JP2003128473A - Ceramic bonded body and its manufacturing method - Google Patents
Ceramic bonded body and its manufacturing methodInfo
- Publication number
- JP2003128473A JP2003128473A JP2001324449A JP2001324449A JP2003128473A JP 2003128473 A JP2003128473 A JP 2003128473A JP 2001324449 A JP2001324449 A JP 2001324449A JP 2001324449 A JP2001324449 A JP 2001324449A JP 2003128473 A JP2003128473 A JP 2003128473A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- ceramics
- compact
- sintered
- bonding layer
- 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.)
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Links
Landscapes
- Ceramic Products (AREA)
- Devices For Post-Treatments, Processing, Supply, Discharge, And Other Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、接合強度に優れ
た、セラミックス成形体同士よりなるセラミックス接合
体およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramics bonded body composed of ceramics molded bodies having excellent bonding strength and a method for producing the same.
【０００２】[0002]
【従来技術とその問題点】セラミックスは金属に比べ
て、耐熱性、耐摩耗性および耐食性に優れていることか
ら産業用構造部品などの分野で積極的に採用されつつあ
る。しかしながら、セラミックスは金属に比べて加工性
に劣るため、複雑形状部品の製造には非常にコストが高
くなるという欠点があった。そのため、セラミックス焼
結体同士の接合により複雑形状部品を製造することが検
討されている。2. Description of the Related Art Ceramics are more and more actively used in the field of industrial structural parts because they are superior in heat resistance, wear resistance and corrosion resistance to metals. However, since ceramics are inferior to metal in workability, there is a drawback that the cost for manufacturing a complex-shaped component is very high. Therefore, manufacturing of a complex-shaped part by joining ceramics sintered compacts is examined.
【０００３】セラミックス焼結体で形成されたセラミッ
クス成形体同士の接合は従来から高温加熱法、高融点金
属法、有機接着剤法などの方法により行われている。し
かしながら、これらの方法で接合したセラミックス成形
体同士よりなるセラミックス接合体は単一構造のセラミ
ックス焼結体よりなるセラミックス成形体に比べて接合
箇所の接合強度、耐食性、耐熱性などが劣り、かつコス
トが高くなるなどの問題点があり、極限られた用途でし
か使用されていない。Conventionally, the joining of the ceramic compacts formed of the sintered ceramics has been performed by a method such as a high temperature heating method, a high melting point metal method, an organic adhesive method or the like. However, a ceramics joined body composed of ceramics compacts joined by these methods is inferior in joint strength, corrosion resistance, heat resistance, etc. at the joint portion as compared with a ceramics compact formed of a ceramic sintered body having a single structure, and the cost is low. However, it is used only for extremely limited purposes.
【０００４】一方、これらの欠点を改善する接合方法と
して、特開平０６−１９１９５９号公報には接合する未
焼結のセラミックス成形体と同原料で作製した泥漿を用
いて未焼結のセラミツクス成形体同士を接合し、焼結さ
せる方法が開示されているが、接合層厚さや接合部分の
強度等についてまで考慮されておらず、産業用機械部品
として使用した場合に強度不足や信頼性が十分と言えな
い問題点などがある。On the other hand, as a joining method for improving these drawbacks, Japanese Unexamined Patent Publication (Kokai) No. 06-191959 discloses an unsintered ceramic molded body using a slurry produced from the same raw material as the unsintered ceramic molded body to be joined. Although a method of joining and sintering each other is disclosed, even the thickness of the joining layer and the strength of the joining part are not considered, and when used as an industrial machine part, insufficient strength and sufficient reliability are considered. There are problems that cannot be said.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、接合
強度に優れた、セラミックス成形体同士よりなるセラミ
ックス接合体およびその製造方法を提供する点にある。SUMMARY OF THE INVENTION An object of the present invention is to provide a ceramics joined body composed of ceramics shaped bodies having excellent joining strength and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】本発明は前記のような現
状を鑑み鋭意研究を重ねてきた結果、未焼結のセラミッ
クス成形体同士の接合において、接合に用いるセラミッ
クス系スラリー接着剤のセラミックス成分組成がセラミ
ックス成形体のセラミックス成分組成を９０重量％以上
含有するセラミックス系スラリー接着剤を用いて、接合
層厚さ、セラミックス成形体と接合層の結晶粒径比を制
御することにより、優れた接合強度を有する、セラミッ
クス成形体同士よりなるセラミックス接合体を見い出し
た。The present invention has been earnestly studied in view of the above situation, and as a result, in the joining of unsintered ceramic compacts, the ceramic component of the ceramic slurry adhesive used for joining. A ceramic-based slurry adhesive containing 90% by weight or more of the ceramic component composition of the ceramic molded body is used to control the thickness of the bonding layer and the crystal grain size ratio between the ceramic molded body and the bonding layer to achieve excellent bonding. We have found a ceramics joined body composed of ceramics molded bodies having strength.
