JPS58150504A - High-strength material for living body and its production - Google Patents

High-strength material for living body and its production

Info

Publication number
JPS58150504A
JPS58150504A JP57154444A JP15444482A JPS58150504A JP S58150504 A JPS58150504 A JP S58150504A JP 57154444 A JP57154444 A JP 57154444A JP 15444482 A JP15444482 A JP 15444482A JP S58150504 A JPS58150504 A JP S58150504A
Authority
JP
Japan
Prior art keywords
calcium phosphate
strength
surface layer
metal material
material base
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
Application number
JP57154444A
Other languages
Japanese (ja)
Inventor
Shinji Nishio
西尾 信二
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Tokushu Togyo KK
Niterra Co Ltd
Original Assignee
NGK Spark Plug Co Ltd
Nippon Tokushu Togyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NGK Spark Plug Co Ltd, Nippon Tokushu Togyo KK filed Critical NGK Spark Plug Co Ltd
Priority to JP57154444A priority Critical patent/JPS58150504A/en
Publication of JPS58150504A publication Critical patent/JPS58150504A/en
Pending legal-status Critical Current

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  • Dental Prosthetics (AREA)
  • Materials For Medical Uses (AREA)
  • Dental Preparations (AREA)

Abstract

PURPOSE:A high-strength material for dental or orthopaedic endo-osseous implant that is made by covering the base of a metallic material such as high- strength stainless steel with calcium phosphate glass, thus showing good compatibility to living bodies and not hurting them. CONSTITUTION:The metallic base material with higher strength than sintered calcium phosphate is coated with calcium phosphate by dipping, brushing, spraying a suspension or slurry containing a powdery material forming calcium phosphate by calcination or combination thereof to give the objective material with the surface layer of calcium phosphate. The resultant material is preferably porous on the surface of the cintered calcium phosphate or crystallized, after coated in a glass state.

Description

【発明の詳細な説明】 本発明は歯科用骨内インブラント或いは整形用骨内イン
ブラン)に用いる為書性がなく高強度の生体用部材に関
する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-deformable and high-strength biological component used for dental intraosseous implants or orthopedic intraosseous implants.

従来このような生体用部材にはステンレス鋼等の耐食性
金属材料あるいはセラセックス材料が使用されていたが
、前者耐食性金属材料は長期間の使用によってクー^、
:Iパルト等の有香な重金属が体内に蓄積されるので後
者−ラミックス材料が注目されるようになった。
Conventionally, corrosion-resistant metal materials such as stainless steel or ceramicsex materials have been used for such biological components, but the former corrosion-resistant metal materials deteriorate due to long-term use.
The latter type of ramix material has attracted attention because fragrant heavy metals such as I-pult are accumulated in the body.

このセラ々ツクス#料としては、幽初高アル曙す磁器あ
るいはサファイア等の高い機械的強度を有するアル建ナ
セツ建ツクスが使用されていたが、該アル電ナセラミッ
クスは高い機械的強度を有する反画、生体の部内、骨材
とのなじみが愚いため骨材と成分が近似する燐酸カルシ
ウム系ガラスが注目される↓うになった。
Aluminum ceramics with high mechanical strength, such as high-altitude porcelain or sapphire, were used as the ceramic materials; Calcium phosphate glass, which has similar composition to aggregate, has been attracting attention because it has poor compatibility with anti-paintings, living body parts, and aggregates.

