JPS6140623B2 - - Google Patents
Info
- Publication number
- JPS6140623B2 JPS6140623B2 JP57154035A JP15403582A JPS6140623B2 JP S6140623 B2 JPS6140623 B2 JP S6140623B2 JP 57154035 A JP57154035 A JP 57154035A JP 15403582 A JP15403582 A JP 15403582A JP S6140623 B2 JPS6140623 B2 JP S6140623B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- apatite
- sintering
- ceramic
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000843 powder Substances 0.000 claims description 35
- 229910052586 apatite Inorganic materials 0.000 claims description 22
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 22
- 229910010293 ceramic material Inorganic materials 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 16
- 239000007769 metal material Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 12
- 239000011162 core material Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000005312 bioglass Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 11
- 239000011257 shell material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000007943 implant Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Dental Preparations (AREA)
- Dental Prosthetics (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
本発明は、医用インプラント材として適するア
パタイト―チタン系複合材料およびその製造法に
関する。
従来、例えば歯科用などに用いるインプラント
材としては、生体に対する親和性の面からアパタ
イト系セラミツクが優れていることが明らかにさ
れているが、強度上靭性が劣る点で実用面で難点
がある。一方、金属は強度面では優れているもの
の中には毒性のあるものもあり、毒性のない金属
でも生体に対する親和性の点では特に期待できる
ものはない。
アルミナ系材料はセラミツクとしては強度的に
優れており、生体に対する毒性もない安定な材料
として最近注目されているが、靭性の点では前記
アパタイトセラミツクと同様にセラミツクの域を
出るほどの物性を示していない。
そこで、本発明では、アパタイト系セラミツク
の生体に対する親和性を利用し、これに金属材料
のもつ靭性を付加して、その欠点をカバーし、イ
ンプラント材として有用な材料を提供せんとする
ものである。
すなわち、本発明第１項の発明はチタン粉末あ
るいはさらにアパタイト粉末を添加した金属材料
をコア材とし、これをアパタイト粉末あるいはさ
らに石英粉末を加えたものにバイオガラス系フリ
ツト粉末を混合したセラミツク材料よりなる外殻
材によつて包被して複合せしめ、同時焼結によつ
て一体化してなることを特徴とするアパタイト―
チタン系複合材料を要旨とするものである。
上記セラミツク材料におけるアパタイト粉末
は、前述のように焼結体としてインプラント材に
適したものであるが、これに石英粉末を加える
と、膨脹と焼成収縮の調節効果がある。又、金属
材料におけるチタンは軽量で靭性に富み、かつ毒
性もなく、これをコア材とし、上記セラミツク材
料よりなる外殻材によつて包被して複合せしめ、
同時焼結によつて一体化することによつて、アパ
タイト系セラミツクの前記欠点を補充し、インプ
ラント材として優れたものとなる。
第２項の発明は、アパタイト粉末50〜100％、
石英粉末０〜50％にバイオガラス系フリツト粉末
を外割で１〜15％添加してなるセラミツク材料と
して、TiH4粉末50〜75％、Ti金属粉末25〜50％
にアパタイト粉末を外割で０〜５％添加してなる
金属材料とを金属材料をコアとし、これをセラミ
ツク材料によつて包被することによつて複合せし
め、不活性又は真空雰囲気で1200〜1300℃で焼結
することを特徴とするアパタイト―チタン系複合
材料の製造法を要旨とするものである。
この第２項の発明におけるセラミツク料に用い
るアパタイト粉末と石英粉末の効果は前述のとお
りであるが、石英粉末の50％以上の添加はアパタ
イト粉末の効果を減殺するので好ましくない。ま
た、セラミツク材料の焼結助剤として、バイオガ
ラス系フリツトを用いるが、これは1200〜1300℃
で焼結させるための助剤としての効果があり、か
つ、アパタイト粉末と石英粉末との焼結時におけ
る親和性と複合材料の生体に対する親和性の向上
効果を奏するものである。
バイオガラスとは、生体親和性の良好なガラス
で本発明に用いるのに好適なものを例示すると、
SiO220.0〜40.0％、Al2O30〜5.0％、B2O335.0〜
45.0％、P2O54.0〜20.0％、CaO1.0〜9.0％、
Na2O5.0〜15.0％なる組成例のものがある。かか
るバイオガラスは100〜1400℃で溶融し、フリツ
ト化して用いる。
このバイオガラス系フリツトは１％未満ではそ
の効果がなく、15％を越える添加はアパタイト粉
末の効果を減殺するとともに、1200〜1300℃での
焼結時に軟化、変形、発泡するので好ましくな
い。
上記セラミツク材料は上記組成の範囲内で第１
図に示す如き膨脹率と第２図に示す如き収縮率並
びに曲げ強度を示す。
本発明の金属材料におけるTiH4粉末は焼成時
に収縮して焼成収縮率を調整する効果があり、
又、アパタイト粉末は焼結体の膨脹率を調節する
効果がある。TiH4は50％未満では焼結金属材料
が焼結セラミツク体よりも収縮率が大きくなり過
