JP2000128655A - Joined structure of ceramic member to metal member, joining of ceramic member to metal member, and ceramic heater using the same - Google Patents
Joined structure of ceramic member to metal member, joining of ceramic member to metal member, and ceramic heater using the sameInfo
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- JP2000128655A JP2000128655A JP30862698A JP30862698A JP2000128655A JP 2000128655 A JP2000128655 A JP 2000128655A JP 30862698 A JP30862698 A JP 30862698A JP 30862698 A JP30862698 A JP 30862698A JP 2000128655 A JP2000128655 A JP 2000128655A
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- brazing material
- ceramic
- inorganic powder
- metal
- material layer
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明が属する技術分野】本発明は、セラミック体と金
属体をロウ材を介して接合した接合構造およびこれを用
いたセラミックヒ−タに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a joining structure in which a ceramic body and a metal body are joined via a brazing material, and a ceramic heater using the same.
【０００２】[0002]
【従来の技術】セラミックヒ−タにおいてセラミック体
の端部に金属リ−ドを接合することが行なわれている。
このような場合に、セラミック体と金属体を接合するに
は、セラミック表面をＭｏ−Ｍｎ法でメタライズ（金属
化）し、さらにＮｉメッキを施したのち、銀ロウ材で金
属とロウ接する方法や、Ｔｉ、Ｚｒ、Ｖ等の金属化合物
層をセラミック−金属界面に形成して層間の密着性を改
善した活性金属法などが広く一般的に利用されている。2. Description of the Related Art In a ceramic heater, a metal lead is joined to an end of a ceramic body.
In such a case, in order to join the ceramic body and the metal body, a method of metallizing (metallizing) the ceramic surface by the Mo-Mn method, further applying Ni plating, and then brazing to the metal with a silver brazing material may be used. An active metal method in which a metal compound layer of Ti, Zr, V, etc. is formed at the ceramic-metal interface to improve the adhesion between the layers is widely and generally used.
【０００３】しかし、先のＭｏ−Ｍｎ法はアルミナ等の
酸化物系セラミックには広く採用されているが、窒化珪
素セラミック等の非酸化物系セラミックへの適用は困難
である。また、活性金属法はメタライズとロウ接とを同
時に行うために、銀ロウ中に活性金属であるＴｉを含有
させたＡｇ- Ｃｕ- Ｔｉ系、Ａｇ−Ｃｕ- Ｉｎ- Ｔｉ系
などのロウ材を使用してセラミックと直接反応させて接
合するなど改善が見られるが、十分な強度を有し、耐酸
化性、耐熱性に優れた接合体は得られていないのが現状
である。However, the Mo-Mn method is widely used for oxide ceramics such as alumina, but is difficult to apply to non-oxide ceramics such as silicon nitride ceramics. In the active metal method, in order to simultaneously perform metallization and brazing, a brazing material such as Ag-Cu-Ti-based or Ag-Cu-In-Ti-based in which Ti as an active metal is contained in a silver braze is used. Although improvements have been seen such as bonding by directly reacting with ceramics during use, a bonded body having sufficient strength and excellent in oxidation resistance and heat resistance has not yet been obtained.
【０００４】通常セラミック体と金属体を加熱接合する
場合、両者の熱膨張差により冷却過程で接合部の付近に
残留応力が働き、接合体の接合強度の低下やセラミック
スに割れ等が発生する。この残留応力を低減するため両
者の間にＭｏ、Ｗ、Ｆｅ−Ｎｉ−Ｃｏ合金等の低熱膨張
金属を挿入して接合したり、Ｎｉ、銅、アルミニウム等
の軟質金属板を挟み込んで接合するようにしている。Usually, when a ceramic body and a metal body are joined by heating, a residual stress acts near the joint in the cooling process due to a difference in thermal expansion between the two, causing a decrease in the joint strength of the joined body and cracking of the ceramic. In order to reduce the residual stress, a low thermal expansion metal such as Mo, W, Fe-Ni-Co alloy or the like is inserted between the two for joining, or a soft metal plate such as Ni, copper, aluminum or the like is sandwiched for joining. I have to.
【０００５】これらの軟質金属のなかで銅は耐力が低い
ため応力がかかる接合体に使用すると銅の部分が変形し
てしまう。アルミニウムも同様であり、さらに融点が低
いために高温で使用する接合体には使用できない。Ｎｉ
は耐力があり、耐酸化性、耐熱性の面で優れた特性を持
っているので、セラミック体と金属体の接合用の緩衝材
として適しているが、熱膨張の小さい高純度の窒化物系
セラミックと、接合される金属の間に単純にＮｉ板を挿
入しても両者（Ｎｉ板とセラミック）の熱膨張差により
冷却過程での残留応力が大きくなり、セラミックに割れ
が発生し高い接合強度を有する接合体は得られない。[0005] Among these soft metals, copper has a low proof stress, so that when used for a joint to which stress is applied, the copper portion is deformed. Similarly, aluminum cannot be used for a joined body used at high temperature because of its low melting point. Ni
Is a high-purity nitride material with low thermal expansion, which is suitable as a cushioning material for joining ceramic and metal bodies because it has high strength and excellent properties in terms of oxidation resistance and heat resistance. Even if a Ni plate is simply inserted between the ceramic and the metal to be joined, residual stress in the cooling process increases due to the difference in thermal expansion between the two (the Ni plate and the ceramic), resulting in cracks in the ceramic and high joining strength Cannot be obtained.
