹ≦０．１および０．０００１≦σＣｅ≦０．０１となっている。
前記ジルコニア焼結材の全体におけるＣｅＯ2 およびＹ2Ｏ3の含有量は、８ mol％〜１５ mol％のＣｅＯ2を含有するジルコニア（Ｃｅ−ＴＺＰ）と２ mol％〜５ mol％のＹ2Ｏ3 を含有するジルコニア（Ｙ−ＴＺＰ）との体積比が９：１〜６：４であることから導かれる値である。直径５ｎｍ以下の微小領域とは、Ｃｅ−ＴＺＰあるいはＹ−ＴＺＰの粉末に比して十分に小さい、ＺｒＯ2 基結晶粒子レベルでの微小領域を意味する。ＮＹ／ＮＺｒをＭＹ2Ｏ3で除し、またＮＣｅ／ＮＺｒをＭＣｅＯ2 で除すのは、Ｙ2Ｏ3あるいはＣｅＯ2 の添加量によってＮＹ／ＮＺｒ、ＮＣｅ／ＮＺｒの値が変動するのを防止し、添加量による影響を捨象して可及的にＣｅ−ＴＺＰ、Ｙ−ＴＺＰの分散状態のみによる分子（原子）の分布を把握するためである。また、前記σＹ、σＣｅの下限値は、８ mol％〜１５ mol％のＣｅＯ2 を含有するジルコニア粉末と２ mol％〜５ mol％のＹ2Ｏ3を含有するジルコニア粉末とを体積比９：１〜６：４で混合、分散した種々の焼結材を用いて後述の実施例で説明した観察手法により観察した結果得られた値である。
When Y 2 O 3 and CeO 2 contained in zirconia are non-uniformly dispersed in the zirconia particles, they interact with each other to increase the binding force of the matrix and stabilize the tetragonal crystal. Therefore, as described above, the zirconia powder containing 8 mol% to 15 mol% of CeO 2 and the zirconia powder containing 2 mol% to 5 mol% of Y 2 O 3 are mixed at a volume ratio of 9: 1 to 6%. : 4, mixed, dispersed and sintered. In such a sintered material, Y 2 O 3 and CeO 2 are dispersed in a non-uniform state, and the non-uniform dispersion state of Y and Ce atoms is statistically expressed as follows. That is, the zirconia sintered material has zirconia as a main component, and 4.7 mol% to 13.4 mol% of CeO 2 and 0.2 mol% to 2.1 mol of Y 2 O 3 in the whole sintered material. In the observation in a minute region having a diameter of 5 nm or less, the ratio NY / NZr of the number of Y atoms NY to the number of Zr atoms NZr divided by the content of Y 2 O 3 MY 2 O 3 (mol%). (NZr · MY 2 O 3) σY the standard deviation of, NCE / obtained by dividing the percentage NCE / NZr of Ce atoms NCE in content MCEO 2 of CeO 2 (mol%) relative to the NZr of (NZr · MCeO 2) Assuming that the standard deviation is σCe, the relations are 0.0015 ≦ σY ≦ 0.1 and 0.0001 ≦ σCe ≦ 0.01.
The content of CeO 2 and Y 2 O 3 in the entire of the zirconia sintered material, zirconia containing 8 mol% ~15 mol% of CeO 2 (Ce-TZP) and 2 mol% ~5 mol% of Y 2 This is a value derived from the fact that the volume ratio to zirconia containing O 3 (Y-TZP) is 9: 1 to 6: 4. The minute region having a diameter of 5 nm or less means a minute region at the level of ZrO 2 -based crystal particles, which is sufficiently smaller than Ce-TZP or Y-TZP powder. The reason for dividing NY / NZr by MY 2 O 3 and dividing NCe / NZr by MCeO 2 is that the values of NY / NZr and NCe / NZr vary depending on the amount of Y 2 O 3 or CeO 2 added. The reason is to prevent the influence of the amount of addition and to understand the distribution of molecules (atoms) only by the dispersion state of Ce-TZP and Y-TZP as much as possible. The lower limits of σY and σCe are as follows: a zirconia powder containing 8 mol% to 15 mol% of CeO 2 and a zirconia powder containing 2 mol% to 5 mol% of Y 2 O 3 at a volume ratio of 9: This is a value obtained as a result of observation using various sintered materials mixed and dispersed in a ratio of 1 to 6: 4 by the observation method described in Examples described later.