燐酸カルシウム系オツス材料については、特@18xi
−’yioit号公@において[カルシウムとリンの原
子比Ca/)をt7以下とし、かつ、リン酸を1%Os
として10重量−以上含有する組成物を焙融することに
よってガラスとし、その熱旭鳳によって得られる曽晶化
度Iから100−結晶化物までの種々の結晶化跋を有す
る燐酸カルシウム系結晶化ガラス材料。」が開示され、
まえ特開18j−一4#/ff号企報において[アバタ
イ)*細体による人工骨および人工m機とそれらの製造
法」としてr Can (POnbOHOffRz〜j
o−とCai(POi)m#aj−10% ヨリfk 
り 、iJ ’)に必要に応じてMgO* Nano 
s K10 * CaFg * AbOi e810m
のうちから選ばれた7種もしくはコ種以上がαt−Uj
チ添加されて焼成されたアパタイト−緒体」が開示され
ているが、何れも強度が不足で骨や歯に大きな応力や衝
撃がかかると折損するおそれがあつ九。
For calcium phosphate based materials, please contact Special@18xi
-'yioit issue@: [atomic ratio of calcium and phosphorus Ca/] is t7 or less, and phosphoric acid is 1%Os
Calcium phosphate-based crystallized glass having various crystallization degrees from I to 100-crystallinity obtained by roasting a composition containing 10-weight or more of material. ” was disclosed,
In the previous Japanese Patent Application Publication No. 18J-14#/ff issue, [Avatai]
o- and Cai (POi) m#aj-10% Yoli fk
MgO*Nano
s K10 * CaFg * AbOi e810m
Seven or more selected species are αt-Uj
However, all of them lack strength and may break if large stress or impact is applied to bones or teeth.

本発明はこれを改良するためKなされたもので、生体に
対してなじみがよく、セラ建ツタ特有O為書性のない燐
酸カルシウム系ガツメを表面層として、該燐酸カルシウ
ム系ガラスよりも機械的強度の高いステンレス鋼等の金
属材料からなる基体上に被着することKよって生体とな
じみがよく、為書性がなく、かつ満足すぺ龜機棹的強度
を具えた^強度生体用部材に関するものである。
The present invention has been developed to improve this problem, and uses calcium phosphate glass as a surface layer, which is compatible with living organisms and does not have the O-formation properties characteristic of Sela-ken ivy. Concerning a strong biological material that is adhered to a substrate made of a metal material such as high-strength stainless steel, has good compatibility with living organisms, is free from paper-like properties, and has satisfactory mechanical strength. It is something.

こζに述べる燐酸カルシウム系ガラス紘、燐酸カルシウ
ムCa畠(POa)麿を初め、Ca/PO原子比がat
−/、’IJ付近のカルシウム燐酸塩やアパタイトを主
成分とし、賛すれば少量の強化剤を含むガラス質あるも
紘#菖化したガラスであって燐酸カルシ☆ム系iIツス
としての基本的特性を具え九ものであれdよく、金属材
料としては鱗酸カルシ゛ウムの纏廖彊係数/ 00 =
 710 X / 0’/’CK近似した熱膨張性で機
械的強度が高く、かつ比重が小さく、しかも燐酸カルシ
ウムの被着層を形成する温[K対しても安定な材質から
―ばれるがステンレス鍋ヤチタン合金が最も好ましい。
Including the calcium phosphate-based glass foam described in this ζ, calcium phosphate Ca Hatake (POa) Maro, the Ca/PO atomic ratio is at.
-/, 'It is a glassy iris-formed glass whose main components are calcium phosphate and apatite near IJ, and a small amount of reinforcing agent. As a metal material, the thermal conductivity coefficient of calcium fluorate / 00 =
710 Yachitan alloy is most preferred.