【０００６】前述したように活性金属法による方法で
は、Ａｇ−Ｃｕ系のロウ材中に活性金属としてＴｉを使
用したものが多い。ここで、このＡｇ−Ｃｕ−Ｔｉ系ロ
ウ材と窒化物系セラミック（ここでは窒化珪素セラミッ
ク）と金属板の３種類の物質の接合を例にその接合メカ
ニズムと実際の問題点について考えてみる。As described above, in the method based on the active metal method, there are many Ag-Cu brazing materials using Ti as an active metal. Here, the joining mechanism and actual problems will be considered by taking as an example the joining of three types of materials of the Ag-Cu-Ti-based brazing material, the nitride-based ceramic (here, silicon nitride ceramic), and the metal plate.
【０００７】図３（ａ）に示すようにたとえばＡｇ−Ｃ
ｕ−Ｔｉ系のようなロウ材層３を用いてセラミック体４
と金属体１を活性金属法で接合する場合、窒化珪素等の
セラミック体４とロウ材層３との界面にはＴｉＮ及びＴ
ｉ5 Ｓｉ3 の反応層が生成され、この層の形成によりロ
ウ材層３と接していたセラミック体４の表面はメタライ
ズ（金属化）されるものと考えられる。As shown in FIG. 3A, for example, Ag-C
Ceramic body 4 using brazing material layer 3 such as u-Ti
When the metal body 1 and the metal body 1 are joined by the active metal method, the interface between the ceramic body 4 such as silicon nitride and the brazing material layer 3 is formed by TiN and T
It is considered that a reaction layer of i 5 Si 3 is generated, and the surface of the ceramic body 4 in contact with the brazing material layer 3 is metallized (metallized) by the formation of this layer.
【０００８】このＴｉＮ及びＴｉ5 Ｓｉ3 の反応層の上
にＡｇ−Ｃｕ合金のロウ材層３が形成され、さらにこの
ロウ材層３と金属体１とがロウ付けされることにより３
種類の物質の接合体が得られる。A brazing material layer 3 of an Ag—Cu alloy is formed on the reaction layer of TiN and Ti 5 Si 3 , and the brazing material layer 3 and the metal body 1 are brazed.
A conjugate of different materials is obtained.
【０００９】[0009]
【発明が解決しようとする課題】しかし、上記の接合構
造において加熱接合される金属体１とセラミック体４と
の熱膨張の差が大きいと冷却過程で接合部付近に残留応
力が発生する。この場合に、接合される金属体１がＮｉ
板であっても、窒化珪素セラミックとＮｉ板の熱膨張の
差で生じる残留応力がロウ材層３の中あるいはセラミッ
クス体４の表面に働き、接合体の接合強度の低下やセラ
ミックの割れが問題となる。However, if the difference in thermal expansion between the metal member 1 and the ceramic member 4 to be heated and joined in the above-described joint structure is large, residual stress is generated in the vicinity of the joint during the cooling process. In this case, the metal body 1 to be joined is Ni
Even in the case of a plate, the residual stress generated due to the difference in thermal expansion between the silicon nitride ceramic and the Ni plate acts in the brazing material layer 3 or on the surface of the ceramic body 4, and there is a problem in that the joining strength of the joined body is reduced and the ceramic is cracked. Becomes
【００１０】また、上記問題を防止するために、一般的
に緩衝層として使用される軟質金属（たとえば銅など）
は耐熱性や耐食性に問題があり十分に満足できる緩衝
材、緩衝層とはならない。In order to prevent the above problem, a soft metal (for example, copper) generally used as a buffer layer is used.
Has a problem in heat resistance and corrosion resistance and cannot be a sufficiently satisfactory buffer material or buffer layer.
【００１１】そのために、例えばセラミックヒータのリ
ード接続部について、信頼性の高い接合ができないとい
う問題点があった。For this reason, for example, there has been a problem that a highly reliable bonding cannot be performed at a lead connection portion of a ceramic heater.
【００１２】本発明は、セラミック体と金属体との接合
を高強度でかつ安定したものとするために必要な緩衝層
の形成方法およびその緩衝層を有する金属とセラミック
の接合を可能にし、接合の信頼性の高いセラミック体と
金属体の接合構造を提供する点にある。The present invention enables a method of forming a buffer layer necessary for making a ceramic body and a metal body to have high strength and stability and a metal-ceramic bonding having the buffer layer. Another object of the present invention is to provide a highly reliable bonding structure between a ceramic body and a metal body.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、セラミッ
ク体と金属体の接合構造において、両者を接合するロウ
材中に炭素粒子等のロウ材に対する濡れ角５０°以上、
融点１２００℃以上の無機粉末を分散させることによっ
て無機粉末付近のロウ材が滑り変形しやすいようにする
ことにより、セラミック体と金属体の熱膨張差を緩和
し、接合部付近のセラミック体へのクラック発生を防止
できることを見出した。Means for Solving the Problems In the joint structure of a ceramic body and a metal body, the present inventors have found that the brazing material for joining the two has a wetting angle of at least 50 ° with respect to the brazing material such as carbon particles.
By dispersing the inorganic powder having a melting point of 1200 ° C. or more, the brazing filler metal near the inorganic powder is liable to slip and deform, so that the difference in thermal expansion between the ceramic body and the metal body is reduced, and the ceramic body near the joint is applied to the ceramic body. It has been found that cracking can be prevented.
【００１４】[0014]
【作用】セラミック体と金属体をロウ付けした構造にお
いては、前述のように、セラミック体と金属体の熱膨張
率の差による熱応力が破壊の原因となる。本発明のよう
に、セラミック体と金属体を接合するロウ材の部分に、
ロウ材に対して濡れ角が５０°以上であり融点が１２０
０℃以上である無機粉末、たとえば炭素粒子を介在させ
ると、前記熱応力をロウ材とロウ材中に分散している炭
素粒子の界面の滑りないしは変形により熱応力を吸収で
きるので、セラミック体の接合部に発生するクラックを
防止することができる。In the structure in which the ceramic body and the metal body are brazed, as described above, thermal stress due to the difference in the coefficient of thermal expansion between the ceramic body and the metal body causes destruction. As in the present invention, in the brazing material portion joining the ceramic body and the metal body,
The wetting angle to the brazing material is 50 ° or more and the melting point is 120.