前記ジルコニア焼結材に、さらにＡｌ2Ｏ3を混合、分散させることによりジルコニア粒子とＡｌ2Ｏ3 粒子とが複合化して、高強度化を図ることができる。そのためには、Ａｌ2Ｏ3 を混合、分散させることが必要であり、３０ vol％を超えると凝集しやすくなり、強度低下を招くので、Ａｌ2Ｏ3含有量は３０ vol％以下に止めるのがよい。Ａｌ2Ｏ3含有のジルコニア焼結材は、ＣｅＯ2 を含有するジルコニア粉末、Ｙ2Ｏ3を含有するジルコニア粉末およびＡｌ2Ｏ3粉末を均一に混合、分散させて焼結すればよく、Ａｌ2Ｏ3粉末のサイズには特に制限はないが、比表面積（Ｂ．Ｅ．Ｔ．値）５ｍ2/ｇ以上の粉末が好ましい。 By further mixing and dispersing Al 2 O 3 into the zirconia sintered material, the zirconia particles and the Al 2 O 3 particles are composited, and the strength can be increased. For that purpose, it is necessary to mix and disperse Al 2 O 3 , and if it exceeds 30 vol%, it tends to agglomerate and the strength is reduced. Therefore, the Al 2 O 3 content is limited to 30 vol% or less. Is good. Al 2 O 3 containing zirconia sintered material of zirconia powder containing CeO 2, mixing the zirconia powder and Al 2 O 3 powder containing Y 2 O 3 uniformly, it is sufficient sintering are dispersed, Al The size of the 2 O 3 powder is not particularly limited, but a powder having a specific surface area (BET value) of 5 m 2 / g or more is preferable.
前記ジルコニア焼結材に、前記Ａｌ2Ｏ3のほか、あるいはこれに加えてＭｇＯもしくはＣａＯを混合、分散させることにより高靱性化を図ることができる。ＭｇＯ、ＣａＯは焼結助剤として作用して密度の上昇のために、靱性を向上させる。そのためには、微量のＭｇＯもしくはＣａＯを混合、分散させる必要があり、含有量は３．０ vol％を上限とする。少なすぎると効果を発揮できないので、下限は０．０１ vol％とする。なお、添加形態は純度２Ｎ以上であるならば、ＭｇＯ、ＣａＯに限定されず、ＭｇＣＯ3、Ｍｇ(ＯＨ)2、ＣａＣＯ3、Ｃａ(ＯＨ)2でもよい。これらの化合物を使用する場合、その添加量はＭｇＯもしくはＣａＯに換算した量が０．０１ vol％〜３．０ vol％となればよい。 By mixing and dispersing MgO or CaO in addition to the Al 2 O 3 or in addition to the Al 2 O 3 to the zirconia sintered material, it is possible to increase the toughness. MgO and CaO act as sintering aids to increase the density and thus improve the toughness. For that purpose, it is necessary to mix and disperse a small amount of MgO or CaO, and the upper limit of the content is 3.0 vol%. If the amount is too small, the effect cannot be exhibited, so the lower limit is set to 0.01 vol%. The addition form is not limited to MgO and CaO as long as the purity is 2N or more, but may be MgCO 3 , Mg (OH) 2 , CaCO 3 , or Ca (OH) 2 . When these compounds are used, the added amount thereof may be 0.01 vol% to 3.0 vol% in terms of MgO or CaO.
なお、本発明のジルコニア焼結材は、上述の成分のみによって形成されることが好ましく、不可避的不純物はできるだけ少ない方がよいが、本発明では特性に影響を及ぼさない範囲として３wt％程度以下の不可避的不純物は許容される。特に、ＺｒＯ2 原料中に存在し分離の難しいＨｆＯ2 の混入は特性に全く影響を及ぼさない。 The zirconia sintered material of the present invention is preferably formed of only the above-mentioned components, and the unavoidable impurities are preferably as small as possible. However, in the present invention, the range of about 3 wt% or less does not affect the characteristics. Inevitable impurities are acceptable. In particular, the incorporation of HfO 2 which is present in the ZrO 2 raw material and is difficult to separate has no effect on the characteristics.
前記ジルコニア焼結材の製法は特に限定されないが、例えば以下のように原料粉末の混合、混合粉末の圧粉成形、成形体の焼結の各工程を通して製造される。粉末の混合方法は常法に従えばよい。もっとも、湿式混合した後、乾燥および造粒して二次粒子としておけば作業上の取り扱い性や成分偏析防止上好ましい。所望体積比となるように配合され、混合されたジルコニア混合粉末は成形圧１〜２ton／cm2で静水圧プレス法により圧粉成形される。このジルコニア成形体は、１３５０〜１５５０℃程度の正方晶安定域で２時間程度焼結される。ここで、焼結方法は常圧焼結してもよく、熱間静水圧加圧焼結（ＨＩＰ）してもよい。ただし、Ａｒ雰囲気化でＨＩＰすればＣｅＯ2 が還元されて表面にクラックを生じるので、酸素雰囲気化でＨＩＰすることが好ましい。例えば、成形体を１４００℃、１５００気圧、８０％Ａｒ−２０％Ｏ2 雰囲気中で２時間ＨＩＰ焼結すればよい。 The method for producing the zirconia sintered material is not particularly limited. For example, the zirconia sintered material is produced through the following steps of mixing raw material powder, compacting the mixed powder, and sintering the compact. The method of mixing the powder may be in accordance with a conventional method. However, it is preferable from the standpoint of workability in operation and prevention of component segregation if secondary mixing is performed after drying and granulation after wet mixing. The zirconia mixed powder mixed and mixed so as to have a desired volume ratio is compacted by isostatic pressing at a compacting pressure of 1 to 2 ton / cm 2 . This zirconia molded body is sintered in a tetragonal stable region of about 1350 to 1550 ° C. for about 2 hours. Here, the sintering method may be normal pressure sintering or hot isostatic pressing sintering (HIP). However, if HIP is performed in an Ar atmosphere, CeO 2 is reduced to cause cracks on the surface. Therefore, HIP is preferably performed in an oxygen atmosphere. For example, the compact may be HIP-sintered at 1400 ° C., 1500 atm, 80% Ar-20% O 2 atmosphere for 2 hours.
