JPH11263671A - Firing tool material - Google Patents
Firing tool materialInfo
- Publication number
- JPH11263671A JPH11263671A JP10062774A JP6277498A JPH11263671A JP H11263671 A JPH11263671 A JP H11263671A JP 10062774 A JP10062774 A JP 10062774A JP 6277498 A JP6277498 A JP 6277498A JP H11263671 A JPH11263671 A JP H11263671A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- dense
- intermediate layer
- porosity
- fired
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、電子部品などの
機能性セラミックスなどの焼成、粉末の熱処理などに用
いられる焼成用道具材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a firing tool used for firing functional ceramics such as electronic parts and the like, and for heat treating powders.
【０００２】[0002]
【従来の技術】焼成用道具材は、電子部品などの機能性
セラミックスの焼成工程で、道具材中の成分と被焼成物
とが反応するのを防止するために、或いは被焼成物に含
まれる成分が道具材の中に吸収されたりすることを防ぐ
ため、緻密質の道具材を使用したり又は道具材の表面に
反応性の低い被膜層を設けることが行われている。2. Description of the Related Art A firing tool material is included in a firing process of a functional ceramic such as an electronic component in order to prevent a component in the tool material from reacting with a firing object or included in the firing object. In order to prevent the components from being absorbed into the tool material, a dense tool material is used, or a low-reactive coating layer is provided on the surface of the tool material.
【０００３】前者の緻密質の道具材としては、気孔率の
小さいＡｌ2 Ｏ3やＭｇＯの磁器、石英ガラスが被焼成
物の種類や使用温度によって選択して使用されている。
かかる緻密質の道具材は一般に難反応性であるが、しか
しこうした低気孔率品は耐熱衝撃性や耐熱性がわるくこ
の点で問題があった。As the former dense tool material, Al 2 O 3 or MgO porcelain having a small porosity or quartz glass is selected and used depending on the type of the material to be fired and the operating temperature.
Such dense tool materials are generally difficult to react with, but such low porosity products suffer from poor thermal shock resistance and heat resistance.
【０００４】即ち、焼成条件に制約があって、焼成スピ
ードや最高温度での制約があった。又耐熱衝撃性が劣る
ために炉内で激しく割れて炉内を汚染する事故を起こす
といった場合もあった。さらに、これらは一般に高価で
もあった。That is, there are restrictions on firing conditions, and there are restrictions on firing speed and maximum temperature. In addition, due to poor thermal shock resistance, there was a case where an accident occurred in which the inside of the furnace was contaminated by severe cracking in the furnace. Furthermore, they were also generally expensive.
【０００５】後者の基材表面に低気孔率の被膜層を設け
た道具材は、ポーラスなＡｌ2 Ｏ3−ＳｉＯ2 質やＳｉ
Ｃ質の基板に被膜層を形成するものである。その形成方
法は成形又は焼成した基材に、被膜層成分のスラリー化
したものを流し込み或いは吹き付けたのち焼成して焼き
付けをする方法、同じようにして得た基材に他の接着性
のある材料を介して被膜層を固定する方法、溶射法で予
め焼成した基材に被膜層を形成すると同時に被膜を基材
に焼付ける方法などであるが、この溶射法が比較的安価
で量産可能な製造方法とされている。[0005] The latter, a tool material having a low porosity coating layer provided on the surface of a substrate, is made of porous Al 2 O 3 —SiO 2 or Si.
A film layer is formed on a C-type substrate. The formation method is a method in which a slurry of the coating layer component is poured or sprayed onto a molded or fired base material and then baked and baked, and another adhesive material is obtained on the base material obtained in the same manner. A method of fixing a coating layer via a method, a method of forming a coating layer on a base material pre-fired by a thermal spraying method, and a method of baking the coating on the base material at the same time. The way has been.
【０００６】基材に溶射膜を設けた焼成用道具材に関す
る特許としては、ＣａＯが４〜３１重量％の安定化Ｚｒ
Ｏ2 を、Ａｌ2 Ｏ3 含有量が８５重量％以上のＡｌ2 Ｏ
3 、ＳｉＯ2 質基材に溶射するもの（特公平３−７７６
５２号）、ＣａＯが４〜１５重量％の安定化ＺｒＯ
2 を、Ａｌ2 Ｏ3 系基材の基材側から表面に向かって次
第にＣａＯ量が少ない安定化ＺｒＯ2 を溶射するもの
（特公平４−５６８号）、Ａｌ2 Ｏ3 系基材とＺｒＯ2
溶射層の間に、Ａｌ2 Ｏ3 溶射層や焼結被膜層を介在さ
せることにより、基材とＺｒＯ2 層の熱膨張差を緩和し
たり或いはこれらの付着性を向上せるもの（特公平４−
２１３３０、特開平５−１７８６７３、特開平２−２２
９７７６）などである。A patent relating to a firing tool material provided with a sprayed film on a substrate includes a stabilized Zr containing 4-31% by weight of CaO.