When an inorganic powder having a temperature of 0 ° C. or higher, for example, carbon particles is interposed, the thermal stress can be absorbed by slipping or deformation of the interface between the brazing material and the carbon particles dispersed in the brazing material. It is possible to prevent cracks generated at the joint.
【００１５】[0015]
【発明の実施の形態】図１（ａ）を用いて、本発明のセ
ラミック体と金属体の接合構造を説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A joining structure between a ceramic body and a metal body according to the present invention will be described with reference to FIG.
【００１６】まず、セラミック体４上に無機粉末を含ま
ないロウ材層３を形成する。その後、ロウ材との濡れ角
が５０°以上であり融点が１２００℃以上である無機粉
末を分散させたロウ材層２を重ね、さらにその上に、金
属体１を重ねて、例えば超音波接合を用いて接合して、
本発明のセラミック体と金属体の接合体を得ることがで
きる。First, a brazing material layer 3 containing no inorganic powder is formed on a ceramic body 4. Thereafter, a brazing material layer 2 in which an inorganic powder having a wetting angle with the brazing material of 50 ° or more and a melting point of 1200 ° C. or more is dispersed, and a metal body 1 is further laminated thereon, for example, by ultrasonic bonding And joined using
The joined body of the ceramic body and the metal body of the present invention can be obtained.
【００１７】また、他の実施形態として、無機粉末を分
散させたロウ材層２と金属体１との間に、さらに無機粉
末を含まないロウ材層３を介在させることもできる。In another embodiment, a brazing material layer 3 containing no inorganic powder may be interposed between the metal material 1 and the brazing material layer 2 in which the inorganic powder is dispersed.
【００１８】そして、この無機粉末を分散させたロウ材
層２として、ロウ材との濡れ角が５０°以上であり融点
が１２００℃以上である無機粉末を分散させたものを用
いることにより、熱膨張差による応力を緩和することが
できる。As the brazing material layer 2 in which the inorganic powder is dispersed, a material in which an inorganic powder having a wetting angle with the brazing material of 50 ° or more and a melting point of 1200 ° C. or more is dispersed is used. The stress due to the difference in expansion can be reduced.
【００１９】ロウ材との濡れ角が５０°以上の無機粉末
とした理由は、もし濡れ角が５０°未満であると無機粉
末と無機粉末を分散させたロウ材層２が強固に密着する
ため、無機粉末とロウ材間の剥離に起因する滑りによ
り、熱膨張差による応力の緩和が期待できなくなるから
である。The reason why the inorganic powder having a wetting angle of 50 ° or more with the brazing material is that if the wetting angle is less than 50 °, the inorganic powder and the brazing material layer 2 in which the inorganic powder is dispersed are firmly adhered. This is because, due to slippage caused by separation between the inorganic powder and the brazing material, relaxation of stress due to a difference in thermal expansion cannot be expected.
【００２０】また、無機粉末の融点を１２００℃以上と
するのは、１２００℃未満では無機粉末同志の焼結もし
くは溶融により無機粉末とロウ材２間の構造が複雑にな
り層間の滑りを期待できなくなるからである。If the melting point of the inorganic powder is set to 1200 ° C. or more, if the temperature is lower than 1200 ° C., the structure between the inorganic powder and the brazing material 2 becomes complicated due to sintering or melting of the inorganic powder, and slip between layers can be expected. Because it is gone.
【００２１】なお、無機粉末の形状としては、球形より
鱗片状もしくは板状である事が好ましい。これは無機粉
末とロウ材２は濡れが悪いので、外部から応力がかかる
と両者の界面が剥離するため、界面でロウ材が滑り変形
することにより応力を緩和できるものである。鱗片状も
しくは板状であれば、ロウ材層形成時にこれらが配向し
やすく、層状に応力緩和層が形成されるので応力を緩和
しやすくなるからである。The shape of the inorganic powder is preferably scaly or plate-like rather than spherical. This is because the inorganic powder and the brazing material 2 have poor wettability, and when an external stress is applied, the interface between the two is peeled off, so that the stress can be relieved by sliding deformation of the brazing material at the interface. This is because if they are scaly or plate-like, they tend to be oriented during the formation of the brazing material layer, and the stress relaxation layer is formed in a layered manner, so that the stress is easily relaxed.
【００２２】また無機粉末の平均粒径は、２〜１００μ
ｍである事が好ましい。２μｍ未満では、無機粉末同士
が凝集しやすく、このため期待通りの応力緩和効果が得
られない。また、後述するように無機粉末表面にメッキ
を形成する際、粒径２μｍ未満では比表面積が大きくな
るので、メッキ液の消費量が大きくなるので好ましくな
い。そして、無機粉末の粒径が１００μｍ以上では、熱
サイクルによりロウ材中にクラックが発生して好ましく
ない。The average particle size of the inorganic powder is 2 to 100 μm.
m is preferred. If it is less than 2 μm, the inorganic powders are likely to agglomerate, so that the expected stress relaxation effect cannot be obtained. Further, when plating is formed on the surface of the inorganic powder as will be described later, when the particle size is less than 2 μm, the specific surface area is increased, and the consumption of the plating solution is undesirably increased. When the particle diameter of the inorganic powder is 100 μm or more, cracks are generated in the brazing material due to the heat cycle, which is not preferable.
【００２３】無機粉末の添加量については、１０〜４０
体積％とすることが好ましい。無機粉末の添加量を１０
体積％未満にすると、添加による応力緩和効果が不十分
であり４点曲げによる強度が低下し破壊源がロウ材端面
のクラックとなり好ましくない。また、添加量を４０体
積％以上にすると、ロウ材自体の強度が劣化して、４点
曲げによる破壊源がロウ材内部となり、強度が低下す
る。The amount of the inorganic powder added is 10 to 40.