前記ジルコニア焼結材を生体材料として用いる場合、例えばインプラントと骨との接合性を強固にするためには、材料の表面部に多孔質層が形成されていることが好ましい。多孔質層はあまり薄ければその効果が発揮し難いので、その層厚を０．１mm以上とすることが好ましい。一方、厚すぎれば素材の強度が低下するので、３mm以下とすることが好ましい。
その気孔率は高いほど骨の浸入がしやすくなるが、素材の強度低下を招くので、気孔率は７５％以下とすることが好ましい。一方、気孔率が低ければ骨が侵入し難くなり、骨との接合力が低下するようになるので、２５％以上とすることが好ましい。
気孔の径は、大き過ぎると素材の強度低下を招き、小さ過ぎると骨の浸入がし難くなる。骨の浸入を可能とするために主体とする気孔径（円相当径）は１０μｍ以上で１５００μｍ以下に制御することが好ましい。前記主体とは、焼結断面を観察したときに認められる気孔のうち、５０％以上の個数の気孔を意味する。さらに、発明者らの経験では骨が適度に入りやすくするには、２００〜１０００μｍ程度のものを主体とすることがより好ましい。なお、上記範囲は気孔の主体が満足しておればよく、その範囲外の気孔を含むことに問題はない。また、気孔は互いに連通している方がより好ましい。
When the zirconia sintered material is used as a biomaterial, a porous layer is preferably formed on the surface of the material, for example, in order to strengthen the bond between the implant and the bone. If the porous layer is too thin, its effect is difficult to exert, so the layer thickness is preferably 0.1 mm or more. On the other hand, if the thickness is too large, the strength of the material is reduced.
The higher the porosity, the more easily the bone can penetrate, but the strength of the material is reduced. Therefore, the porosity is preferably 75% or less. On the other hand, if the porosity is low, the bone is less likely to penetrate, and the bonding strength with the bone is reduced.
If the diameter of the pores is too large, the strength of the material is reduced, and if the diameter is too small, penetration of bone is difficult. It is preferable that the pore diameter (equivalent circle diameter), which is the main component, is controlled to be 10 μm or more and 1500 μm or less in order to allow the penetration of bone. The main body means 50% or more of the pores observed when the sintered cross section is observed. Further, according to the experience of the inventors, it is more preferable that the main body be about 200 to 1000 μm in order to easily enter bone. The above range only needs to be satisfied by the main body of the pores, and there is no problem in including pores outside the range. It is more preferable that the pores communicate with each other.
多孔質構造の製造方法については特に制限はないが、次のような方法を採ることができる。例えば、アクリル、ポリエチレンなどの有機物などとともに成形し、その後、焼結時に加熱により前記気孔形成剤を除去すればよい。また、ラウリルベタイン、ノニルフェノール系界面活性剤などの起泡剤を混合時に添加した後、焼結時に加熱により上記発泡剤を発砲させて気孔を形成させるようにすればよい。いずれも気孔形成剤の添加量により気孔率、気孔径を制御することができる。 方法 The method for producing the porous structure is not particularly limited, but the following method can be employed. For example, it may be molded together with an organic substance such as acrylic or polyethylene, and then, the sintering agent may be removed by heating during sintering. In addition, after adding a foaming agent such as lauryl betaine or a nonylphenol-based surfactant at the time of mixing, the foaming agent may be fired by heating during sintering to form pores. In any case, the porosity and the pore diameter can be controlled by the amount of the pore-forming agent added.
前記多孔質層の表面にハイドロキシアパタイトなどのリン酸カルシウム系材料によってコーティング層を形成することによって生体親和性を増すことができる。
多孔質層の表面へのコーティング方法にも特に制限はないが、次のようなものがあげられる。上記多孔質層の表層部の表面のみをコーティングするにはプラズマスプレー法、プラズマ溶射法などを適用することができる。また、多孔質層の内部の表面までコーティングするには、コーティング剤をスラリー塗布法、ゾルゲル法などにより塗布した後、焼結する方法を採ることができる。焼結により強固な薄膜を被覆することができる。なお、被覆強度を確保するために、被覆前処理として、サンドブラスト、化学エッチングなどにより、焼結体表面を粗面化しておくことが望ましい。
By forming a coating layer on the surface of the porous layer with a calcium phosphate-based material such as hydroxyapatite, biocompatibility can be increased.
The method for coating the surface of the porous layer is not particularly limited, and the following methods are available. In order to coat only the surface of the surface portion of the porous layer, a plasma spray method, a plasma spray method, or the like can be applied. Further, in order to coat the inner surface of the porous layer, a method of applying a coating agent by a slurry coating method, a sol-gel method, or the like, and then sintering can be adopted. A strong thin film can be coated by sintering. In order to secure the coating strength, it is desirable to roughen the surface of the sintered body by sandblasting, chemical etching, or the like as a coating pretreatment.