次にその製法を述べれば、その1つは燐酸、炭酸カルシ
ウムおよび二水素燐酸カルシウムなど細麺によって燐酸
カルシウムを生成する材料を原料としてよく混合し、半
溶融となる温fK鉤成することによりセルベンとし、こ
れを粉砕して燐酸カルシウム粉ム末を得る。この中Kt
i結晶質燐酸カルシウムおよび/lえはガラスが存在し
ている。これを周知のバインダーを加えた水に懸濁して
泥漿となし、前記高強度金属材料基体の所望の形状より
も僅かに小さく仕上げられ先高強度材料基体を浸し、乾
燥後燐酸カルシウムの溶融する温度に焼成することKよ
り表面Ka/−前後の燐酸カルシウムの被覆を設けるこ
とがで愈る。tた燐酸カルシウムセルベンに焼成中蒸発
ま九は焼失する有機物粉末を混入すれば多孔質となる。
Next, the manufacturing method is as follows: phosphoric acid, calcium carbonate, calcium dihydrogen phosphate, and other materials that produce calcium phosphate by thin noodles are thoroughly mixed as raw materials, and the mixture is heated to a semi-molten temperature by heating. This is ground to obtain calcium phosphate powder. Among these Kt
Crystalline calcium phosphate and/or glass are present. This is suspended in water containing a well-known binder to form a slurry, which is finished to a size slightly smaller than the desired shape of the high-strength metal material base.The high-strength metal base is immersed in the slurry and dried at a temperature at which calcium phosphate melts. It can be cured by providing a coating of calcium phosphate around the surface Ka/- of the surface. If organic powder that evaporates during firing is mixed into the calcium phosphate ceramic, it becomes porous.

この表面層が多孔質である゛ことは基体との熱膨張係数
の差による内部応力を緩和し、またインブラント材料と
して生体とのなじみを改善する効果を有する。別の製法
の1つは上記燐酸カルシウム粉末をグツズマtたは酸素
アセチレン炎等を用い溶射により上記蟲強に金属材料基
体の表面に被覆することがで自る。この場合被覆層を多
孔質にすることは、高強度金属材料基体と蛤射ノズルO
距離を調節することにより自由に調節することができる
The fact that this surface layer is porous has the effect of alleviating internal stress due to the difference in thermal expansion coefficient with the substrate and improving compatibility with living organisms as an implant material. Another manufacturing method is to coat the surface of the metal material substrate with the above calcium phosphate powder by thermal spraying using a spray gun or an oxyacetylene flame. In this case, making the coating layer porous means that the high-strength metal material base and the shell spray nozzle O
It can be freely adjusted by adjusting the distance.

また、燐酸カルシウム粉末はセルベンとじて用いてもよ
いし、その原料着京を未焼成の状態て用いてもよ<、を
九燐酸カルシクムの表面層はガラス質でも結晶質でもよ
く、鉤成後ガラス質を結晶化するための熱l&環を行な
ってもよい。
In addition, the calcium phosphate powder may be used in the form of Cerben, or its raw material may be used in an unfired state.The surface layer of the calcium phosphate powder may be glassy or crystalline, and after baking Heat l&ring may be performed to crystallize the glass.

以下実施例によりさらに具体的に説明する。This will be explained in more detail below with reference to Examples.

実施例l CaCO5J O−とPsOs/4’leを混合し11
00℃に一時間焼成をして生動状態とし燐酸カルシウム
のガラスと結晶の混合物を生成した。この場合のCa/
Pの原子比は約lである。これをトロンメルにて!μ以
下の粒子が41L0−となる如く看砕した。これをメチ
ルセルローズl悌を溶解した水に入れ攪拌して燐酸カル
シウムの泥漿とした0次にステンレススチールで製作し
九参xJxコj111の寸法の高強度金属材料基体を前
記燐酸カルシウムの泥11に浸漬し乾燥し大気中で70
0℃に焼成して表面に厚さa/■の燐酸カルシウムを被
覆し九14強度生体用部材を製作し、同じ燐酸カルシウ
ムの泥策を用いて一体に鋳込成形して大気中700℃で
一成して得た参xJrxJj■の比較品について抗折力
を測定し九紬果、後者比較品はIh/−にて折損したの
に対して前者の本発明品は40−/−の荷重においても
燐酸カルシウムの被覆層に剥離、中表等の異状を生ぜず
満足すぺ自機械的強度を得ることに成功した。
Example 1 Mixing CaCO5J O- and PsOs/4'le 11
The mixture was calcined at 00° C. for 1 hour to bring it to a living state, producing a mixture of calcium phosphate glass and crystals. Ca/ in this case
The atomic ratio of P is approximately 1. Enjoy this at Trommel! The particles were crushed so that the particles were 41L0-. This was put into water in which methyl cellulose was dissolved and stirred to make a slurry of calcium phosphate.The slurry was made of stainless steel and a high strength metal material base with dimensions of 9 x J x 111 was added to the calcium phosphate slurry 11. Soaked and dried in air for 70 minutes
A 914-strength biological component was produced by baking at 0°C and coating the surface with calcium phosphate with a thickness of a/cm, and then molding it by casting using the same calcium phosphate slurry in the atmosphere at 700°C. The transverse rupture strength was measured for the comparative product of the same product, and it was found that the latter comparative product broke at Ih/-, while the former invention product broke at a load of 40-/- Also, we succeeded in obtaining satisfactory mechanical strength in the calcium phosphate coating layer without causing any abnormalities such as peeling or middle surface.