ぎて好ましくなく、75％を越えると、収縮率が焼
結セラミツク材料よりも小さくなり過ぎて好まし
くない。アパタイト粉末は５％を越えると、金属
材料の特性、特に靭性を阻害して好ましくない。
かかる金属材料の焼結体は、上記組成の範囲内
で第３図に示す如き膨脹率と第４図に示す如き収
縮率並びに曲げ強度を示す。
上記セラミツク材料と金属材料とは、例えば第
５図に示したように、プレス成形などにより金属
材料１をコアとし、セラミツク材料２を外殻層と
する複合圧粉成形体とする。両材料は前記第１〜
４図に示した膨脹・収縮率に基づいて、それぞれ
の値がなるべく一致するように組成を選定する。
圧粉成形体は不活性又は真空雰囲気中で焼結す
る。すなわち、不活性雰囲気の場合はアルゴンガ
ス気流中で、又、真空雰囲気の場合は10-3Torr
以下で、1200〜1300℃で焼結する。この温度範囲
は、チタンの焼結温度が1200〜1400℃、一方、ア
パタイトの焼結温度が1100〜1300℃であることか
ら、両者の焼結温度範囲である1200〜1300℃を採
つたものである。不活性又は真空雰囲気でなく、
例えば酸素分圧の存在下ではチタンが酸化するの
で好ましくない。
本発明によれば、コアは金属化し、外殻は焼結
セラミツク化した二層構造をなした複合体が得ら
れる。そして、セラミツクと金属とは膨脹係数が
ほぼ等しくその界面には20〜30μｍのチタン酸化
物よりなる中間層が形成され、両層の結合の強固
になつている。
外殻材にアパタイト系セラミツクを使うことで
生体親和性に優れ、又、コアにチタンを用いるこ
とにより軽量で高強度な物質が得られ、医用イン
プラント材として有用な材料となる。
又、粉末焼結法によるので形状は自由にするこ
とができる利点もある。
つぎに実施例について説明する。
下記に示した組成によりＡ、B2種の材料を用
意した。表中の単位は重量％である。
The present invention relates to an apatite-titanium composite material suitable as a medical implant material and a method for producing the same. Conventionally, apatite-based ceramics have been shown to be excellent as implant materials for use in dental applications, etc., in terms of their affinity for living organisms, but they have drawbacks in terms of practical use due to their inferior strength and toughness. On the other hand, although metals are superior in terms of strength, some are toxic, and even non-toxic metals are not particularly promising in terms of affinity for living organisms. Alumina-based materials have excellent strength as ceramics, and have recently attracted attention as stable materials that are not toxic to living organisms.However, in terms of toughness, they exhibit physical properties that are superior to those of ceramics, similar to the apatite ceramics mentioned above. Not yet. Therefore, the present invention aims to provide a material useful as an implant material by utilizing the affinity of apatite ceramic for living organisms and adding the toughness of a metal material to this to cover the drawbacks. . That is, the invention of item 1 of the present invention uses a metal material to which titanium powder or further apatite powder is added as a core material, and this is made from a ceramic material in which bioglass frit powder is mixed with apatite powder or quartz powder. Apatite is characterized in that it is composited by being covered with an outer shell material, and is integrated by simultaneous sintering.
The focus is on titanium-based composite materials. As mentioned above, the apatite powder in the ceramic material is suitable as an implant material as a sintered body, but when quartz powder is added thereto, it has the effect of controlling expansion and firing contraction. In addition, titanium as a metal material is lightweight, has high toughness, and is non-toxic, so titanium is used as a core material and covered with an outer shell material made of the above-mentioned ceramic material to form a composite.