以下、実施例によって本発明をより具体的に説明するが、本発明はかかる実施例によって限定的に解釈されるものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not construed as being limited to such Examples.
表１に示すようにＣｅＯ2 を８、１０もしくは１２ｍｏｌ％含有する平均粒子径０．３μｍで比表面積１１ｍ2/ｇのＣｅジルコニア粉末、Ｙ2Ｏ3を２、３もしくは４ｍｏｌ％含有する平均粒子径０．３μｍで比表面積１６ｍ2/ｇのＹジルコニア粉末、純度４Ｎ(nine)、平均粒径０．１μm 、比表面積１４．５ｍ2/ｇのＡｌ2Ｏ3粉末、純度３Ｎで平均粒径０．３μm のＭｇＯ粉末、純度３ＮのＣａＣＯ3 粉末、並びに純度９８％以上、比表面積１５．６ｍ2/ｇの酸化ジルコニア粉末、純度２Ｎの酸化セリウムおよび酸化イットリア粉末を準備し、下記の方法によりジルコニア焼結材を製作した。なお、表１では、ＣａＣＯ3 粉末量はＣａＯ粉末量に換算して表示した。 As shown in Table 1, Ce zirconia powder containing 8, 10 or 12 mol% of CeO 2 and having an average particle diameter of 0.3 μm and a specific surface area of 11 m 2 / g, and average particles containing 2, 3 or 4 mol% of Y 2 O 3 Y zirconia powder having a diameter of 0.3 μm and a specific surface area of 16 m 2 / g, purity 4N (nine), an average particle diameter of 0.1 μm, Al 2 O 3 powder having a specific surface area of 14.5 m 2 / g, and an average particle diameter of 3N A 0.3 μm MgO powder, a 3N purity CaCO 3 powder, a zirconia oxide powder having a purity of 98% or more and a specific surface area of 15.6 m 2 / g, a 2N purity cerium oxide and a yttria oxide powder were prepared by the following method. A zirconia sintered material was manufactured. In Table 1, the amount of CaCO 3 powder was converted to the amount of CaO powder and displayed.
Ｃｅジルコニア粉末とＹジルコニア粉末とをφ３mmのジルコニア製ボールと共にポリエチレン製容器に入れ、エタノール溶媒で２４時間湿式混合した。必要に応じてＭｇＯ粉末もしくはＣａＣＯ3 粉末も同時添加して混合した。その後、乾燥して得られた混合粉末をメッシュパスした。Ａｌ2Ｏ3粉末を添加する場合には、得られた混合粉末とＡｌ2Ｏ3粉末とを上記と同様に２４時間湿式混合し、同じく乾燥後、メッシュパスした。一方、酸化ジルコニア、酸化セリウムおよび酸化イットリア粉末を混合する場合には、エタノール溶媒で２４時間湿式混合した粉末を乾燥した後、１０００℃で３時間仮焼した。この粉末を粉砕し、メッシュパスした。以上により原料混合粉末を製造した。 Ce zirconia powder and Y zirconia powder were placed in a polyethylene container together with a zirconia ball having a diameter of 3 mm, and wet-mixed with an ethanol solvent for 24 hours. If necessary, MgO powder or CaCO 3 powder was simultaneously added and mixed. Thereafter, the mixed powder obtained by drying was passed through a mesh. When the Al 2 O 3 powder was added, the obtained mixed powder and the Al 2 O 3 powder were wet-mixed for 24 hours in the same manner as described above, dried, and then passed through a mesh. On the other hand, when zirconia oxide, cerium oxide, and yttria oxide powder were mixed, the powder wet-mixed with an ethanol solvent for 24 hours was dried, and then calcined at 1000 ° C. for 3 hours. This powder was pulverized and passed through a mesh. Thus, a raw material mixed powder was produced.
得られた混合粉末は冷間静水圧プレスにより１．５ｔ／cm2 で成形された。得られた成形体を大気中、焼結温度１４５０℃で２時間焼結した。 The obtained mixed powder was formed at 1.5 t / cm 2 by a cold isostatic press. The obtained molded body was sintered in the atmosphere at a sintering temperature of 1450 ° C. for 2 hours.
上記のようにして製作された各種ジルコニア焼結体を用いて、アルキメデス法により密度を測定して相対密度が９７％以上であることを確認し、曲げ試験、靭性試験、相変態試験および生物学的試験を行った。また、前記ジルコニア焼結体の一部のものについて、ＣｅおよびＹ元素の分布状態を調べた。 Using the various zirconia sintered bodies manufactured as described above, the density was measured by the Archimedes method to confirm that the relative density was 97% or more, and the bending test, toughness test, phase transformation test, and biology Test was performed. Further, the distribution of Ce and Y elements was examined for a part of the zirconia sintered body.