【０００７】すなわち、本発明の第一は、本質的に同一
組成をもつセラミックス焼結体で形成されたセラミック
ス成形体同士を接合してなるセラミックス接合体におい
て、接合層はセラミックス成形体のセラミックス成分組
成を９０重量％以上含有するセラミックス焼結体であっ
て、その厚さが５０〜５００μｍで、セラミックス成形
体を構成しているセラミックス燒結体の平均結晶粒径と
接合層を形成しているセラミックス焼結体の平均結晶粒
径との比が０．５〜２．０であることを特徴とするセラ
ミックス成形体同士よりなるセラミックス接合体に関す
る。本発明の第二は、セラミックス成形体を構成してい
るセラミックス焼結体がジルコニア質焼結体である請求
項１記載のセラミックス成形体同士よりなるセラミック
ス接合体に関する。本発明の第三は、セラミックス成形
体を構成しているセラミックス焼結体がアルミナ質焼結
体である請求項１記載のセラミックス成形体同士よりな
るセラミックス接合体に関する。本発明の第四は、本質
的に同一のセラミックス成分組成をもつ焼結前のセラミ
ックス成形体同士を、セラミックス系スラリー接着剤を
用いて接着、焼成し、セラミックス成形体同士よりなる
セラミックス接合体を製造する方法において、該セラミ
ックス系スラリー接着剤におけるセラミックス粒子の成
分組成がセラミックス成形体を構成しているセラミック
ス成分組成を９０重量％以上含有し、その平均粒子径が
１．０μｍ以下で、セラミックス系スラリー接着剤の含
水率が５〜２５重量％であり、セラミックス系スラリー
接着剤を希釈しただけで測定した平均粒子径
（ＤＡＶＥ）と式That is, the first aspect of the present invention is a ceramics joined body obtained by joining ceramics shaped bodies formed of ceramics sintered bodies having essentially the same composition, wherein the joining layer is a ceramic component of the ceramics shaped body. A ceramic sintered body containing 90% by weight or more of the composition, having a thickness of 50 to 500 μm, and forming a bonding layer with the average crystal grain size of the ceramic sintered body constituting the ceramic molded body. The present invention relates to a ceramic bonded body composed of ceramic molded bodies, wherein the ratio to the average crystal grain size of the sintered body is 0.5 to 2.0. A second aspect of the present invention relates to a ceramics joined body composed of ceramics compacts according to claim 1, wherein the ceramics sintered compact constituting the ceramics compact is a zirconia sintered compact. A third aspect of the present invention relates to a ceramics joined body composed of ceramics compacts according to claim 1, wherein the ceramics sintered compact that constitutes the ceramics compact is an alumina sintered compact. A fourth aspect of the present invention is to bond a ceramics compact before sintering having essentially the same ceramics component composition with each other by using a ceramic-based slurry adhesive and fire the resulting ceramics compact to form a ceramics joined body. In the method for producing, the composition of the ceramic particles in the ceramic-based slurry adhesive contains 90% by weight or more of the composition of the ceramics forming the ceramic compact, and the average particle size is 1.0 μm or less, The water content of the slurry adhesive is 5 to 25% by weight, and the average particle diameter (D AVE ) and the formula measured only by diluting the ceramic slurry adhesive
【数２】ＤＢＥＴ＝６÷（ρ・ＳＢＥＴ）
（式中、ＳＢＥＴはセラミックス系スラリー接着剤を乾
燥させて窒素吸着法により測定した比表面積であり、ρ
はスラリーを構成する粒子密度である。）を用いて算出
した粒子径（ＤＢＥＴ）との比〔（ＤＡＶＥ）／（Ｄ
ＢＥＴ）〕が３〜１０であるセラミックス系スラリー接
着剤を用いて該焼結前のセラミックス成形体同士を接合
し、１２５０〜１８００℃で焼成することを特徴とする
セラミックス成形体同士よりなるセラミックス接合体の
製造方法に関する。本発明の第五は、請求項４記載の製
造方法において、相対密度９６％以上の焼結体密度にな
る温度で焼結した後、該温度±１００℃の温度でＨＩＰ
処理することを特徴とするセラミックス成形体同士より
なるセラミックス接合体の製造方法に関する。## EQU2 ## D BET = 6 ÷ (ρ · S BET ) (In the formula, S BET is a specific surface area measured by a nitrogen adsorption method after drying the ceramic slurry adhesive, and ρ
Is the density of the particles that make up the slurry. ) Ratio of the calculated particle diameter (D BET) using [(D AVE) / (D
BET )] is 3 to 10, and the ceramic molded bodies before sintering are bonded to each other by using a ceramic-based slurry adhesive, and the ceramic molded bodies are bonded to each other at 1250 to 1800 ° C. A method of manufacturing a body. A fifth aspect of the present invention is the manufacturing method according to claim 4, wherein after the sintering is performed at a temperature at which the relative density is 96% or more, the HIP is performed at a temperature of ± 100 ° C.
The present invention relates to a method for producing a ceramics joined body composed of ceramics shaped bodies, which is characterized by being treated.
【０００８】以下に本発明のセラミックス接合体が充足
すべき各要件について詳細に説明する。The requirements to be satisfied by the ceramic bonded body of the present invention will be described in detail below.
