JP3531838B2 - Method of forming metal layer on zirconia ceramics surface - Google Patents
Method of forming metal layer on zirconia ceramics surfaceInfo
- Publication number
- JP3531838B2 JP3531838B2 JP34678693A JP34678693A JP3531838B2 JP 3531838 B2 JP3531838 B2 JP 3531838B2 JP 34678693 A JP34678693 A JP 34678693A JP 34678693 A JP34678693 A JP 34678693A JP 3531838 B2 JP3531838 B2 JP 3531838B2
- Authority
- JP
- Japan
- Prior art keywords
- metal layer
- metal
- zirconia ceramics
- zirconium
- zirconia
- 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 - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、セラミックス表面に金
属層を形成する方法に関し、特にジルコニアセラミック
ス表面に金属層を形成する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a metal layer on the surface of ceramics, and more particularly to a method for forming a metal layer on the surface of zirconia ceramics.
【０００２】[0002]
【従来の技術】従来のジルコニアセラミックス表面への
金属層の形成方法は、例えば高融点金属であるＭｏ−Ｍ
ｎやＮｉ−Ｗなどから成る金属を１５００℃程度の高温
でセラミックス表面に焼き付けて金属層を形成する方法
が採られている。しかしこの方法では、製造に高温を要
するため、生産効率が悪く、歩留りを悪くしたり、製造
原価を高くしたりなどの問題があった。そのため、低い
温度で安価で簡便に金属層を形成することができる方法
が望まれていた。2. Description of the Related Art A conventional method for forming a metal layer on the surface of zirconia ceramics is, for example, Mo-M which is a refractory metal.
A method of forming a metal layer by baking a metal such as n or Ni—W on the surface of ceramics at a high temperature of about 1500 ° C. is adopted. However, in this method, since high temperature is required for manufacturing, there are problems such as poor production efficiency, poor yield, and high manufacturing cost. Therefore, a method that can inexpensively and easily form a metal layer at a low temperature has been desired.
【０００３】このような要望の中で、金属層を形成する
安価で簡便な方法として、非酸化物セラミックスに対し
ては最近、従来より使用されている銀と銅との共晶組成
から成るロウ中に、活性金属であるチタンを含んだ金属
ロウを使用して、８００℃〜９００℃の低い温度でセラ
ミックス表面にロウ付けして金属層を形成する方法が採
られ始めている。In view of such demands, as a cheap and simple method for forming a metal layer, a brazing alloy having a eutectic composition of silver and copper, which has been used conventionally for non-oxide ceramics, has been used recently. A method of forming a metal layer by brazing a metal braze containing titanium as an active metal on a ceramic surface at a low temperature of 800 ° C. to 900 ° C. has been started.
【０００４】この方法を使えば、酸化物であるジルコニ
アに対しても、ロウ中のチタン（Ｔｉ）とジルコニア中
の酸素（Ｏ）とが反応して、脆い酸化物であるＴｉＯｘ
が生成するものの、同時に酸素を取られたジルコニウム
（Ｚｒ）がセラミックス表面に金属層として生成し、そ
のＺｒ金属層と金属ロウとが強固に結び付くので、接合
強度が実用強度（５０ＭＰａ）前後のかなり高い金属層
を形成することができる。Using this method, titanium (Ti) in the wax and oxygen (O) in the zirconia react with zirconia, which is an oxide, and TiO x , which is a brittle oxide.
However, zirconium (Zr) from which oxygen has been removed is simultaneously formed as a metal layer on the ceramic surface, and the Zr metal layer and the metal braze are firmly bound to each other, so that the bonding strength is considerably higher than the practical strength (50 MPa). High metal layers can be formed.
【０００５】しかしながら、この方法では、接合強度は
まだ充分でなく、さらに、Ｚｒ層とロウとが強固に結び
付くけれども、ロウの濡れ性が悪いためロウ付けする時
のロウの広がりがほとんどなく、ジルコニアセラミック
スと金属ロウとの間に大きな残留応力が生じてしまう。
そのため、生じた大きな残留応力により、時間が経過す
るに従ってセラミックスとロウとの界面の弱い部分に少
しずつ亀裂が入り、セラミックスとロウとの接合強度が
時間とともに大きく低下するという問題があった。However, according to this method, the bonding strength is not yet sufficient, and although the Zr layer and the brazing are strongly bonded, the brazing property of the brazing is poor and the brazing is hardly spread during brazing. A large residual stress is generated between the ceramics and the metal solder.
For this reason, there is a problem that due to the large residual stress generated, a crack is gradually formed in a weak portion of the interface between the ceramics and the solder with the passage of time, and the bonding strength between the ceramics and the solder is greatly reduced with time.