なお、上記本発明品の燐酸カルシウムの被覆層の機械的
強度(耐剥離、耐キ裂)40b/−はts@高フル1?
磁器の杭折力参s W4/−14[K比しても高い数値
である。
In addition, the mechanical strength (peeling resistance, cracking resistance) of the calcium phosphate coating layer of the above-mentioned product of the present invention is 40b/- ts @ high full 1?
This is a high value even compared to the pile breaking force of porcelain W4/-14[K.

実施例コ 実施例/に用い九燐酸カルシウム泥漿にその固形分(燐
酸カルシクム分)の/j重量IJ6に相幽する平均粒*
1pの炭素粉末を添加、温合した後、その他の条件は実
施例Iと全く同様として、ステンレススチールからなる
高強直金属基材のlI函に多孔質の表層を有する燐酸カ
ルシウム焼結体からなる厚さα/jmo被覆層を形成し
た高強度生体部材を得た。
The average grain size of the solid content (calcicium phosphate) of the calcium nonaphosphate slurry used in Example /J weight IJ6*
After adding 1p of carbon powder and heating it, the other conditions were exactly the same as in Example I, and a calcium phosphate sintered body having a porous surface layer was placed in an 1I box made of a high-strength metal base material made of stainless steel. A high-strength biomaterial having a coating layer having a thickness of α/jmo was obtained.

この部材の燐酸カルシウムからなる表面層は実施例IO
緻密質と異な9、出発原料として添加し九嶽素粉末が焼
成時において酸化して酸化炭素となって焼失し、該炭素
のガス化、膨張によって生じ九J0〜!00μの大きな
気孔を表層に無数に含む多孔質で、その気孔率Fiay
参であつ九。この多孔質化は高強度材料基体と表面層と
の間の熱廖饅係数の違いによる内部応力を緩和して焼成
時における剥離、キ豐の発生を防ぐので基体の材質を撰
択する幅を拡げ、また一方表面層の増加と凹凸化により
血管や筋肉のまつわりをよくして接着力を向上する。な
お、表向層そのものの硬度は低下して実施例1と同様の
抗折力試験によって40−/−の荷重によって表面のノ
ツチと接触する部分Kll化がみられ九が、このような
硬質ノツチによる線接触は生体においては起り得ないこ
とであり、高アルミす磁器の抗折力よりも高い値である
The surface layer of this member made of calcium phosphate was as described in Example IO.
9.Different from dense, 9J0~! The 9J0~, which is added as a starting material, is oxidized during firing to become carbon oxide and burnt out, and the carbon is gasified and expanded. A porous material containing countless large pores of 00μ on the surface layer, and its porosity is Fiay
Part 9. This porous structure alleviates the internal stress caused by the difference in thermal expansion coefficient between the high-strength material base and the surface layer, and prevents peeling and cracking during firing, so there is a wide range in the selection of the base material. On the other hand, by increasing the surface layer and making it uneven, it improves the connection of blood vessels and muscles and improves adhesive strength. In addition, the hardness of the surface layer itself decreased, and the same transverse rupture strength test as in Example 1 showed that the part of the surface that contacted the notch became Kll due to a load of 40-/-. Line contact cannot occur in living organisms, and its transverse rupture strength is higher than that of high-aluminum porcelain.