曲げ試験はＪＩＳ Ｒ１６０１に準じて行った。上記焼結材を３×４×５０mmのテストピースに加工し、上スパン１０mm、下スパン３０mmの４点曲げ試験を実施した。 The bending test was performed according to JIS R1601. The sintered material was processed into a 3 × 4 × 50 mm test piece, and a four-point bending test was performed with an upper span of 10 mm and a lower span of 30 mm.
靱性試験はＪＩＳ Ｒ１６０７に準じて行った。上記焼結材を平面研削機で研削した後，表面を３μm ダイヤモンド砥粒で鏡面仕上げしたサンプルを用いた。 The toughness test was performed according to JIS R1607. After grinding the sintered material with a surface grinder, a sample whose surface was mirror-finished with 3 μm diamond abrasive grains was used.
相変態試験は以下の要領にて実施した。上記焼結材を平面研削機で研削した後、表面を３μm のダイヤモンド砥粒で鏡面仕上げした。このサンプルを１５０℃熱水中に４８時間浸漬する試験を行った。このサンプルを理学電機製ＲＩＮＴ−１５００を用いて、ターゲットＣｕ、ターゲット出力５０ｋＶ、モノクロメータ受光スリット０．６mm、走査速度４°／min の条件でピーク強度を測定した。この測定結果より、下記の式により単斜晶率を求めた。
〔Im(111)+Im(11-1)〕/〔Im(111)+Im(11-1)+It(111)+Ic(111)〕×100
ここで、Ｉは各反射のピーク強度、添字ｍ、ｔおよびｃはそれぞれ単斜晶、正方晶、立方晶を示す。
The phase transformation test was performed as follows. After grinding the sintered material with a surface grinder, the surface was mirror-finished with 3 μm diamond abrasive grains. A test was conducted in which this sample was immersed in 150 ° C. hot water for 48 hours. The peak intensity of this sample was measured using RINT-1500 manufactured by Rigaku Corporation under the conditions of a target Cu, a target output of 50 kV, a monochromator receiving slit of 0.6 mm, and a scanning speed of 4 ° / min. From the measurement results, the monoclinic fraction was determined by the following equation.
(Im (111) + Im (11-1)) / (Im (111) + Im (11-1) + It (111) + Ic (111)) × 100
Here, I indicates the peak intensity of each reflection, and the subscripts m, t, and c indicate monoclinic, tetragonal, and cubic, respectively.
生物学的試験は『医療用具および医療材料の基礎的な生物学的試験のガイドライン』（平成７年６月２７日発行、薬機第９９号）に準拠し、Ｖ７９細胞を用いて、コロニー形成阻害試験を行った。上記焼結材を平面研削機で研削した後、表面を３μm のダイヤモンド砥粒で鏡面仕上げしたサンプルをクリーンベンチ中で表裏３０分間ずつ紫外線照射滅菌し、表面積５cm2 に対しＭＯ５培地を１ｍＬの割合で加えて、３７℃の５％ＣＯ2 インキュベーター中で２４時間抽出し、これを試験原液（１００％）とした。この試験原液を、ＭＯ５培地を用いて希釈し、０．５〜１００％および３．１３〜１００％の濃度で試験を繰り替えし行い、細胞毒性の有無を確認した。 The biological test conforms to the “Guidelines for Basic Biological Tests of Medical Devices and Medical Materials” (issued on June 27, 1995, Pharmaceutical Machine No. 99), and uses V79 cells to form colonies. An inhibition test was performed. After grinding the above sintered material with a surface grinder, the sample whose surface was mirror-finished with 3 μm diamond abrasive grains was sterilized by ultraviolet irradiation for 30 minutes on each of the front and back sides in a clean bench, and 1 mL of MO5 medium per 5 cm 2 of surface area. And extracted for 24 hours in a 5% CO 2 incubator at 37 ° C. to give a test stock solution (100%). This test stock solution was diluted using an MO5 medium, and the test was repeated at concentrations of 0.5 to 100% and 3.13 to 100% to confirm the presence or absence of cytotoxicity.