【０００９】（ａ）接合層がセラミックス成形体を構成
するセラミックス焼結体のセラミックス成分組成を９０
重量％以上含有するセラミックス焼結体で構成されてい
る点。本発明においては、接合層を構成するセラミック
ス焼結体の組成がセラミックス成形体を構成するセラミ
ックス焼結体のセラミックス成分組成を９０重量％以上
含有することが必要であり、好ましくは９２重量％以
上、より好ましくは９５重量％以上含有することが望ま
しい。接合層を構成するセラミックス焼結体の組成がセ
ラミックス成形体を構成するセラミックス焼結体のセラ
ミックス成分組成の９０重量％未満の場合には、接合層
に多くの第２相を含有するためセラミックス成形体と接
合層の焼成収縮率の差や熱膨張差が大きくなりセラミッ
クス焼結体よりなるセラミックス成形体と接合層との界
面にクラックの発生や歪みが残存したり、セラミックス
焼結体と接合層との界面の接合性が低下するため強度が
低くなったり繰り返しの応力負荷がかかった場合にセラ
ミックス成形体同士が外れたりするので好ましくない。
なお、「接合層を構成するセラミックス焼結体の組成が
セラミックス成形体を構成するセラミックス焼結体のセ
ラミックス成分組成を９０重量％以上含有する」とは、
たとえば、セラミックス成形体を構成するセラミックス
焼結体が９９．９重量％のアルミナ、０．０５重量％の
ＭｇＯ、その他の金属酸化物０．０５重量％よりなる組
成の場合、接合層は９０（９０≒９９．９×０．９）〜
９９．９重量％のアルミナ、０．０４５（０．０４５≒
０．０５×０．９）〜０．０５重量％のＭｇＯ、残部が
その他の金属酸化物であることを意味している。(A) The bonding layer has a ceramic component composition of the ceramic sintered body constituting the ceramic compact of 90.
It is composed of a ceramics sintered body containing at least wt%. In the present invention, it is necessary that the composition of the ceramics sintered body forming the bonding layer contains 90% by weight or more of the ceramics component composition of the ceramics sintered body forming the ceramics compact, preferably 92% by weight or more. , And more preferably 95% by weight or more. When the composition of the ceramic sintered body forming the bonding layer is less than 90% by weight of the ceramic component composition of the ceramic sintered body forming the ceramic molded body, the bonding layer contains a large amount of the second phase, and thus the ceramic molded body is formed. The difference in the firing shrinkage ratio and the difference in thermal expansion between the body and the bonding layer become large, and cracks and strains remain at the interface between the ceramic molded body made of the ceramic sintered body and the bonding layer, or the ceramic sintered body and the bonding layer. Since the bondability at the interface with and is reduced, the strength is lowered, and the ceramic molded bodies may come off when repeated stress loads are applied, which is not preferable.
In addition, "the composition of the ceramics sintered body forming the bonding layer contains 90% by weight or more of the ceramic component composition of the ceramics sintered body forming the ceramics compact" means
For example, when the ceramic sintered body forming the ceramic compact has a composition of 99.9 wt% alumina, 0.05 wt% MgO, and 0.05 wt% of other metal oxides, the bonding layer is 90 ( 90 ≈ 99.9 x 0.9) ~
99.9 wt% alumina, 0.045 (0.045 ≈
0.05 × 0.9) to 0.05% by weight of MgO, and the balance being other metal oxides.
【００１０】（ｂ）接合層厚さが５０〜５００μｍであ
る点。本発明においては接合層厚さは５０〜５００μｍ
であることが必要であり、とくに１００〜４００μｍで
あることが好ましい。接合層厚さが５０μｍ未満の場合
は、接合強度が低下するので好ましくなく、５００μｍ
を越える場合には接合層厚さが厚くなって接合層強度の
低下が起こるので好ましくない。(B) The thickness of the bonding layer is 50 to 500 μm. In the present invention, the bonding layer thickness is 50 to 500 μm.
It is necessary to be, and it is particularly preferable that the thickness is 100 to 400 μm. When the thickness of the bonding layer is less than 50 μm, the bonding strength decreases, which is not preferable, and the thickness is 500 μm.
If it exceeds, the thickness of the bonding layer becomes thicker and the strength of the bonding layer lowers, which is not preferable.
【００１１】（ｃ）セラミックス成形体を構成している
セラミックス焼結体の平均結晶粒径と接合層を構成して
いるセラミックス焼結体の平均結晶粒径との比が０．５
〜２．０である点。本発明においてはセラミックス成形
体を構成しているセラミックス焼結体の平均結晶粒径と
接合層を構成するセラミックス焼結体の平均結晶粒径と
の比（セラミックス成形体平均結晶粒径／接合層平均結
晶粒径）が０．５〜２．０であることが必要であり、と
くに０．７〜１．５とすることが好ましい。セラミック
ス成形体平均結晶粒径／接合層平均結晶粒径が０．５未
満もしくは２．０を越える場合は、セラミックス成形体
と接合層との接合面における結晶粒径差が大きくなり、
その結果、強度差が大きくなったり、その他の機械的特
性に差が生じて、接合面の耐熱性、耐摩耗性および耐食
性の低下につながるので好ましくない。(C) The ratio of the average crystal grain size of the ceramic sintered body constituting the ceramic compact to the average crystal grain size of the ceramic sintered body constituting the bonding layer is 0.5.