It is preferred to be volume%. Add inorganic powder of 10
If the content is less than the volume%, the stress relaxation effect by the addition is insufficient, the strength by four-point bending is reduced, and the fracture source is unfavorably cracked on the end face of the brazing material. Further, when the addition amount is 40% by volume or more, the strength of the brazing material itself is deteriorated, and a fracture source due to four-point bending is inside the brazing material, and the strength is reduced.
【００２４】このような無機粉末としては、炭素、窒化
ホウ素、マイカ等の粉末、あるいは炭化珪素、窒化珪
素、窒化アルミニウム、酸化アルミニウム、酸化シリコ
ン、酸化マグネシウム、炭化タングステン等のセラミッ
クス粉末が使用可能であるが、特に炭素が好適である。As such an inorganic powder, a powder of carbon, boron nitride, mica or the like, or a ceramic powder of silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, silicon oxide, magnesium oxide, tungsten carbide or the like can be used. However, carbon is particularly preferred.
【００２５】また、無機粉末を分散させたロウ材層２の
マトリックス成分としては、Ａｇ−Ｃｕ、Ａｇ−Ｃｕ−
Ｉｎ、Ａｕ−Ｃｕ等を主成分としたロウ材を用いること
が可能である。The matrix components of the brazing material layer 2 in which the inorganic powder is dispersed include Ag-Cu, Ag-Cu-
It is possible to use a brazing material containing In, Au-Cu or the like as a main component.
【００２６】そして、無機粉末として炭素粒子を分散さ
せる場合は、炭素粒子表面にＮｉ等のメッキを施すと、
ロウ材と炭素粒子混合粉焼結時の焼結状態を改善でき
る。以下、Ｎｉメッキの形成方法を説明する。まず、炭
素粒子を水中に分散させた懸濁液を作製し、前記懸濁液
中に適量のＰｄ系の活性剤を滴下して炭素粒子表面を活
性化処理する。この懸濁液を濾紙を用いて濾過したの
ち、蒸留水で十分洗浄して余分な活性液を除去し、蒸留
水中に再度分散させて前記炭素粒子の懸濁液を再度作製
する。その後、液温を適正温度に保持したＮｉメッキ液
中に前記懸濁液を徐々に投入して、表面にＮｉメッキを
施した炭素粒子を得ることができる。When carbon particles are dispersed as an inorganic powder, the surface of the carbon particles is plated with Ni or the like.
The sintering state at the time of sintering the mixed powder of the brazing material and the carbon particles can be improved. Hereinafter, a method for forming Ni plating will be described. First, a suspension is prepared by dispersing carbon particles in water, and an appropriate amount of a Pd-based activator is dropped into the suspension to activate the surface of the carbon particles. The suspension is filtered using a filter paper, washed sufficiently with distilled water to remove an excess of the active liquid, and dispersed again in distilled water to prepare a suspension of the carbon particles again. Thereafter, the suspension is gradually introduced into a Ni plating solution in which the solution temperature is maintained at an appropriate temperature to obtain carbon particles having a Ni-plated surface.
【００２７】ここで、さらに図２を用いて、本発明によ
るセラミックヒータの例を説明する。このセラミックヒ
ータは、無機導電材からなる発熱体およびリード部を内
蔵したセラミック体４の電極取出用の端子部上７にＡｇ
−Ｃｕ−Ｔｉを主成分とした無機粉末を含まないロウ材
層３が形成され、その上に炭素粉末２０体積％とＡｇ−
Ｃｕ合金粉末８０体積％からなる、無機粉末を分散させ
たロウ材層２が形成され、さらにその上にＮｉリード線
６を接合した応力緩和層８が形成されたセラミックヒー
タである。Here, an example of the ceramic heater according to the present invention will be described with reference to FIG. This ceramic heater has a heating element made of an inorganic conductive material and a lead 7 built in a ceramic body 4 with an electrode extraction terminal 7 on an electrode extraction terminal 7.
-A brazing material layer 3 containing no inorganic powder containing Cu-Ti as a main component is formed, on which 20% by volume of carbon powder and Ag-
This is a ceramic heater in which a brazing material layer 2 composed of 80% by volume of a Cu alloy powder and in which an inorganic powder is dispersed is formed, and a stress relaxation layer 8 to which a Ni lead wire 6 is bonded is further formed thereon.
【００２８】この場合も、無機粉末を分散させたロウ材
層２を備えたことにより、熱膨張差による応力を緩和す
ることができる。Also in this case, by providing the brazing material layer 2 in which the inorganic powder is dispersed, the stress due to the difference in thermal expansion can be reduced.
【００２９】なお、本発明において、無機粉末とロウ材
の濡れ角は、以下のようにして評価する。板状に加工し
表面を平面研削した無機粉末焼結体上に、成形圧１ｔｏ
ｎ／ｃｍ2 で成形し５ｍｍφ×５ｍｍに加工したロウ材
を載せた後、１０-3torr以下の真空炉中でロウ材の融点
以上の温度で熱処理してロウ材を溶融させ、ロウ材の形
状を真横から観察し、無機粉末焼結体とロウ材の接触部
分の角度を測定する。In the present invention, the wetting angle between the inorganic powder and the brazing material is evaluated as follows. Forming pressure 1 to on inorganic powder sintered body processed into plate shape and surface ground
A brazing material molded at n / cm 2 and processed to 5 mmφ × 5 mm is placed and then heat-treated at a temperature not lower than the melting point of the brazing material in a vacuum furnace of 10 −3 torr or less to melt the brazing material. The shape is observed from the side, and the angle of the contact portion between the inorganic powder sintered body and the brazing material is measured.