ジルコニア焼結体におけるＣｅおよびＹ元素の分布状態は、微小領域におけるＺｒ原子数ＮＺｒに対するＹ原子数ＮＹの割合ＮＹ／ＮＺｒをＹ2Ｏ3の含有量ＭＹ2Ｏ3（ｍｏｌ％）で除したＮＹ／（ＮＺｒ・ＭＹ2Ｏ3）の標準偏差σＹ、前記ＮＺｒに対するＣｅ原子数ＮＣｅの割合ＮＣｅ／ＮＺｒをＣｅＯ2 の含有量ＭＣｅＯ2 （ mol％）で除したＮＣｅ／（ＮＺｒ・ＭＣｅＯ2 ）の標準偏差σＣｅを求めることによって評価した。焼結材全体に含まれるＹ2Ｏ3、ＣｅＯ2 の含有量ＭＹ2Ｏ3、ＭＣｅＯ2 （ mol％）は、Ｃｅジルコニア粉末とＹジルコニア粉末の配合量から算出した。
前記Ｃｅ、Ｙ、Ｚｒの原子数は、ＴＥＭ分析によって以下の要領にて測定した。上記ジルコニア焼結体をダイヤモンドカッターで切り出し、厚さ３０〜４０μｍ以下まで薄片化してバフ研磨仕上げした。その後、Ｇａｔａｎ社製 ＰＩＰＳ Ｍｏｄｅｌ ６９１を用いてイオンミーリング法によりＴＥＭ観察用試料を作製した。その試料をＦＥ−ＴＥＭ（日立製作所製、ＨＦ−２０００電界放射型透過電子顕微鏡）を用い、加速電圧：２００ｋＶで観察した。定量分析は、同ＴＥＭに装着したＥＤＸ（Ｋｅｖｅｘ社製、Ｓｉｇｍａエネルギー分散型Ｘ線検出器）を用いて、ビーム径を５ｎｍ以下に絞り、定量分析元素をＣｅ、Ｙ、Ｚｒ、Ｏとして点分析によってそれぞれの原子数濃度ａｔｏｍ％を測定した。測定部位は、ジルコニアをベースとした粒子で粒径の確認できる領域で、粒内、粒界近傍、粒界などを問わず、ランダムに１５〜２０点測定した。
なお、本実施例では、Ｙ2Ｏ3、ＣｅＯ2 の含有量（ mol％）をＣｅジルコニア粉末とＹジルコニア粉末の配合量から算出したが、下記の手法により化学分析によっても含有量を求めることができる。供試材を白金るつぼに測り取り、アルカリ融剤（Ｎａ2ＣＯ3＋Ｎａ2Ｂ4Ｏ7 ）を加えて溶融し、溶融物を塩酸で抽出した後、メスフラスコに移し入れ測定溶液とする。その測定溶液をＩＣＰ質量分析装置（例えば、セイコーインスツルメンツ社製ＳＰＱ８０００）にて定量分析し、その値を酸化物換算することによってＹ2Ｏ3およびＣｅＯ2 量を求めことができる。
The distribution state of the Ce and Y elements in the zirconia sintered body was obtained by dividing the ratio NY / NZr of the number of Y atoms NY to the number of Zr atoms NZr in the minute region by the content of Y 2 O 3 MY 2 O 3 (mol%). The standard deviation σY of NY / (NZr · MY 2 O 3 ), the ratio of the number of Ce atoms NCe to NZr NCe / NZr divided by the CeO 2 content MCeO 2 (mol%) NCe / (NZr · MCeO 2 ) Was evaluated by determining the standard deviation σCe of The contents MY 2 O 3 and MCeO 2 (mol%) of Y 2 O 3 and CeO 2 contained in the whole sintered material were calculated from the blended amounts of Ce zirconia powder and Y zirconia powder.
The number of atoms of Ce, Y, and Zr was measured by TEM analysis in the following manner. The zirconia sintered body was cut out with a diamond cutter, sliced to a thickness of 30 to 40 μm or less, and finished by buffing. Thereafter, a sample for TEM observation was prepared by an ion milling method using PIPS Model 691 manufactured by Gatan. The sample was observed using an FE-TEM (HF-2000 field emission transmission electron microscope manufactured by Hitachi, Ltd.) at an acceleration voltage of 200 kV. Quantitative analysis was performed using an EDX (Sigma energy dispersive X-ray detector, manufactured by Kevex) mounted on the TEM, narrowing the beam diameter to 5 nm or less, and performing point analysis with Ce, Y, Zr, and O as quantitative analysis elements. , The atomic number concentration of each atom was measured. The measurement site was a region in which the particle size could be confirmed with zirconia-based particles, and 15 to 20 points were measured at random regardless of the inside of the grain, the vicinity of the grain boundary, the grain boundary, and the like.
In this example, the contents (mol%) of Y 2 O 3 and CeO 2 were calculated from the blended amounts of the Ce zirconia powder and the Y zirconia powder. However, the contents may be determined by chemical analysis according to the following method. Can be. The test material is measured in a platinum crucible, melted by adding an alkali flux (Na 2 CO 3 + Na 2 B 4 O 7 ), and the melt is extracted with hydrochloric acid, then transferred to a volumetric flask to obtain a measurement solution. The measurement solution is quantitatively analyzed by an ICP mass spectrometer (for example, SPQ8000 manufactured by Seiko Instruments Inc.), and the values are converted to oxides to determine the amounts of Y 2 O 3 and CeO 2 .
これらの試験結果を表１に併せて示す。同表には、Ｃｅジルコニア粉末中のＣｅＯ2 含有量を「内ＣｅＯ2 」として、Ｙジルコニア粉末中のＹ2Ｏ3含有量を「内Ｙ2Ｏ3」として記載している。また、試料No. ２５，２６は、ＺｒＯ2 粉末、ＣｅＯ2 粉末およびＹ2Ｏ3 粉末の混合粉末を焼結したものであり、ＣｅＯ2とＹ2Ｏ3は全粉末に対する含有量を示す。曲げ強度は１５本の平均値、靱性は５点の平均値を記載している。 The results of these tests are also shown in Table 1. In the table, the CeO 2 content in the Ce zirconia powder is described as “Inner CeO 2 ”, and the Y 2 O 3 content in the Y zirconia powder is described as “Inner Y 2 O 3 ”. Samples Nos. 25 and 26 were obtained by sintering a mixed powder of ZrO 2 powder , CeO 2 powder and Y 2 O 3 powder, and the contents of CeO 2 and Y 2 O 3 are based on the total powder. The bending strength is an average value of 15 pieces, and the toughness is an average value of 5 points.