A point of ~ 2.0. In the present invention, the ratio of the average crystal grain size of the ceramic sintered body constituting the ceramic molded body to the average crystal grain size of the ceramic sintered body constituting the bonding layer (ceramic molded body average crystal grain size / bonding layer) The average crystal grain size) is required to be 0.5 to 2.0, and particularly preferably 0.7 to 1.5. If the average crystal grain size of the ceramic compact / bonding layer average crystal grain size is less than 0.5 or exceeds 2.0, the difference in crystal grain size between the ceramic compact and the joint layer becomes large.
As a result, the strength difference becomes large, and other mechanical properties become different, which leads to deterioration in heat resistance, wear resistance, and corrosion resistance of the joint surface, which is not preferable.
【００１２】なお、平均結晶粒径はセラミックス成形体
を構成するセラミックス焼結体およびセラミックス接合
層表面を鏡面まで研磨し、次いで熱エッチングもしくは
化学エッチングを施した後、走査電子顕微鏡で観察して
インターセプト法により１０点測定した平均値とする。
算出式は下記の通りである。The average crystal grain size is obtained by polishing the surfaces of the ceramics sintered body and the ceramics bonding layer constituting the ceramics molded body to a mirror surface and then performing thermal etching or chemical etching, and then observing with a scanning electron microscope. The average value is obtained by measuring 10 points by the method.
The calculation formula is as follows.
【数３】Ｄ＝１．５×Ｌ／ｎ 〔Ｄ：平均結晶粒径（μｍ）、 ｎ：長さＬ当たりの結晶粒子数、 Ｌ：測定長さ（μｍ）〕(3) D = 1.5 × L / n [D: average crystal grain size (μm), n: number of crystal particles per length L, L: measurement length (μm)]
【００１３】本発明におけるジルコニア質焼結体からな
るセラミックス成形体は、ＺｒＯ２とＹ２Ｏ３、ＭｇＯ
およびＣａＯ等の安定化剤との合計量が９９．５重量％
以上のものであり、アルミナ質焼結体からなるセラミッ
クス成形体はアルミナ含有量が９９重量％以上のもので
ある。なお、本発明におけるＺｒＯ２にはＨｆＯ２が含
まれていても良く、ＨｆＯ２量も含めたＺｒＯ２をＺｒ
Ｏ２量とする。The ceramic molded body made of the zirconia-based sintered body according to the present invention is ZrO 2 , Y 2 O 3 , and MgO.
And the total amount of stabilizers such as CaO is 99.5% by weight.
As described above, the ceramic compact made of the alumina sintered body has an alumina content of 99% by weight or more. Note that the ZrO 2 in the present invention may contain HfO 2, a ZrO 2, including the HfO 2 amount Zr
Let O 2 amount.
【００１４】本質的に同一組成をもつセラミックス焼結
体で形成されたセラミックス成形体とは、一方のセラミ
ックス成形体Ａのセラミックス成分組成が他方のセラミ
ックス成形体Ｂのセラミックス成分組成を９０重量％以
上含有していることを意味している。したがって、接合
層を形成しているセラミックス焼結体のセラミックス成
分組成は、セラミックス成形体Ａのセラミックス成分組
成を９０重量％以上含有しているとともに、セラミック
ス成形体Ｂのセラミックス成分組成をも９０重量％以上
含有していることが必要である。なお、本明細書の各実
施例においては、セラミックス成形体Ａとセラミックス
成形体Ｂとは、同一セラミックス成分組成のものを使用
している。A ceramic compact formed of a ceramic sintered body having essentially the same composition means that the ceramic component composition of one ceramic compact A is 90% by weight or more of the ceramic component composition of the other ceramic compact B. It means that it contains. Therefore, the ceramic component composition of the ceramic sintered body forming the bonding layer contains 90% by weight or more of the ceramic component composition of the ceramic molded body A and 90% by weight of the ceramic component composition of the ceramic molded body B. % Or more is required. In each example of the present specification, the ceramic molded body A and the ceramic molded body B have the same ceramic component composition.
【００１５】つぎに本発明のセラミックス接合体の製造
方法について説明する。セラミックス系スラリー接着剤
は、接合するセラミックス成形体を構成するセラミック
ス焼結体のセラミックス成分組成を９０重量％以上含有
する粉体を用い、含水率が５〜２５重量％になるように
水もしくは水と有機溶媒の混合物を添加し、必要に応じ
て所定量の分散剤およびバインダーを添加して粉砕・分
散させる。分散剤としてはたとえばポリカルボン酸アン
モニウム塩、ＰＶＡなどが使用でき、バインダーとして
はたとえばワックスエマルジョン、ＰＶＡ、アクリル樹
脂などが使用できる。Next, a method for manufacturing the ceramic joined body of the present invention will be described. As the ceramic-based slurry adhesive, powder containing 90% by weight or more of the ceramic component composition of the ceramics sintered body forming the joined ceramic compact is used, and water or water is used so that the water content is 5 to 25% by weight. And a mixture of organic solvent and, if necessary, a predetermined amount of a dispersant and a binder are added and pulverized and dispersed. As the dispersant, for example, polycarboxylic acid ammonium salt, PVA and the like can be used, and as the binder, wax emulsion, PVA, acrylic resin and the like can be used.