【００３０】ロウ材と良く濡れる材料をロウ材中に入れ
ても、溶融時に完全に一体化してしまい応力緩和効果が
期待できないことから、少なくとも、ロウ材との濡れ角
が５０°以上の材料を用いるのが好ましい。Even if a material that wets well with the brazing material is put into the brazing material, the material is completely integrated during melting and a stress relaxation effect cannot be expected. Therefore, at least a material having a wetting angle with the brazing material of 50 ° or more is used. It is preferably used.
【００３１】無機粉末の粒径および体積分率は、セラミ
ックスと金属の接合部分を直角にダイヤモンドカッター
を用いて切断し、切断面の１００〜２０００倍のＳＥＭ
（電子顕微鏡写真）から測定する。体積分率は、画像解
析装置を用いて評価する。それぞれ５回測定し、その平
均値をとる。The particle diameter and the volume fraction of the inorganic powder are determined by cutting the joint between the ceramic and the metal at a right angle using a diamond cutter, and using an SEM 100 to 2000 times the cut surface.
(Electron micrograph). The volume fraction is evaluated using an image analyzer. Measure each five times and take the average value.
【００３２】[0032]
【実施例】実施例１ 図１（ｃ）を用いて本発明の実施例を説明する。まず、
平均粒径２μｍの炭素粉末の表面に、厚み０．２μｍの
Ｎｉメッキを施す。その後、前記炭素粉末２０体積％
と、Ａｕ−Ｃｕ−Ｔｉ合金粉末８０体積％とを混合し、
適量のバインダーを加えた後１ｔｏｎ／ｃｍ2 でプレス
成形し、９００〜１０００℃で予備焼結させたロウ材の
焼結体を得る。これが、無機粉末を分散させたロウ材層
２となる。Embodiment 1 An embodiment of the present invention will be described with reference to FIG. First,
The surface of the carbon powder having an average particle size of 2 μm is plated with Ni having a thickness of 0.2 μm. Then, the carbon powder 20% by volume
And 80% by volume of Au—Cu—Ti alloy powder,
After adding an appropriate amount of binder, it is press-formed at 1 ton / cm 2 and a sintered body of brazing material pre-sintered at 900 to 1000 ° C. is obtained. This becomes the brazing material layer 2 in which the inorganic powder is dispersed.
【００３３】次に、接合面を＃３２０番の砥石で研磨し
た円柱状窒化珪素からなるセラミック体４と、相手材の
Ｎｉからなる金属体１のそれぞれの接合面に、Ａｇ−Ｃ
ｕ−Ｔｉ系のロウ材を塗布した後、１０-3torr以下の真
空炉中で無機粉末を含まないロウ材層３’を形成する。
前記円柱状窒化珪素からなるセラミック体４の表面の無
機粉末を含まないロウ材層３上に、前記無機粉末を分散
させたロウ材の焼結体と金属体１を重ねて、１０-3torr
以下の真空炉中で熱処理してこれらを接合する。Next, Ag-C is applied to each of the joining surfaces of the ceramic body 4 made of columnar silicon nitride whose joining surface is polished with a # 320 grindstone and the metal body 1 made of Ni as a mating material.
After applying the u-Ti brazing material, a brazing material layer 3 ′ containing no inorganic powder is formed in a vacuum furnace of 10 −3 torr or less.
The sintered body of the brazing material in which the inorganic powder is dispersed and the metal body 1 are superposed on the brazing material layer 3 containing no inorganic powder on the surface of the ceramic body 4 made of the cylindrical silicon nitride, and 10 −3 torr
These are joined by heat treatment in the following vacuum furnace.
【００３４】その結果、窒化珪素セラミック表面にロウ
接した前述の無機粉末を分散したロウ材層２は、光沢の
ない銀色ないしは灰黒色を呈した。このように無機粉末
を分散したロウ材層２の両側に無機粉末を含まないロウ
材層３’を設けた後、加熱ロウ付けすることにより、緩
衝材を間に挟んだ構造のセラミック体と金属体の接合体
が得られる。As a result, the brazing material layer 2 in which the above-mentioned inorganic powder was dispersed and brazed to the surface of the silicon nitride ceramic exhibited a dull silver or gray black color. After the brazing material layer 3 'containing no inorganic powder is provided on both sides of the brazing material layer 2 in which the inorganic powder is dispersed in this manner, the brazing material layer is heated and brazed to form a ceramic body and metal having a structure in which a buffer material is interposed therebetween. A conjugate of the body is obtained.
【００３５】この方法で接合した円柱状の金属体とセラ
ミック体の接合体に対し、接合面に対して平行に４点曲
げ応力を印加して、破断強度を測定した。強度として
は、５個のデータを平均したものを用いた。本発明の試
料は、４点曲げ試験強度で３８０ＭＰａと高い接合強度
が得られた。この時の破断は、セラミックス界面のメタ
ライズ層を一部含む炭素粒子を含有する金属層内部で起
きた。A four-point bending stress was applied to the cylindrical body and ceramic body joined in this manner in parallel to the joint surface, and the breaking strength was measured. As the intensity, an average of five data was used. The sample of the present invention exhibited a high bonding strength of 380 MPa in a four-point bending test strength. The fracture at this time occurred inside the metal layer containing the carbon particles partially including the metallized layer at the ceramic interface.