実施例J 実施例1で用いた燐酸カルシウム粉末を同じく実施例1
で使用した高強度金属材料基体に酸素−アセチレン炎に
より火炎溶射を行ない、表面に厚さaJ■の燐酸カルシ
ウム層を設けた為強度生体用部材は急熱急冷にも拘らず
表面層に剥離、中裂を生ぜず抗折力試験においても該実
施例/と略々間等の機械的強度を得た。
Example J The calcium phosphate powder used in Example 1 was also used in Example 1.
The high-strength metal material base used in the above was flame-sprayed with an oxygen-acetylene flame, and a calcium phosphate layer with a thickness of aJ■ was provided on the surface, so that the high-strength biomaterial could peel off on the surface layer despite rapid heating and cooling. Even in the transverse rupture strength test, the mechanical strength was approximately equal to that of Example 1 without causing any intermediate cracks.

まえ、火炎溶射を行なつ先後、再び400℃の熱処理に
よって結晶化度をfj−1で高めえ場合は表面層の機械
的強度を一段と高めるものである。
If the degree of crystallinity can be increased to fj-1 by heat treatment at 400° C. before flame spraying, the mechanical strength of the surface layer can be further increased.

以上のとおり、本発明は高強度の金属材料からなる基体
の表面に生体となじみがよく、また為書性のない燐酸カ
ルシウムの焼結体の薄層を形成するものであるから、充
分の機械的強度と共に健康上の安全性を保持し、しかも
生体の血管、筋肉のまつわりを改善する等極めて優れ先
生体用部材とその製造方法を提供するものである。
As described above, the present invention forms a thin layer of a sintered body of calcium phosphate, which is compatible with living organisms and has no textural properties, on the surface of a substrate made of a high-strength metal material, and therefore has sufficient mechanical properties. The object of the present invention is to provide an extremely excellent member for a patient's body, which maintains physical strength and health safety, and improves connections between blood vessels and muscles of the living body, and a method for manufacturing the same.

なお、前記の各実施例は燐酸カルシウムの焼結体の出発
原料として炭酸カルシウムと燐酸を用い九が、前述のと
お)二水素燐酸カルシクム等焼成によって燐酸カルシウ
ムを生成する#科を使用することができるが、いずれの
場合においても燐酸カルシウムの焼結体は次に述べる高
gIi度金属材料基体との焼成時における熱膨張差の影
響を避ける九めaJ−程度以下、%yctxoz〜ai
j■S度が好ましい、また、高強度金属材料基体もステ
ンレススチールに限らず、他のチタン合金等信の金属で
もよく、さらKa基体の表面をナンドプラスト勢周知の
手段によって凹凸を設けることKよって表面層との接着
強度を鳥めることができる。
In each of the above examples, calcium carbonate and phosphoric acid were used as the starting materials for the sintered body of calcium phosphate. However, in any case, the sintered body of calcium phosphate must be 9.9J- or less, %yctxoz~ai to avoid the influence of the difference in thermal expansion during firing with the high-gIi metal material substrate described below.
The high-strength metal material base is preferably not limited to stainless steel, but may also be made of other metals such as titanium alloys, and the surface of the Ka base may be made uneven by a well-known method such as Nando Plast. Therefore, the adhesive strength with the surface layer can be increased.