【００１６】セラミックス系スラリー接着剤の含水率が
５重量％未満の場合は、流動性の高いスラリーが得られ
ず、接合ムラが発生したり、接合層にポアが残存したり
して、強度低下を引き起こすなどの問題が有り、２５重
量％を越える場合は、焼成前の接合層強度が低くなり、
ハンドリング性に欠けたり、焼成後の接合層の組織が粗
密になったり、焼成時にセラミックス成形体と接合層と
の間に大きな熱収縮差が発生し、剥離や焼結したセラミ
ックス成形体と接合層との界面にクラックや歪みが発生
し、接合面の強度低下や耐久性の低下の原因となるので
好ましくない。含水率はより好ましくは５〜２０重量％
である。When the water content of the ceramic-based slurry adhesive is less than 5% by weight, a slurry having a high fluidity cannot be obtained and uneven bonding occurs or pores remain in the bonding layer, resulting in a decrease in strength. If it exceeds 25% by weight, the strength of the bonding layer before firing becomes low,
Lack of handleability, the structure of the bonding layer after firing becomes coarse and dense, or a large difference in heat shrinkage occurs between the ceramic molded body and the bonding layer during firing, resulting in peeling or sintering of the ceramic molded body and bonding layer. It is not preferable because cracks and strains are generated at the interface between and, which causes a decrease in strength and durability of the joint surface. Water content is more preferably 5 to 20% by weight
Is.
【００１７】粉砕・分散したセラミックス系スラリー接
着剤を構成するセラミックス粒子の平均粒子径は１．０
μｍ以下、より好ましくは０．８μｍ以下である（現状
ではセラミックス粒子の下限は約０．０２μｍであ
る）。このセラミックス粒子の平均粒子径はスラリーを
そのまま希釈し、粒度分析を行う前に分散剤添加および
超音波分散して測定した値である。平均粒子径が１．０
μｍを越えると接合部の焼結性が低下するだけでなく、
焼成後の接合部にポアなどの欠陥を多く含有したり、セ
ラミックス部との接合性が低下し、強度低下を招くので
好ましくない。The average particle diameter of the ceramic particles constituting the crushed / dispersed ceramic slurry adhesive is 1.0.
It is less than or equal to μm, more preferably less than or equal to 0.8 μm (currently, the lower limit of the ceramic particles is about 0.02 μm). The average particle size of the ceramic particles is a value measured by diluting the slurry as it is and adding a dispersant and ultrasonically dispersing it before performing particle size analysis. Average particle size is 1.0
If it exceeds μm, not only the sinterability of the joint will deteriorate, but
It is not preferable because the bonded part after firing contains many defects such as pores and the bondability with the ceramic part is deteriorated, resulting in a decrease in strength.
【００１８】また、セラミックス系スラリー接着剤の平
均粒子径が上記の要件を満足しているだけでは充分でな
く、下記で述べるスラリー中の粉体粒子の分散度も重要
である。スラリー中の粉体粒子の分散度は、スラリーを
希釈のみの状態で測定した平均粒子径（ＤＡＶＥ）とス
ラリーを乾燥させて窒素吸着法により測定した比表面積
（ＳＢＥＴ）と粉体密度（ρ）から下式Further, it is not enough that the average particle diameter of the ceramic slurry adhesive satisfies the above requirements, and the degree of dispersion of powder particles in the slurry described below is also important. The dispersity of the powder particles in the slurry is the average particle diameter (D AVE ) measured in a state where the slurry is diluted, the specific surface area (S BET ) and the powder density (S BET ) measured by a nitrogen adsorption method after drying the slurry. from ρ)
【数４】ＤＢＥＴ（μｍ）＝６÷（ρ・ＳＢＥＴ）
を用いて算出した粒子径（ＤＢＥＴ）との比、すなわち
（ＤＡＶＥ）／（ＤＢＥ Ｔ）が３〜１０になるまで粉砕
・分散させることが必要である。好ましい（ＤＡ ＶＥ）
／（ＤＢＥＴ）は４〜８である。スラリーを希釈して測
定した平均粒子径（ＤＡＶＥ）／比表面積から求まる粒
子径（ＤＢＥＴ）が３未満の場合はスラリーの分散性が
良すぎて接合するセラミックス成形体とのなじみが低下
し、焼成前の接合層強度の低下や焼成後の接合強度が低
くなるため好ましくなく、１０を越える場合にはスラリ
ー中の粉体粒子の凝集が強いために焼成後の接合層に多
くのポアを含有したり、焼結したセラミックス成形体と
接合層との界面強度が低下し、その結果、強度低下が起
こるので好ましくない。Equation 4] D BET (μm) = 6 ÷ (ρ · S BET) ratio between the calculated particle diameter (D BET) using, i.e. (D AVE) / (D BE T) is 3 to 10 It is necessary to pulverize and disperse. Preferred (D A VE )
/ (D BET ) is 4 to 8. If the average particle size (D AVE ) measured by diluting the slurry / the particle size (D BET ) obtained from the specific surface area is less than 3, the dispersibility of the slurry is too good, and the compatibility with the ceramic molded body to be bonded decreases. However, it is not preferable because the strength of the bonding layer before firing and the strength of the bonding layer after firing become low, and when it exceeds 10, many pores are formed in the bonding layer after firing due to the strong aggregation of the powder particles in the slurry. The interface strength between the ceramic compact containing or sintered and the bonding layer is reduced, and as a result, the strength is reduced, which is not preferable.