【０００６】本発明は、上述した従来技術が有する課題
に鑑みなされたものであって、その目的は、ジルコニア
セラミックス表面に接合した金属層の接合強度が、実用
強度を充分に満足し、しかも時間が経過しても接合強度
の低下が少ない金属層を安価で簡便に形成する方法を提
供することにある。The present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is that the bonding strength of the metal layer bonded to the surface of the zirconia ceramics sufficiently satisfies the practical strength and the time. An object of the present invention is to provide a method for inexpensively and easily forming a metal layer in which the bonding strength is less likely to decrease even after the lapse of time.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、上記目的
を達成するため鋭意研究した結果、ジルコニアセラミッ
クス表面に金属層を形成する方法として、ジルコニアセ
ラミックスの周囲に炭素を配設した後、窒素雰囲気中に
て１１００℃以上の温度で加熱処理することにより該セ
ラミックス表面に、該セラミックス中のジルコニウムと
の反応によるジルコニウムの窒化相と該セラミックス中
のジルコニウムとの反応によるジルコニウムの炭化相か
ら成る層を形成し、その面上に活性金属を含有するロウ
で金属層を形成する方法を採れば目的を達成することが
できるとの知見を得て、本発明を完成した。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result of arranging carbon around the zirconia ceramics as a method for forming a metal layer on the surface of the zirconia ceramics , In a nitrogen atmosphere
Heat treatment at a temperature of 1100 ° C or higher for
On the surface of the Lamix, a layer composed of a nitriding phase of zirconium by the reaction with zirconium in the ceramic and a carbonized phase of zirconium by the reaction with zirconium in the ceramic is formed, and a layer containing an active metal is formed on the surface. The present invention has been completed based on the finding that the object can be achieved by adopting a method of forming a metal layer.
【０００８】本発明にかかるジルコニアセラミックス表
面への金属層形成方法によれば、先ず、ジルコニアセラ
ミックスの周囲に炭素を配設した後、窒素雰囲気中にて
１１００℃以上の温度で加熱処理することにより該セラ
ミックス表面に、該セラミックス中のジルコニウムとの
反応によるジルコニウムの窒化相と該セラミックス中の
ジルコニウムとの反応によるジルコニウムの炭化相から
成る層を形成する。 According to the method for forming a metal layer on the surface of zirconia ceramics according to the present invention , first, zirconia ceramic
After placing carbon around the mix, in a nitrogen atmosphere
By heating at a temperature of 1100 ° C or higher, the ceramic
The mix surface, you form a layer of a carbide phase of zirconium by reaction with zirconium nitride phase and the ceramics of zirconium by reacting zirconium in said ceramic.
【０００９】このジルコニアの周囲に配設した炭素が、
加熱処理中に飛散してジルコニア中のジルコニウム（Ｚ
ｒ）と反応してジルコニア表面に炭化相（ＺｒＣ）を形
成し、この炭化相が金属ロウの濡れ性を良くする。濡れ
性が改善されることによりロウが広がり、このロウが広
がることにより、金属ロウをセラミックスにロウ付けす
る時に生ずる残留応力を小さくすることができる。The carbon disposed around this zirconia is
Zirconium in the zirconia (Z
It reacts with r) to form a carbonized phase (ZrC) on the zirconia surface, and this carbonized phase improves the wettability of the metal wax. The improved wettability spreads the solder, and the spread of the solder can reduce the residual stress generated when the metal solder is brazed to the ceramic.
【００１０】また、上記活性金属を含有する金属ロウと
しては、銀と銅から成るマトリックス中に、チタンの活
性金属を含むロウであるとした。The metal braze containing the active metal is a braze containing an active metal of titanium in a matrix of silver and copper.
【００１１】炭化相を形成するために、窒素雰囲気中で
加熱処理するので、ジルコニア中のジルコニウムと反応
して、ジルコニア表面に窒化相（ＺｒＮ）が炭化相と同
時に形成され、両者で層を形成し、この窒化相中の窒素
（Ｎ）や炭化相中の炭素（Ｃ）が、ロウ付けする時に金
属ロウ中のチタン（Ｔｉ）と反応して、ロウとセラミッ
クスとの界面に窒化物であるＴｉＮや炭化物であるＴｉ
Ｃが形成されてより一層強固に接合される。Since heat treatment is performed in a nitrogen atmosphere to form a carbonized phase , it reacts with zirconium in zirconia to form a nitriding phase (ZrN) on the zirconia surface simultaneously with the carbonized phase, and forms a layer with both. and the carbon of the nitrogen in the nitride phase in the (N) or carbide phase (C) reacts with titanium in the metal brazing (Ti) when brazing is the nitride at the interface between the wax and ceramic TiN and carbide Ti
C is formed and is more firmly bonded.