【００３６】比較のため無機粉末を含まないロウ材層で
接合した金属体とセラミック体の接合体を作成し４点曲
げ強度を測定した。図３（ｂ）に示したように、セラミ
ック体４上に無機粉末を含まないロウ材層３を形成し、
その上に金属体１を重ねて真空中で熱処理してこれらを
接合することにより測定用サンプルを準備した。４点曲
げ強度測定後のサンプルの破壊面を観察したところ、一
部接合界面を含むセラミック内部で破断し、その強度は
２１０ＭＰａと低いものであった。For comparison, a joined body of a metal body and a ceramic body joined with a brazing material layer containing no inorganic powder was prepared, and the four-point bending strength was measured. As shown in FIG. 3B, a brazing material layer 3 containing no inorganic powder is formed on the ceramic body 4,
The sample for measurement was prepared by stacking the metal body 1 thereon and heat-treating it in a vacuum to join them. Observation of the fracture surface of the sample after the four-point bending strength measurement revealed that the fracture occurred inside the ceramic including a part of the bonding interface, and the strength was as low as 210 MPa.
【００３７】実施例２ 本発明の他の実施例を図１（ｂ）を用いて説明する。図
１（ｂ）に示すように円柱状の窒化珪素（Ｓｉ3 Ｎ4 ）
セラミック体４と円柱状のＮｉからなる金属体１を接合
する場合である。まず、平均粒径５μｍの鱗片状炭素粉
末の表面に、不図示のＮｉメッキを施し、さらに、前記
炭素粒子を水素ガスを含む還元雰囲気中１０００℃で熱
処理する。その後、前記炭素粉末２０体積％と、Ａｇ−
Ｃｕ−Ｔｉ合金粉末８０体積％とを混合し、適量のバイ
ンダーを加えた後１ｔｏｎ／ｃｍ2 でプレス成形し、７
００〜８００℃で予備焼結させたロウ材層の焼結体を得
る。これが無機粉末を分散させたロウ材層２となる。Embodiment 2 Another embodiment of the present invention will be described with reference to FIG. As shown in FIG. 1B, cylindrical silicon nitride (Si 3 N 4 )
This is a case where the ceramic body 4 and the metal body 1 made of cylindrical Ni are joined. First, Ni plating (not shown) is applied to the surface of the flaky carbon powder having an average particle size of 5 μm, and the carbon particles are further heat-treated at 1000 ° C. in a reducing atmosphere containing hydrogen gas. Then, the carbon powder 20% by volume and Ag-
After mixing with 80% by volume of Cu-Ti alloy powder, adding an appropriate amount of binder, press-forming at 1 ton / cm 2 ,
A sintered body of a brazing material layer pre-sintered at 00 to 800 ° C is obtained. This becomes the brazing material layer 2 in which the inorganic powder is dispersed.
【００３８】この時、前述のロウ材層２の焼結体の気孔
率は、１０％以下にする。気孔率を１０％以下にするの
は１０％を越えるとロウ材層自身の強度が低くなりロウ
材層部分から破壊する可能性があるからである。At this time, the porosity of the sintered body of the brazing material layer 2 is set to 10% or less. The reason why the porosity is set to 10% or less is that if the porosity exceeds 10%, the strength of the brazing material layer itself is reduced, and there is a possibility that the brazing material layer is broken from the portion.
【００３９】次に、接合面を＃３２０番の砥石で研磨し
た円柱状窒化珪素からなるセラミック体４に、Ａｇ−Ｃ
ｕを主成分としたロウ材を塗布した後、１０-3torr以下
の真空炉中７００〜９００℃で熱処理し、無機粉末を含
まないロウ材層３を形成する。前記無機粉末を含まない
ロウ材層３の表面に、前記無機粉末を分散させたロウ材
層２と金属体１を重ねて超音波接合により両者を接合す
る。Next, Ag-C was added to the ceramic body 4 made of columnar silicon nitride whose joining surface was polished with a # 320 grindstone.
After a brazing material containing u as a main component is applied, heat treatment is performed at 700 to 900 ° C. in a vacuum furnace of 10 −3 torr or less to form a brazing material layer 3 containing no inorganic powder. The brazing material layer 2 in which the inorganic powder is dispersed and the metal body 1 are superimposed on the surface of the brazing material layer 3 containing no inorganic powder, and the two are joined by ultrasonic joining.
【００４０】このサンプルの４点曲げ強度を測定したと
ころ、３８０ＭＰａと高い接合強度が得られた。When the four-point bending strength of this sample was measured, a high bonding strength of 380 MPa was obtained.
【００４１】実施例３ 図２に示したセラミックヒータの製造方法を説明する。
無機導電材からなる発熱体およびリード部を内蔵したセ
ラミック体４の電極取出用の端子部上７にＡｇ−Ｃｕ−
Ｔｉを主成分とするロウ材を塗布し、１０-3torr以下の
真空中９００〜１０００℃で熱処理して無機粉末を含ま
ないロウ材層３を形成する。その後、炭素粉末２０体積
％と、Ａｇ−Ｃｕ合金粉末８０体積％とを混合、適量の
バインダーを加えた後１ｔｏｎ／ｃｍ2 で所定の形状に
プレス成形し、８５０〜９５０℃で予備焼結させたロウ
材の焼結体を得る。これが無機粉末を分散させたロウ材
層２となる。前記無機粉末を含まないロウ材層３上に無
機粉末を分散させたロウ材層２およびＮｉリード線６を
固定した応力緩和層８を重ねて、超音波接合によりこれ
らを一体化して完成したセラミックヒータを得た。Embodiment 3 A method for manufacturing the ceramic heater shown in FIG. 2 will be described.
Ag-Cu- is formed on the terminal 7 for taking out an electrode of the ceramic body 4 containing a heating element made of an inorganic conductive material and a lead portion.