By integrating the materials through simultaneous sintering, the above-mentioned drawbacks of apatite-based ceramics can be compensated for, making them excellent as implant materials. The invention of item 2 provides apatite powder of 50 to 100%,
A ceramic material made by adding 1 to 15% of bioglass frit powder to 0 to 50% of quartz powder, 50 to 75% of TiH 4 powder and 25 to 50% of Ti metal powder.
and a metal material obtained by adding 0 to 5% of apatite powder in total, the metal material is used as a core, and this is covered with a ceramic material to form a composite. The gist of this paper is a method for producing an apatite-titanium composite material, which is characterized by sintering at 1300°C. The effects of the apatite powder and quartz powder used in the ceramic material in the invention of item 2 are as described above, but addition of 50% or more of the quartz powder is not preferable because it reduces the effect of the apatite powder. In addition, bioglass frit is used as a sintering aid for ceramic materials, but this
It is effective as an auxiliary agent for sintering, and also has the effect of improving the affinity between apatite powder and quartz powder during sintering and the affinity of the composite material for living organisms. Bioglass is a glass with good biocompatibility and suitable for use in the present invention is exemplified by:
SiO2 20.0~40.0%, Al2O3 0 ~5.0%, B2O3 35.0 ~
45.0%, P2O5 4.0 ~20.0%, CaO1.0~9.0%,
There is an example of a composition of 5.0 to 15.0% Na 2 O. Such bioglass is melted at 100 to 1400°C and used as a frit. If the bioglass frit is less than 1%, it has no effect, and if it exceeds 15%, the effect of the apatite powder is diminished, and the frit softens, deforms, and foams during sintering at 1200 to 1300°C, which is not preferable. The ceramic material is the first ceramic material within the above composition range.
The expansion ratio as shown in the figure, the contraction ratio as shown in FIG. 2, and the bending strength are shown. The TiH 4 powder in the metal material of the present invention has the effect of shrinking during firing and adjusting the firing shrinkage rate,
Furthermore, the apatite powder has the effect of adjusting the expansion rate of the sintered body. If TiH 4 is less than 50%, the shrinkage rate of the sintered metal material becomes too large than that of the sintered ceramic body, which is undesirable, and if it exceeds 75%, the shrinkage rate becomes too small than that of the sintered ceramic material, which is not preferable. If the amount of apatite powder exceeds 5%, it is not preferable because it impairs the properties of the metal material, especially the toughness. A sintered body of such a metal material exhibits an expansion rate as shown in FIG. 3, a contraction rate and bending strength as shown in FIG. 4 within the above composition range. As shown in FIG. 5, the ceramic material and the metal material are press-molded to form a composite powder compact having the metal material 1 as a core and the ceramic material 2 as an outer shell layer, for example, as shown in FIG. Both materials are the first to
Based on the expansion/contraction rates shown in Figure 4, the composition is selected so that the respective values match as much as possible. The compact is sintered in an inert or vacuum atmosphere. That is, in an inert atmosphere, in an argon gas flow, or in a vacuum atmosphere, at 10 -3 Torr.
Sintering is performed at 1200-1300°C below. The sintering temperature of titanium is 1200-1400℃, while the sintering temperature of apatite is 1100-1300℃, so this temperature range is 1200-1300℃, which is the sintering temperature range of both. be. not an inert or vacuum atmosphere;
For example, titanium is undesirably oxidized in the presence of oxygen partial pressure. According to the present invention, a composite body having a two-layer structure in which the core is metallized and the outer shell is made of sintered ceramic is obtained. Ceramic and metal have substantially the same coefficient of expansion, and an intermediate layer of titanium oxide with a thickness of 20 to 30 μm is formed at the interface, thereby strengthening the bond between the two layers. By using apatite ceramic for the outer shell material, it has excellent biocompatibility, and by using titanium for the core, a lightweight and high-strength material can be obtained, making it a useful material as a medical implant material. Furthermore, since the powder sintering method is used, there is an advantage that the shape can be made freely. Next, examples will be described. Two types of materials, A and B, were prepared with the compositions shown below. The units in the table are weight %.