【００１９】接合に当っては、あらかじめセラミックス
成形体の接合面のみに、下記プライマーを塗布し、その
後でセラミックス系スラリー接着剤を適用することが好
ましい。前記プライマーとしては、接合するセラミック
ス成形体組成を９０重量％以上含有する粉体スラリー
（含水率を５０％以上とする。下記の水のみを用いる場
合は含水率１００％に相当している）あるいは水、有機
溶媒、水と有機溶媒の混合溶媒を挙げることができる。
プライマーである水、有機溶媒、水と有機溶媒との混合
溶媒あるいはスラリーの適用をセラミックス成形体全体
に施すと成形体に割れや水、有機溶媒、水と有機溶媒の
混合溶媒あるいはスラリーを適用したことによる作業性
の低下や崩壊が起こるので、プライマーの適用は、接合
面のみとすることが重要である。プライマーの塗布量
は、接合面がわずかに湿る程度とし、プライマー塗布
後、湿った状態を失わないうちに（それが乾かないうち
に）セラミックス系スラリー接着剤を適用する。For joining, it is preferable to apply the following primer in advance only to the joining surface of the ceramic molded body, and then apply the ceramic-based slurry adhesive. As the primer, a powdery slurry containing 90% by weight or more of the composition of the ceramic compact to be bonded (water content is 50% or more. When only the following water is used, it corresponds to 100% water content) or Examples thereof include water, an organic solvent, and a mixed solvent of water and an organic solvent.
When the application of water as a primer, an organic solvent, a mixed solvent of water and an organic solvent or a slurry is applied to the entire ceramic molded body, cracks or water, an organic solvent, or a mixed solvent or slurry of water and an organic solvent is applied to the molded body. It is important that the primer is applied only to the joint surface because the workability may be deteriorated or collapsed. The amount of primer applied is such that the bonding surface is slightly wet, and after applying the primer, the ceramic-based slurry adhesive is applied before the wet state is lost (before it dries).
【００２０】接合面にセラミックス系スラリー接着剤を
適用した後、セラミックス成形体同士を接合する。接合
した成形体は十分に乾燥させた後、１２５０〜１８００
℃、より好ましくは１３００〜１７５０℃で焼成する。After applying the ceramic-based slurry adhesive to the joint surfaces, the ceramic compacts are joined together. The joined molded body is thoroughly dried, and then 1250 to 1800
C., more preferably 1300 to 1750.degree.
【００２１】さらに、焼成後、Ａｒなどの不活性雰囲
気、またはＮ２もしくはＯ２雰囲気下１８００℃以下の
温度でＨＩＰ処理することにより一層接合強度の高いセ
ラミックス接合体が得られる。Furthermore, after firing, HIP treatment is carried out at a temperature of 1800 ° C. or lower in an inert atmosphere such as Ar or in an N 2 or O 2 atmosphere to obtain a ceramics joined body having higher joining strength.
【００２２】[0022]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこれにより何ら限定されるものではない。The present invention will be described below with reference to examples.
The present invention is not limited thereby.
【００２３】実施例１〜５、比較例１〜７
実施例１と５はアルミナ含有量が９９．６重量％、Ｍｇ
Ｏが０．０５重量％含有し、粒子径が０．５μｍ、比表
面積が６ｍ２／ｇからなるアルミナ粉体をポットミルで
溶媒として水を用いて粉砕・分散し、バインダーを添加
し、スプレードライヤー乾燥して成形用粉体を作製し
た。実施例３はアルミナ含有量が９９．９重量％、Ｍｇ
Ｏが０．０５重量％含有し、粒子径が０．１８μｍ、比
表面積が１４ｍ２／ｇからなるアルミナ粉体をポットミ
ルで溶媒として水を用いて粉砕・分散し、バインダーを
添加し、スプレードライヤー乾燥して成形用粉体を作製
した。また、実施例２と４は、加水分解法により作製し
た「Ｙ２Ｏ３を３ｍｏｌ％含有するＹ２Ｏ３とＺｒＯ２
の合計量が９９．８重量％からなるジルコニア粉体」を
上記のアルミナ成形用粉体の作製と同様にして成形用粉
体を作製した。このようにして得られたそれぞれの成形
用粉体を用いて、１ｔｏｎｆ／ｃｍ２でプレス成形し、
５×５×５０ｍｍの棒状セラミックス成形体（実施例１
〜５）を作製した。比較例１〜７のものもこれに準じて
作成した。一方、セラミックス系スラリー接着剤Ｎｏ．
１〜１０を表１に示す粉体を用いて作製し、セラミック
ス成形体と同材質系統のセラミックス系スラリー接着剤
を用いて、同材質の未焼成セラミックス成形体２本を長
手方向に２倍の長さになるように接合して５×５×１０
０ｍｍの棒状体とし、これを焼成し、セラミックス接合
体を作製した。得られたセラミックス接合体の特性を表
２に示す。なお、比較例７のみは、１４５０℃で焼成し
た焼結体よりなるジルコニア成形体をセラミックス系ス
ラリー接着剤の代りに室温硬化型エポキシ樹脂接着剤
（日本チバガイギー製、商品名アラルダイト）を用いて
接合した。このようにして得られたセラミックス接合体
を３×４×４０ｍｍの棒状テストピースに加工し、ＪＩ
Ｓ１６０１に準じて４点曲げにより曲げ強さを各１０本
測定し、平均値を算出した。なお、セラミックス接合体
は、図１に示すように接合層を上スパンの中央部に位置
するようにして測定した。表２にセラミックス接合体の