A brazing material containing Ti as a main component is applied and heat-treated at 900 to 1000 ° C. in a vacuum of 10 −3 torr or less to form a brazing material layer 3 containing no inorganic powder. Thereafter, 20% by volume of the carbon powder and 80% by volume of the Ag-Cu alloy powder are mixed, and after adding an appropriate amount of a binder, the mixture is press-formed into a predetermined shape at 1 ton / cm 2 and pre-sintered at 850 to 950 ° C. A sintered body of the brazing material is obtained. This becomes the brazing material layer 2 in which the inorganic powder is dispersed. The brazing material layer 2 in which the inorganic powder is dispersed and the stress relaxation layer 8 to which the Ni lead wires 6 are fixed are superposed on the brazing material layer 3 not containing the inorganic powder, and these are integrated by ultrasonic bonding to complete the ceramic. A heater was obtained.
【００４２】実施例４ ここで、図１（ｂ）に示すテストサンプルを、無機粉末
の粒径を１〜１３０μｍ間、また体積分率を４〜５０％
間で変量したサンプルを作製して、各条件のサンプルに
ついて、４点曲げ強度を測定しその破壊モードを確認し
た。その結果を、表１に示した。無機粉末として鱗片状
炭素粒子であるグラファイトを用いて、粒径と体積分率
を変量して作製したサンプルの評価結果を表１に示し
た。本発明の範囲内であるサンプル２、３、５、６、
７、８、１０、１１、１２は、４点曲げ強度が３５０Ｍ
Ｐａ以上と高い値を示しているが、サンプル１に示した
ようにグラファイトの粒径が１μｍ程度と小さくなる
と、４点曲げ強度が２０５ＭＰａ程度と低くなる。逆に
グラファイトの粒径が１００μｍより大きくなるとロウ
材層内部で破壊し、４点曲げ強度が２００ＭＰａと低下
してしまう。また、グラファイトの体積分率が１０％よ
り低いサンプル４は、磁器内部にクラックが発生し、４
点曲げ強度が１９０ＭＰａ程度と低くなる。逆にグラフ
ァイトの体積分率が４０％より多いサンプル９は、メタ
ライズ層内部で破壊し、４点曲げ強度は１９０ＭＰａと
低くなる。Example 4 Here, the test sample shown in FIG. 1 (b) was prepared by adjusting the particle size of the inorganic powder to 1 to 130 μm and the volume fraction to 4 to 50%.
Samples varied between the samples were prepared, and the four-point bending strength of the sample under each condition was measured to confirm the fracture mode. The results are shown in Table 1. Table 1 shows the evaluation results of the samples prepared by using graphite, which is flaky carbon particles, as the inorganic powder and varying the particle size and volume fraction. Samples 2, 3, 5, 6, within the scope of the invention
7, 8, 10, 11, and 12 have a 4-point bending strength of 350M.
Although the value is as high as Pa or more, as shown in Sample 1, when the graphite particle size is reduced to about 1 μm, the four-point bending strength is reduced to about 205 MPa. Conversely, if the graphite particle size is larger than 100 μm, the graphite will be broken inside the brazing material layer, and the four-point bending strength will be reduced to 200 MPa. Sample 4 having a graphite volume fraction lower than 10% had cracks inside the porcelain,
The point bending strength is as low as about 190 MPa. Conversely, Sample 9 having a graphite volume fraction of more than 40% is broken inside the metallized layer, and the four-point bending strength is as low as 190 MPa.
【００４３】無機粉末の例としては、実施例に示した炭
素粒子以外に、窒化ホウ素粉末、マイカ等の鱗片状粉末
や炭化珪素、窒化珪素、窒化アルミニウム、酸化アルミ
ニウム、酸化シリコン、酸化マグネシウム等のセラミッ
クス粉末が使用可能である。無機粉末としては、ロウ材
と反応し難い、できれば鱗片状のものを用いる方が好ま
しい。Examples of the inorganic powder include, in addition to the carbon particles shown in the examples, scaly powders such as boron nitride powder and mica, and silicon carbide, silicon nitride, aluminum nitride, aluminum oxide, silicon oxide and magnesium oxide. Ceramic powder can be used. As the inorganic powder, it is preferable to use a scaly one which does not easily react with the brazing material, if possible.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【発明の効果】本発明によれば、セラミックスと金属の
接合に際して、両者の間に挟まれるロウ材中に無機粉末
を分散させることにより、無機粉末表面においてロウ材
の滑りもしくは変形により、セラミックス、金属、ロウ
材間の熱膨張差を緩和することにより、セラミックスに
発生するクラックの発生を防止し、信頼性の高い接合を
行うことを可能にすることができる。According to the present invention, at the time of joining a ceramic and a metal, the inorganic powder is dispersed in a brazing material sandwiched between the ceramic and the metal. By alleviating the difference in thermal expansion between the metal and the brazing material, it is possible to prevent the occurrence of cracks in the ceramics and to perform highly reliable bonding.
【図１】（ａ）は本発明のセラミック体と金属体の接合
構造の断面構造図、（ｂ）（ｃ）は４点曲げ強度測定サ
ンプルを示す図である。FIG. 1A is a cross-sectional structural view of a joint structure between a ceramic body and a metal body according to the present invention, and FIGS. 1B and 1C are views showing a sample for measuring four-point bending strength.
【図２】本発明のセラミックヒ−タのリ−ド接合部の拡
大図である。FIG. 2 is an enlarged view of a lead joint of the ceramic heater according to the present invention.
【図３】（ａ）は従来のセラミック体と金属体の接合構
造の断面図、（ｂ）は４点曲げ強度測定サンプルを示し
た図である。3A is a cross-sectional view of a conventional joint structure between a ceramic body and a metal body, and FIG. 3B is a view showing a sample for measuring a four-point bending strength.