【００１２】また、加熱処理する温度としては、１１０
０℃以上が必要であり、１１００℃よりも低いとジルコ
ニアセラミックス中のＺｒと炭素（Ｃ）及び窒素（Ｎ）
との反応がしにくく、ＺｒＣ及びＺｒＮが形成されにく
いため、高い接合強度が得られず、濡れ性も悪くなる。
高い方の上限の温度は、セラミックスが分解する温度ま
で可能であるが、高くしてもメリットは特にないので、
経済性の面等から適した温度を選べばよい。The heat treatment temperature is 110
0 ° C or higher is required, and if lower than 1100 ° C, Zr, carbon (C) and nitrogen (N) in zirconia ceramics
Difficult reaction is the, for Zr C 及 beauty Zr N is formed hard, high bonding strength can not be obtained, wettability becomes poor.
The upper limit temperature, which is higher, is possible up to the temperature at which the ceramics decompose, but there is no particular advantage in raising it, so
A suitable temperature may be selected from the viewpoint of economy.
【００１３】以上の方法を採ることにより、ジルコニア
セラミックス表面に実用強度を常に上回る高い接合強度
を持ち、しかも接合強度が時間が経過しても低下するこ
とが少ない金属ロウ、即ち金属層を、安価で簡便にジル
コニアセラミックス表面に形成することが出来る。By adopting the above method, it is possible to obtain a metal braze, which has a high bonding strength, which is always higher than the practical strength, on the surface of zirconia ceramics, and whose bonding strength does not decrease with time, that is, a metal layer, at a low cost. Can be easily formed on the surface of zirconia ceramics.
【００１４】[0014]
【実施例】以下、本発明の実施例を比較例と共に挙げ、
本発明をより詳細に説明する。EXAMPLES Examples of the present invention will be given below together with comparative examples.
The present invention will be described in more detail.
【００１５】（実施例１〜４）１０ｍｍ角で、厚さ３ｍ
ｍのジルコニアセラミックス〔（株）日本セラテック社
製〕の周囲に炭素を配設し、１１００℃以上の窒素雰囲
気中で加熱処理した。加熱処理後、ジルコニアセラミッ
クスの面上に直径６ｍｍ、厚さ０．０５ｍｍの活性金属
を含有するロウ（７１Ａｇ−２７Ｃｕ−２Ｔｉｗｔ％）
を敷き、加熱してロウ付けした。また、ロウ付けした金
属層の上面に直径３ｍｍのコバール〔住友特殊金属
（株）社製 ＫＶ−２〕を接合し、それを引っ張ること
によりアルミナセラミックスに接合した金属層の接合強
度を求めた。(Examples 1 to 4) 10 mm square and 3 m thick
m was placed around zirconia ceramics [manufactured by Nippon Ceratech Co., Ltd.] and heat-treated in a nitrogen atmosphere at 1100 ° C. or higher. After the heat treatment, a braze (71Ag-27Cu-2Tiwt%) containing an active metal having a diameter of 6 mm and a thickness of 0.05 mm on the surface of the zirconia ceramics.
Was laid, heated and brazed. Further, Kovar [KV-2 manufactured by Sumitomo Special Metals Co., Ltd.] having a diameter of 3 mm was joined to the upper surface of the brazed metal layer, and the joint strength of the metal layer joined to the alumina ceramics was obtained by pulling the joint.
【００１６】なお、濡れ性の良否は、ロウ付けした金属
ロウの広がりによって判断するため（広がりが大きいほ
ど濡れ性がよい）、ロウ付けした後のロウの直径を測定
して面積を求め、その面積の大小で濡れ性を判断した。
また、コバールの接合は、真空雰囲気中で８００℃に加
熱処理することにより行い、接合したコバールを垂直方
向に引っ張り、破壊に至るまでの引っ張り強度を測定
し、その強度をロウ（金属層）の接合強度とした。それ
らの結果を表１に示す。Since the wettability is judged by the spread of the brazed metal wax (the wider the spread, the better the wettability), the diameter of the solder after brazing is measured to obtain the area, and The wettability was judged by the size of the area.
In addition, joining of Kovar is carried out by heat treatment at 800 ° C. in a vacuum atmosphere, the joined Kovar is pulled in the vertical direction, and the tensile strength up to the fracture is measured, and the strength of the wax (metal layer) is measured. The bonding strength was used. The results are shown in Table 1.