接合層の平均曲げ強さおよびセラミックス接合体の接合
層の平均曲げ強さとセラミックス成形体の平均曲げ強さ
との比を示す。Examples 1-5, Comparative Examples 1-7 Examples 1 and 5 have an alumina content of 99.6% by weight and Mg
Alumina powder containing 0.05% by weight of O, having a particle size of 0.5 μm and a specific surface area of 6 m 2 / g is pulverized and dispersed in a pot mill using water as a solvent, a binder is added, and a spray dryer is used. It was dried to prepare a molding powder. Example 3 has an alumina content of 99.9% by weight, Mg
Alumina powder containing 0.05% by weight of O, having a particle size of 0.18 μm and a specific surface area of 14 m 2 / g is pulverized and dispersed in a pot mill using water as a solvent, a binder is added, and a spray dryer is used. It was dried to prepare a molding powder. In addition, in Examples 2 and 4, “Y 2 O 3 containing 3 mol% of Y 2 O 3 and ZrO 2 produced by the hydrolysis method were used.
A zirconia powder having a total amount of 99.8% by weight was prepared in the same manner as the above-mentioned alumina molding powder. Each of the molding powders thus obtained was press-molded at 1 tonf / cm 2 ,
5 × 5 × 50 mm rod-shaped ceramic compact (Example 1
~ 5) were produced. The thing of Comparative Examples 1-7 was also created according to this. On the other hand, ceramic-based slurry adhesive No.
1 to 10 were produced using the powders shown in Table 1, and two unfired ceramic compacts of the same material were doubled in the longitudinal direction using a ceramic-based slurry adhesive of the same material system as the ceramic compact. 5 x 5 x 10 by joining them to length
A rod-shaped body of 0 mm was formed and fired to produce a ceramics joined body. Table 2 shows the characteristics of the obtained ceramic bonded body. In addition, only in Comparative Example 7, a zirconia molded body made of a sintered body fired at 1450 ° C. was bonded by using a room temperature curable epoxy resin adhesive (manufactured by Nippon Ciba Geigy, trade name Araldite) instead of the ceramic slurry adhesive. did. The ceramic bonded body thus obtained was processed into a 3 × 4 × 40 mm rod-shaped test piece, and
According to S1601, ten bending strengths were measured by four-point bending, and an average value was calculated. The ceramic bonded body was measured with the bonding layer positioned at the center of the upper span as shown in FIG. Table 2 shows the average bending strength of the bonding layer of the ceramic bonded body and the ratio of the average bending strength of the bonding layer of the ceramic bonded body to the average bending strength of the ceramic molded body.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】上記実施例からも明らかなように本発明の
セラミックス接合体は、接合強度が高いことが明らかで
ある。As is clear from the above examples, it is clear that the ceramic bonded body of the present invention has high bonding strength.
【００２７】[0027]
【発明の効果】本発明のセラミックス接合体は接合強度
が高く、接合していないセラミックス焼結体特性と同等
の耐熱性、耐摩耗性および耐食性を有し、しかも低コス
トで複雑形状品の作製が可能なため産業用機械部品に広
く適用できる。EFFECTS OF THE INVENTION The ceramic bonded body of the present invention has a high bonding strength, has heat resistance, wear resistance and corrosion resistance equivalent to the characteristics of the unsintered ceramic sintered body, and at the same time manufactures a complex shaped product at low cost. It can be widely applied to industrial machine parts.