【表】
外殻材に用いるフリツトはNaCO3：SiO2：
CaHPO4・2H2O：CaCO3：Na2O・B2O510H2O＝
２：３：１：２（重量比）の乾式混合物を1000℃
で溶融フリツト化したものである。
Ａ，Ｂともにアクリル系バインダを用いて造粒
し、乾式プレスで第５図に示す如き二層構造体の
圧粉体を成形した。ついで、これらを1250℃でア
ルゴンガス中で焼成した。
その結果、コアは金属化し、外殻は焼結セラミ
ツク化した二層構造の複合体が得られた。コアと
外殻との界面は20〜30μｍのチタン酸化物層を中
間層として強固な結合となつていた。
上記は不活性雰囲気で焼結した例を示したが、
真空中で焼結しても同様のものが得られた。[Table] The frit used for the outer shell material is NaCO 3 :SiO 2 :
CaHPO 4・2H 2 O: CaCO 3 : Na 2 O・B 2 O 5 10H 2 O=
Dry mixture of 2:3:1:2 (weight ratio) at 1000℃
It is made into melted frit. Both A and B were granulated using an acrylic binder and molded into a two-layer structured powder compact as shown in FIG. 5 using a dry press. These were then calcined at 1250°C in argon gas. As a result, a two-layer composite was obtained, with a metalized core and a sintered ceramic outer shell. The interface between the core and the outer shell was strongly bonded with a 20-30 μm titanium oxide layer as an intermediate layer. The above example shows sintering in an inert atmosphere, but
A similar product was obtained by sintering in vacuum.
第１図は本発明に用いるセラミツク材料の膨脹
率を示すグラフ、第２図は同収縮率を強度を示す
グラフ、第３図は本発明に用いる金属材料の膨脹
率を示すグラフ、第４図は同収縮率と強度を示す
グラフ、第５図は実施例の成形体の一例を示す斜
視図である。
１……コア、２……外殻。
Fig. 1 is a graph showing the expansion rate of the ceramic material used in the present invention, Fig. 2 is a graph showing the shrinkage rate as a function of strength, Fig. 3 is a graph showing the expansion rate of the metal material used in the present invention, Fig. 4 5 is a graph showing the shrinkage rate and strength, and FIG. 5 is a perspective view showing an example of the molded article of the example. 1...Core, 2...Outer shell.
Claims (1)
添加した金属材料をコア材とし、これをアパタイ
ト粉末あるいはさらに石英粉末を加えたものにバ
イオガラス系フリツト粉末を混合したセラミツク
材料よりなる外殻材によつて包被して複合せし
め、同時焼結によつて一体化してなることを特徴
とするアパタイト―チタン系複合材料。 ２ アパタイト粉末50〜100％（重量。以下同
じ）、石英粉末０〜50％にバイオガラス系フリツ
ト粉末を外割で１〜15％添加してなるセラミツク
材料と、TiH4粉末50〜75％、Ti金属粉末25〜50
％にアパタイト粉末を外割で０〜５％添加してな
る金属材料とを金属材料をコアとし、これをセラ
ミツク材料によつて包被することによつて複合せ
しめ、不活性又は真空雰囲気1200〜1300℃で焼結
することを特徴とするアパタイト―チタン系複合
材料の製造法。[Scope of Claims] 1. The core material is a metal material to which titanium powder or apatite powder is added, and the outer shell is made of a ceramic material in which bioglass frit powder is mixed with apatite powder or quartz powder. An apatite-titanium composite material characterized by being wrapped in a composite material and integrated by simultaneous sintering. 2. A ceramic material made by adding 1 to 15% of bioglass frit powder to 50 to 100% apatite powder (by weight; the same applies hereinafter) and 0 to 50% of quartz powder, and 50 to 75% of TiH 4 powder, Ti metal powder 25~50
% and a metal material with an external addition of 0 to 5% apatite powder, the metal material is used as a core, and this is covered with a ceramic material to form a composite, and an inert or vacuum atmosphere of 1200 ~ A manufacturing method for apatite-titanium composite material characterized by sintering at 1300℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57154035A JPS5945976A (en) | 1982-09-06 | 1982-09-06 | Apatite-titanium complex material and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57154035A JPS5945976A (en) | 1982-09-06 | 1982-09-06 | Apatite-titanium complex material and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5945976A JPS5945976A (en) | 1984-03-15 |
| JPS6140623B2 true JPS6140623B2 (en) | 1986-09-10 |
Family
ID=15575481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57154035A Granted JPS5945976A (en) | 1982-09-06 | 1982-09-06 | Apatite-titanium complex material and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5945976A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62132756A (en) * | 1985-12-04 | 1987-06-16 | 株式会社アドバンス | High strength calcium phosphate base ceramic material |
-
1982
- 1982-09-06 JP JP57154035A patent/JPS5945976A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5945976A (en) | 1984-03-15 |
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