表１より、所定量のＣｅを含有するジルコニアとＹ2Ｏ3を含有するジルコニアとからなり、混合比を９：１〜６：４としたジルコニア焼結材の試料１〜１４（実施例）は、強度・靱性も高く、相変態もほとんど生じていないことがわかる。これに対して、試料No. ２１〜２７（比較例）では、強度、靱性、水熱試験による変態のいずれかが劣っている。なお、細胞毒性は、いずれの実施例ならびに比較例においても認められなかった。 As shown in Table 1, samples 1 to 14 of zirconia sintered material composed of zirconia containing a predetermined amount of Ce and zirconia containing Y 2 O 3 and having a mixing ratio of 9: 1 to 6: 4. It can be seen that has high strength and toughness, and hardly any phase transformation occurs. On the other hand, Sample Nos. 21 to 27 (Comparative Example) are inferior in any of strength, toughness, and transformation by a hydrothermal test. No cytotoxicity was observed in any of the examples and comparative examples.
次に、表１の試料No. ２の配合割合のＣｅジルコニア粉末およびＹジルコニア粉末との混合粉末Ａを準備するとともに、これらの粉末と径３００μm のアクリルビーズとをＶ型混合機にて３時間乾式混合してアクリルビーズを含む混合粉末Ｂを準備した。混合粉末Ｂについては、ビーズ量が異なる種々のものを準備した。混合粉末ＡおよびＢを１軸プレスの型内に２層になるように装入し、５００kg／cm2 でプレス成形した。このプレス成形体をさらに冷間静水圧プレス１．５ｔ／cm2 で成形した。得られた成形体を大気中、焼結温度１４５０℃で２時間焼結した。得られた焼結材の多孔質層を平面研削盤によって研削して１mm程度の厚さに調整した。このようにして得られた、種々の気孔率を有する多孔質層を備えたジルコニア焼結体を表２に示す。
このジルコニア焼結体において、多孔質層中に存在する空隙を気孔とし、ある一定領域における空隙の存在する割合を気孔率とした。その測定方法は、次の通りである。供試材を切り出し、切断面を鏡面研磨した。その断面をＳＥＭ（日立製作所製Ｓ−４５００）にて加速電圧２０ｋＶで気孔径に応じ２００〜１０００倍で写真撮影した。ＳＥＭの観察領域はおよそ０．０６mm2 程度である。そのＳＥＭ写真を画像解析（使用ソフト：Media Cybernetics社製のImage-Pro Plus Version 4.0 for Windows。なお、Windowsは登録商標です。）によりマトリックス部分と気孔部分とに2値化して気孔率を算出した。
Next, a mixed powder A of Ce zirconia powder and Y zirconia powder having a blending ratio of Sample No. 2 in Table 1 was prepared, and these powders and acrylic beads having a diameter of 300 μm were mixed for 3 hours with a V-type mixer. Dry mixing was performed to prepare a mixed powder B containing acrylic beads. Regarding the mixed powder B, various powders having different bead amounts were prepared. The mixed powders A and B were charged into a uniaxial press mold in two layers and press-molded at 500 kg / cm 2 . This press-formed body was further formed by a cold isostatic press of 1.5 t / cm 2 . The obtained molded body was sintered in the atmosphere at a sintering temperature of 1450 ° C. for 2 hours. The obtained porous layer of the sintered material was ground with a surface grinder to adjust the thickness to about 1 mm. Table 2 shows the zirconia sintered bodies provided with the porous layers having various porosity thus obtained.
In this zirconia sintered body, voids in the porous layer were defined as pores, and the ratio of voids in a certain region was defined as porosity. The measuring method is as follows. The test material was cut out and the cut surface was mirror-polished. The cross section was photographed with an SEM (S-4500 manufactured by Hitachi, Ltd.) at an accelerating voltage of 20 kV at a magnification of 200 to 1000 times depending on the pore diameter. The observation area of the SEM is about 0.06 mm 2 . The SEM photograph was binarized into a matrix portion and a pore portion by image analysis (software used: Image-Pro Plus Version 4.0 for Windows manufactured by Media Cybernetics, Inc., Windows is a registered trademark), and the porosity was calculated. .