【図１】セラミックス接合体の曲げ強さをＪＩＳ １６
０１に準じた方法で測定する態様の概略図である。FIG. 1 shows the bending strength of a ceramics bonded body according to JIS 16
It is a schematic diagram of the mode which measures by the method according to 01.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 一茂 大阪府堺市遠里小野町３丁２番24号 株式 会社ニッカトー内 (72)発明者 垣内 千一 大阪府堺市遠里小野町３丁２番24号 株式 会社ニッカトー内 (72)発明者 大西 宏司 大阪府堺市遠里小野町３丁２番24号 株式 会社ニッカトー内 Ｆターム(参考） 4G026 BA03 BA05 BB03 BB05 BC01 BD14 BF04 BF48 BG05 BG22 BH01 4G055 AA08 AC09 BA14 BA21 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kazushige Yamaguchi Osaka Prefecture Sakai City Tozato Onocho 3-22-24 Stock Company Nikkato (72) Inventor Chikazu Kakiuchi Osaka Prefecture Sakai City Tozato Onocho 3-22-24 Stock Company Nikkato (72) Inventor Koji Onishi Osaka Prefecture Sakai City Tozato Onocho 3-22-24 Stock Company Nikkato F term (reference) 4G026 BA03 BA05 BB03 BB05 BC01 BD14 BF04 BF48 BG05 BG22 BH01 4G055 AA08 AC09 BA14 BA21
Claims (5)
結体で形成されたセラミックス成形体同士を接合してな
るセラミックス接合体において、接合層はセラミックス
成形体のセラミックス成分組成を９０重量％以上含有す
るセラミックス焼結体であって、その厚さが５０〜５０
０μｍで、セラミックス成形体を構成しているセラミッ
クス焼結体の平均結晶粒径と接合層を形成しているセラ
ミックス焼結体の平均結晶粒径との比が０．５〜２．０
であることを特徴とするセラミックス成形体同士よりな
るセラミックス接合体。1. A ceramics joined body obtained by joining together ceramics shaped bodies formed of ceramics sintered bodies having essentially the same composition, wherein the joining layer contains 90% by weight or more of the ceramic component composition of the ceramics shaped body. A ceramics sintered body having a thickness of 50 to 50
0 μm, the ratio of the average crystal grain size of the ceramic sintered body forming the ceramic compact to the average crystal grain size of the ceramic sintered body forming the bonding layer is 0.5 to 2.0.
A ceramic bonded body composed of ceramic molded bodies, wherein
ミックス焼結体がジルコニア質焼結体である請求項１記
載のセラミックス成形体同士よりなるセラミックス接合
体。2. A ceramics joined body composed of ceramics compacts according to claim 1, wherein the ceramics sintered compact constituting the ceramics compact is a zirconia sintered compact.
ミックス焼結体がアルミナ質焼結体である請求項１記載
のセラミックス成形体同士よりなるセラミックス接合
体。3. A ceramics joined body composed of ceramics compacts according to claim 1, wherein the ceramics sintered compact constituting the ceramics compact is an alumina sintered compact.
もつ焼結前のセラミックス成形体同士を、セラミックス
系スラリー接着剤を用いて接着、焼成し、セラミックス
成形体同士よりなるセラミックス接合体を製造する方法
において、該セラミックス系スラリー接着剤におけるセ
ラミックス粒子の成分組成がセラミックス成形体を構成
しているセラミックス成分組成を９０重量％以上含有
し、その平均粒子径が１．０μｍ以下で、セラミックス
系スラリー接着剤の含水率が５〜２５重量％であり、セ
ラミックス系スラリー接着剤を希釈しただけで測定した
平均粒子径（ＤＡＶＥ）と式 【数１】ＤＢＥＴ＝６÷（ρ・ＳＢＥＴ） （式中、ＳＢＥＴはセラミックス系スラリー接着剤を乾
燥させて窒素吸着法により測定した比表面積であり、ρ
はスラリーを構成する粒子密度である。）を用いて算出
した粒子径（ＤＢＥＴ）との比〔（ＤＡＶＥ）／（Ｄ
ＢＥＴ）〕が３〜１０であるセラミックス系スラリー接
着剤を用いて該焼結前のセラミックス成形体同士を接合
し、１２５０〜１８００℃で焼成することを特徴とする
セラミックス成形体同士よりなるセラミックス接合体の
製造方法。4. A ceramics joined body having essentially the same ceramics component composition is adhered and fired with each other by using a ceramic-based slurry adhesive to produce a ceramics joined body composed of the ceramics shaped bodies. In the method, the composition of the ceramic particles in the ceramic-based slurry adhesive contains 90% by weight or more of the ceramic component composition that constitutes the ceramic compact, and the average particle size is 1.0 μm or less. The water content of the agent is 5 to 25% by weight, and the average particle diameter (D AVE ) measured by simply diluting the ceramic-based slurry adhesive and the formula [Formula 1] D BET = 6 ÷ (ρ · S BET ) ( In the formula, SBET is the specific surface area measured by the nitrogen adsorption method after drying the ceramic slurry adhesive, and ρ
Is the density of the particles that make up the slurry. ) Ratio of the calculated particle diameter (D BET) using [(D AVE) / (D
BET )] is 3 to 10, and the ceramic molded bodies before sintering are bonded to each other by using a ceramic-based slurry adhesive, and the ceramic molded bodies are bonded to each other at 1250 to 1800 ° C. Body manufacturing method.
度９６％以上の焼結体密度になる温度で焼結した後、該
温度±１００℃の温度でＨＩＰ処理することを特徴とす
るセラミックス成形体同士よりなるセラミックス接合体
の製造方法。5. The manufacturing method according to claim 4, wherein after the sintering is performed at a temperature at which the relative density is 96% or more, the HIP process is performed at the temperature of ± 100 ° C. A method for manufacturing a ceramics joined body comprising ceramics molded bodies.
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|---|---|---|---|
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|---|---|
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2001
- 2001-10-23 JP JP2001324449A patent/JP3943366B2/en not_active Expired - Lifetime
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