Claims (1)

【特許請求の範囲】 (1)  、1111力ルシクム鉤艙体により11画層
と鋏表面層6cs?おわれる、誼鉤艙体よ〕も機械強震
が大、自い高強直金属材料基体とよ)なる高強度生体用
部材。 榊 前記燐酸カルシウム焼結体の表面層が多孔質層で弗
る特許請求osssz項記載の高強度生体用部材。 −) 前記高強直金属材料基体が耐食性金属材料である
特許請求の@II第1第1九★九2項記載の高強直生体
用部材。 −) 燐酸カルシウムの表面層がガラスO状態で被着さ
れた後、紬晶化されたものである特許請求の*mwti
−第J項のいずれかに記載の高強直生体用部材。 に)憐酸カルシ☆ムー曽体よりも強直の大暑い高強度金
属材料基体OII画に、燐酸カルシクム壕九紘焼成によ
)燐酸カルシウムを生成する材料の着京を懸濁を九は溶
解し九泥秦を浸漬、華mp、*m付けのいずれかまたは
總会せによ〉被着し乾燥し―成することを特徴とし良、
表11に1111酸★ルシウムO表面層を形威し良高強
度肱体用部材の調造方法。 偵) 曽記鱗酸カルシウム梶INK鉤成により鉤失すゐ
物質を懸濁することを特徴とする特許請求の範lll1
Ij項記60表面に燐酸カルシウムや多孔質表面層を形
成し良高強度生体用部材O製造方法。 (7)燐酸カルシウム焼結体よ)も強度の大暑い高強度
金属材料基体の表面に燐酸カルシクム粉末をプツズ−t
tえは火炎溶射をもって吹自付けることを特徴とした、
表面に燐酸カルシウムの表面層を形成した高m度生体用
部#O製造方法。
[Claims] (1) 11 layers and 6 cs of scissor surface layer due to 1111 force Lucicum hook body? It is a high-strength biomedical component made of a high-strength metal material base that has a high mechanical strength and strong mechanical shock. Sakaki The high-strength biological member according to claim osssz, wherein the surface layer of the calcium phosphate sintered body is a porous layer. -) The highly rigid biological member according to claim @II, Paragraph 1, Paragraph 9, 92, wherein the highly rigid metallic material base is a corrosion-resistant metallic material. -) *mwti of the patent claim, in which the surface layer of calcium phosphate is deposited in a glass O state and then crystallized.
- The highly rigid biological component according to any one of Section J. (2) Calcium phosphate is made into a high-strength metal material base OII that is more rigid than the body of the earth, and the material that produces calcium phosphate is dissolved in the suspension. It is characterized by being formed by dipping, applying, *m, or combining 9 mud and drying.
Table 11 shows a method for preparing a high-strength member for the elbow body by forming a surface layer of 1111 oxide*lucium O. Claim 1, characterized in that a substance that is hooked by Zengji's calcium scalinate bucket INK is suspended.
Item Ij Item 60: A method for producing a high-strength biomaterial O by forming calcium phosphate or a porous surface layer on the surface. (7) Calcium phosphate sintered body) Apply calcium phosphate powder to the surface of a high-strength metal material base.
TE is characterized by being self-attached using flame spraying.
A method for manufacturing a high-molecular-weight biomedical part #O in which a surface layer of calcium phosphate is formed on the surface.
JP57154444A 1982-09-03 1982-09-03 High-strength material for living body and its production Pending JPS58150504A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP57154444A JPS58150504A (en) 1982-09-03 1982-09-03 High-strength material for living body and its production

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57154444A JPS58150504A (en) 1982-09-03 1982-09-03 High-strength material for living body and its production

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP52115720A Division JPS5945384B2 (en) 1977-09-27 1977-09-27 Manufacturing method for high-strength biological components

Publications (1)

Publication Number Publication Date
JPS58150504A true JPS58150504A (en) 1983-09-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP57154444A Pending JPS58150504A (en) 1982-09-03 1982-09-03 High-strength material for living body and its production

Country Status (1)

Country Link
JP (1) JPS58150504A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03149060A (en) * 1989-11-06 1991-06-25 Kobe Steel Ltd Coating of living body activating substance

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03149060A (en) * 1989-11-06 1991-06-25 Kobe Steel Ltd Coating of living body activating substance

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