表２の試料No. ３１〜３４については、多孔質層を２００ｍＭのＣａＣｌ2 と５０ｍＭのTris／ＨＣＬとの混合溶液に５分間浸漬して液切りし、１２０ｍＭのＮａ2ＨＰＯ4と５０ｍＭのTris／ＨＣＬとの混合溶液に５分間浸漬して水洗・乾燥し、リン酸カルシウムを多孔質層にコーティングした。その後、３７℃の疑似体液中（Ｎａ+ １４２．０ｍＭ、Ｋ+ ５．０ｍＭ、Ｍｇ2+１．５ｍＭ、Ｃａ2+２．５ｍＭ、Ｃｌ- １４８．８ｍＭ、ＨＣＯ3-４．２ｍＭ、ＨＰＯ4 2-１．０ｍＭ、ＳＯ4 2-０．５ｍＭ）に３日間浸漬し、アパタイトのコーティング層を多孔質層の表面に形成した。 For sample Nos. 31 to 34 in Table 2, the porous layer was immersed in a mixed solution of 200 mM CaCl 2 and 50 mM Tris / HCL for 5 minutes to drain the liquid, and 120 mM Na 2 HPO 4 and 50 mM Tris / HCL and immersed in a mixed solution for 5 minutes, washed with water and dried to coat the porous layer with calcium phosphate. Then, in a simulated body fluid at 37 ° C. (Na + 142.0 mM, K + 5.0 mM, Mg 2+ 1.5 mM, Ca 2+ 2.5 mM, Cl − 148.8 mM, HCO 3− 4.2 mM, HPO 4 2-1.0 mM, and immersed SO 4 2- 0.5mM) for 3 days to form a coating layer of apatite on the surface of the porous layer.
これらの多孔質層を有するジルコニア焼結体を犬の大腿骨に埋入し、４週間および１６週間経過した後、大腿骨ごと取り出し、組織学的評価を行った。試料No. ３１〜３３では、４週間経過後に骨が焼結体に侵入し、生体骨との直接的な結合が認められ、１６週間経過後では気孔全体に新生骨が入り、強固に結合していることが確認された。
一方、試料No. ３４および３５では、４週間経過後に新生骨の侵入が認められるものの、その程度はわずかであった。No. ３４はアパタイトをコーティングしたものであるが、同様にアパタイトをコーティングしたNo. ３１〜３３に比較して気孔率が低いため新生骨の侵入が抑制されていることがわかる。１６週間経過後では新生骨と気孔表面との結合は確認できたが、骨が全気孔に侵入するには至らなかった。
The zirconia sintered body having these porous layers was implanted in a femur of a dog, and after 4 weeks and 16 weeks, the whole femur was taken out and histologically evaluated. In sample Nos. 31 to 33, bone penetrated into the sintered body after 4 weeks, and a direct bond with living bone was observed. After 16 weeks, new bone entered all the pores and was strongly bonded. It was confirmed that.
On the other hand, in Samples Nos. 34 and 35, invasion of new bone was observed after 4 weeks, but the degree was small. No. 34 was coated with apatite, but the porosity was lower than that of Nos. 31 to 33 coated with apatite, indicating that the invasion of new bone was suppressed. After 16 weeks, the connection between the new bone and the surface of the stoma could be confirmed, but the bone did not penetrate into all stomas.
Claims (7)
前記ＣｅＯ2 を含んだジルコニアと、前記Ｙ2Ｏ3を含んだジルコニアとの体積比が９：１〜６：４である高強度・高靱性ジルコニア焼結材。 A zirconia sintered material in which zirconia containing 8 mol% to 15 mol% of CeO 2 and zirconia containing 2 mol% to 5 mol% of Y 2 O 3 are dispersed,
A high-strength, high-toughness zirconia sintered material in which the volume ratio of the zirconia containing CeO 2 to the zirconia containing Y 2 O 3 is 9: 1 to 6: 4.
直径５ｎｍ以下の微小領域での観察において、Ｚｒ原子数ＮＺｒに対するＹ原子数ＮＹの割合ＮＹ／ＮＺｒをＹ2Ｏ3の含有量ＭＹ2Ｏ3（ mol％）で除したＮＹ／（ＮＺｒ・ＭＹ2Ｏ3）の標準偏差をσＹとし、前記ＮＺｒに対するＣｅ原子数ＮＣｅの割合ＮＣｅ／ＮＺｒをＣｅＯ2 の含有量ＭＣｅＯ2 （ mol％）で除したＮＣｅ／（ＮＺｒ・ＭＣｅＯ2 ）の標準偏差をσＣｅとしたとき、前記σＹが０．００１５以上、０．１以下および前記σＣｅが０．０００１以上、０．０１以下である高強度・高靱性ジルコニア焼結材。 Zirconia as a main component, a CeO 2 4.7 mol% ~13.4 mol% and Y 2 O 3 to a zirconia sintered material containing 0.2 mol% ~2.1 mol%,
In observation in a minute region having a diameter of 5 nm or less, the ratio NY / NZr of the number of Y atoms NY to the number of Zr atoms NZr divided by the content of Y 2 O 3 MY 2 O 3 (mol%), NY / (NZr · MY) the standard deviation of the 2 O 3) and ShigumaY, the standard deviation of dividing the NCe / (NZr · MCeO 2) the percentage NCE / NZr of Ce atoms NCE for the NZr in content MCEO 2 of CeO 2 (mol%) A high-strength and high-toughness zirconia sintered material in which the σY is 0.0015 or more and 0.1 or less and the σCe is 0.0001 or more and 0.01 or less, when σCe.
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