【００１７】（比較例１〜２）また、比較のため、実施
例と同一のジルコニアセラミックスを用い、表１に示す
雰囲気と温度で加熱処理してロウ付けして金属ロウの面
積を求めた。また、実施例と同様にコバールを接合し、
その接合体に対して、同じく実施例と同様に接合強度を
求めた。それらの結果を表１に示す。(Comparative Examples 1 and 2) For comparison, the same zirconia ceramics as those of the example were used, and heat treatment was performed under the atmosphere and temperature shown in Table 1 and brazing was performed to obtain the area of the metal braze. Also, by joining Kovar as in the example,
The bonding strength of the bonded body was determined in the same manner as in the example. The results are shown in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１から明らかなように、実施例において
は、ロウ付けした後のロウの面積は最初のロウの面積
（２８．３ｍｍ２）よりかなり広がっており、そのた
め、接合直後の接合強度はいずれも実用強度（５０ＭＰ
ａ）を充分に満たす接合体が得られているのは勿論のこ
と、１カ月経過後も接合強度の低下は少なく、実用強度
を満たしている。これに対して比較例１では、加熱処理
する温度が低いため、ＴｉＣやＴｉＮがセラミックス表
面に生成されず、加熱処理しない場合と同様の結果とな
り、ロウの広がりはほとんどなく、接合強度も接合直後
では実用強度を僅かに超す強度が得られているが、１カ
月経過後では著しく低下しており、満足な結果は得られ
ていない。また、比較例２では、加熱雰囲気が窒素雰囲
気でないため、これも加熱処理しない場合と同様の結果
となっている。As is clear from Table 1, in the examples, the area of the solder after brazing is considerably larger than the area of the first solder (28.3 mm 2 ), and therefore the bonding strength immediately after bonding is Practical strength (50MP)
It goes without saying that a joined body sufficiently satisfying the requirement a) has been obtained, and even after one month has passed, the joint strength does not decrease so much that the practical strength is satisfied. On the other hand, in Comparative Example 1, since the temperature for the heat treatment was low, TiC and TiN were not generated on the ceramic surface, and the same results as in the case where the heat treatment was not performed were obtained. The strength obtained was slightly higher than the practical strength, but the strength was remarkably reduced after one month, and satisfactory results were not obtained. Further, in Comparative Example 2, since the heating atmosphere is not a nitrogen atmosphere, this also has the same result as in the case where no heat treatment is performed.
【００２０】[0020]
【発明の効果】以上、説明した本発明にかかるジルコニ
アセラミックス表面への金属層形成方法によれば、ジル
コニアセラミックスの表面に接合強度が実用強度（５０
ＭＰａ）を常に上回るほど高く、しかも時間が経過して
も接合強度の低下が少ない金属層を接合することが出
来、その結果、ジルコニアセラミックス表面に安価で簡
便に金属層を形成することが出来る。As described above, according to the method for forming a metal layer on the surface of zirconia ceramics according to the present invention, the bonding strength on the surface of the zirconia ceramic is practical strength (50).
It is possible to bond a metal layer that is always higher than (MPa) and whose bonding strength does not decrease with time, and as a result, a metal layer can be easily and inexpensively formed on the zirconia ceramic surface.
Claims (2)
配設した後、窒素雰囲気中にて１１００℃以上の温度で
加熱処理することにより該セラミックス表面に、該セラ
ミックス中のジルコニウムとの反応によるジルコニウム
の窒化相と該セラミックス中のジルコニウムとの反応に
よるジルコニウムの炭化相から成る層を形成し、その面
上に活性金属を含有する金属ロウをロウ付けして金属層
を形成することを特徴とするジルコニアセラミックス表
面への金属層形成方法。1. Carbon is provided around the zirconia ceramics.
After arranging, at a temperature of 1100 ° C or higher in a nitrogen atmosphere
The heat treatment forms a layer on the surface of the ceramic, which is composed of a nitriding phase of zirconium by the reaction with zirconium in the ceramic and a carbonized phase of zirconium by the reaction with zirconium in the ceramic, and an active metal is formed on the surface. A method for forming a metal layer on the surface of a zirconia ceramics, which comprises forming a metal layer by brazing a metal braze containing the metal.
成るマトリックス中に、チタンの活性金属を含むロウで
あることを特徴とする請求項１記載のジルコニアセラミ
ックス表面への金属層形成方法。2. A wax containing an active metal comprises silver and copper.
The method for forming a metal layer on the surface of a zirconia ceramics according to claim 1 , wherein the matrix is a wax containing an active metal of titanium .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34678693A JP3531838B2 (en) | 1993-12-14 | 1993-12-14 | Method of forming metal layer on zirconia ceramics surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34678693A JP3531838B2 (en) | 1993-12-14 | 1993-12-14 | Method of forming metal layer on zirconia ceramics surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07172964A JPH07172964A (en) | 1995-07-11 |
| JP3531838B2 true JP3531838B2 (en) | 2004-05-31 |
Family
ID=18385806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34678693A Expired - Fee Related JP3531838B2 (en) | 1993-12-14 | 1993-12-14 | Method of forming metal layer on zirconia ceramics surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3531838B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679611A (en) * | 1996-10-09 | 1997-10-21 | Eastman Kodak Company | Ceramic article containing a core comprising tetragonal zirconia and a shell comprising zirconium nitride |
-
1993
- 1993-12-14 JP JP34678693A patent/JP3531838B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07172964A (en) | 1995-07-11 |
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