１：金属体 ２：無機粉末を分散させたロウ材層 ３：無機粉末を含まないロウ材層 ４：セラミック体 ６：Ｎｉリード線 ７：リード取出部 ８：応力緩衝層 1: metal body 2: brazing material layer in which inorganic powder is dispersed 3: brazing material layer not containing inorganic powder 4: ceramic body 6: Ni lead wire 7: lead extraction portion 8: stress buffer layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ２３Ｋ 33/00 ３１０ Ｂ２３Ｋ 33/00 ３１０Ａ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) B23K 33/00 310 B23K 33/00 310A
Claims (7)
合した接合構造において、上記ロウ材中に、該ロウ材の
濡れ角が５０°以上であり、かつ融点が１２００℃以上
である無機粉末が分散していることを特徴とするセラミ
ック体と金属体の接合構造。In a bonding structure in which a ceramic body and a metal body are bonded via a brazing material, an inorganic material having a wetting angle of 50 ° or more and a melting point of 1200 ° C. or more in the brazing material. A bonded structure of a ceramic body and a metal body, wherein the powder is dispersed.
状であり、且つその平均粒径が２〜１００μｍである事
を特徴とする請求項１記載のセラミック体と金属体の接
合構造。2. The joint structure between a ceramic body and a metal body according to claim 1, wherein said inorganic powder is in the form of a scale or a plate, and has an average particle size of 2 to 100 μm.
であることを特徴とする請求項１記載のセラミック体と
金属体の接合構造。3. The content of the inorganic powder is 10 to 40% by volume.
The joint structure for a ceramic body and a metal body according to claim 1, wherein:
する請求項１及至３記載のセラミック体と金属体の接合
構造。4. A joint structure between a ceramic body and a metal body according to claim 1, wherein said inorganic powder is carbon particles.
ウ材層を形成した後、この上に、ロウ材の濡れ角が５０
°以上であり、且つ融点が１２００℃以上である無機粉
末を分散させたロウ材層を形成し、更にその上に金属体
を重ねて超音波接合もしくは熱処理を施す工程からなる
セラミック体と金属体の接合方法。5. After a brazing material layer containing no inorganic powder is formed on the surface of the ceramic body, the wetting angle of the brazing material is
° or more, and a step of forming a brazing material layer in which an inorganic powder having a melting point of 1200 ° C. or more is dispersed, further superposing a metal body thereon and subjecting it to ultrasonic bonding or heat treatment. Joining method.
にＮｉメッキを施してロウ材粉末中に分散させたことを
特徴とする請求項５記載のセラミック体と金属体の接合
方法。6. The method according to claim 5, wherein the inorganic powder is carbon particles, and the surface thereof is plated with Ni and dispersed in the brazing material powder.
を接合してなるセラミックヒ−タにおいて、請求項１〜
４記載の接合構造を用いて上記セラミック体と金属リ−
ドを接合したことを特徴とするセラミックヒ−タ。7. A ceramic heater in which a metal lead is joined to a ceramic body having a heating element.
The above ceramic body and metal lead are formed using the joint structure described in Item 4.
A ceramic heater characterized by joining a metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30862698A JP2000128655A (en) | 1998-10-29 | 1998-10-29 | Joined structure of ceramic member to metal member, joining of ceramic member to metal member, and ceramic heater using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30862698A JP2000128655A (en) | 1998-10-29 | 1998-10-29 | Joined structure of ceramic member to metal member, joining of ceramic member to metal member, and ceramic heater using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000128655A true JP2000128655A (en) | 2000-05-09 |
Family
ID=17983322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30862698A Pending JP2000128655A (en) | 1998-10-29 | 1998-10-29 | Joined structure of ceramic member to metal member, joining of ceramic member to metal member, and ceramic heater using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000128655A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1500455A1 (en) * | 2003-07-24 | 2005-01-26 | Ansaldo Ricerche S.p.A. | Method for obtaining high-resistance brazed joints of multiple-layer composite materials of ceramic/ceramic and metal/ceramic type, and multiple-layer composite materials obtained through the said method |
| JP2007043128A (en) * | 2005-07-04 | 2007-02-15 | Kyocera Corp | Junction, wafer supporting member using same, and wafer processing method |
| JP2008159831A (en) * | 2006-12-25 | 2008-07-10 | Kyocera Corp | Jointer, wafer support member using the same, and method for processing wafer |
| JP2012201582A (en) * | 2011-03-28 | 2012-10-22 | Ngk Insulators Ltd | Heat conduction member |
| JP2014118310A (en) * | 2012-12-14 | 2014-06-30 | Denki Kagaku Kogyo Kk | Ceramic circuit board |
| JP2015166297A (en) * | 2014-03-04 | 2015-09-24 | 日本碍子株式会社 | honeycomb structure |
| JP2016046289A (en) * | 2014-08-20 | 2016-04-04 | デンカ株式会社 | Ceramics circuit board |
-
1998
- 1998-10-29 JP JP30862698A patent/JP2000128655A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1500455A1 (en) * | 2003-07-24 | 2005-01-26 | Ansaldo Ricerche S.p.A. | Method for obtaining high-resistance brazed joints of multiple-layer composite materials of ceramic/ceramic and metal/ceramic type, and multiple-layer composite materials obtained through the said method |
| JP2007043128A (en) * | 2005-07-04 | 2007-02-15 | Kyocera Corp | Junction, wafer supporting member using same, and wafer processing method |
| JP2008159831A (en) * | 2006-12-25 | 2008-07-10 | Kyocera Corp | Jointer, wafer support member using the same, and method for processing wafer |
| JP2012201582A (en) * | 2011-03-28 | 2012-10-22 | Ngk Insulators Ltd | Heat conduction member |
| JP2014118310A (en) * | 2012-12-14 | 2014-06-30 | Denki Kagaku Kogyo Kk | Ceramic circuit board |
| JP2015166297A (en) * | 2014-03-04 | 2015-09-24 | 日本碍子株式会社 | honeycomb structure |
| JP2016046289A (en) * | 2014-08-20 | 2016-04-04 | デンカ株式会社 | Ceramics circuit board |
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