The O 2, Al 2 O 3 content is more than 85 wt% Al 2 O
3. What sprays onto SiO 2 substrate (Japanese Patent Publication No. 3-776)
No. 52), stabilized ZrO containing 4 to 15% by weight of CaO
2, which spraying gradually CaO amount is less stabilized ZrO 2 toward the surface from the substrate side of the Al 2 O 3 based substrate (Kokoku No. 4-568), and Al 2 O 3 base material ZrO Two
By interposing an Al 2 O 3 sprayed layer or a sintered coating layer between the sprayed layers, the thermal expansion difference between the base material and the ZrO 2 layer is reduced or the adhesion between them is improved (Japanese Patent Publication No. −
21330, JP-A-5-178673, JP-A-2-22
9776).
【０００７】溶射法は比較的緻密質な被膜が得られる点
で優れており、また被膜自体耐摩耗性が高い。さらに、
被焼成物中の成分（Ｐｂ，Ｂｉ，Ｎａ，Ｋなど）が被膜
層を通過して基材に浸透し、基材が劣化して割れ、反り
といった不具合を生じることが防止できて良好である。
被膜の材質は、コストと被焼成物との反応性及び耐用性
を考慮してＡｌ2 Ｏ3 質又はＺｒＯ2 質とすることが一
般的である。特に、耐反応性が重要な場合はＺｒＯ2 質
が選択される。[0007] The thermal spraying method is excellent in that a relatively dense coating can be obtained, and the coating itself has high wear resistance. further,
Components (Pb, Bi, Na, K, etc.) in the material to be fired pass through the coating layer and penetrate into the base material, thereby preventing the base material from being deteriorated and causing problems such as cracking and warpage, which is favorable. .
The material of the coating is generally made of Al 2 O 3 or ZrO 2 in consideration of cost, reactivity with the material to be fired, and durability. In particular, when reaction resistance is important, ZrO 2 is selected.
【０００８】しかしながら、溶射被膜を形成した道具材
においても、一部のソフトフェライトや誘電体セラミッ
クス、特殊粉末などの熱処理にあっては、被焼成物中の
成分の一部が道具材被膜側に吸収されて、被焼成物本来
の特性が得られないといった問題の起こることがあっ
た。[0008] However, even in the case of a tool material on which a sprayed coating is formed, in the heat treatment of some soft ferrites, dielectric ceramics, special powders, etc., some of the components in the material to be fired are on the tool material film side. There is a case where a problem such as absorption of the material to be baked cannot be obtained due to absorption.
【０００９】このために、このような微量成分の移動に
よって被焼成物の特性が左右され易い用途では、これま
では溶射被膜を有する道具材より緻密質の磁器などの焼
成用道具材が、上記ような問題を抱えながらも使用され
ていた。こうした被焼成物成分の移動は、焼成用道具材
の被膜層の気孔率が高いことに起因するものと考えられ
る。このように、溶射法で緻密な被膜を形成した焼成用
道具材にあっても、前述のような被焼成物では被膜の緻
密性は必ずしも十分ではなかった。[0009] For this reason, in applications where the characteristics of the object to be fired are easily influenced by the movement of such trace components, hitherto, firing tools such as porcelain, which are denser than tools having a sprayed coating, have been used. It was used while having such problems. It is considered that such movement of the components to be fired is caused by the high porosity of the coating layer of the firing tool material. As described above, even in a firing tool material in which a dense coating is formed by the thermal spraying method, the denseness of the coating is not necessarily sufficient for the above-described fired object.
【００１０】即ち、溶射法でも水プラズマ溶射法で成形
されたＡｌ2 Ｏ3 やＺｒＯ2 の溶射膜は、その気孔率が
１０〜２０％であり、微量の成分のずれが特性に影響が
及ぼす恐れのあるような場合は使用することが難しかっ
た。また、ガスプラズマ法で形成されたＡｌ2 Ｏ3 やＺ
ｒＯ2 の溶射膜は、気孔率が７％以下で水プラズマ法に
比べて緻密な被膜が得られ、被焼成物からの成分の移動
や浸透、被膜成分との反応は少なくなるが、反面でこの
場合は被膜が緻密であるためにその耐剥離性が不十分と
なるといった問題があった。That is, even in the thermal spraying method, the sprayed film of Al 2 O 3 or ZrO 2 formed by the water plasma spraying method has a porosity of 10 to 20%, and a small amount of component deviation affects the characteristics. It was difficult to use when there was fear. Further, Al 2 O 3 or Z formed by a gas plasma method may be used.
The sprayed film of rO 2 has a porosity of 7% or less, and a denser film can be obtained as compared with the water plasma method, and the movement and penetration of components from the material to be fired and the reaction with the film components are reduced. In this case, there is a problem that the peel resistance is insufficient because the coating is dense.
【００１１】さらに、被焼成物が反応性の高い物質であ
る場合は、被焼成物質が溶射被膜と反応して溶射被膜が
体積変化し、これが原因で被膜の膨れ、反りといった問
題を生じ被膜が剥離するおそれがあった。また、ガスプ
ラズマ法などを用いて気孔率が７％以下の緻密質の溶射
膜を形成した場合は、被膜が剥離するといった問題があ
った。Further, when the material to be fired is a substance having a high reactivity, the material to be fired reacts with the sprayed film to change the volume of the sprayed film. There was a risk of peeling. Further, when a dense sprayed film having a porosity of 7% or less is formed by using a gas plasma method or the like, there is a problem that the coating is peeled off.
【００１２】[0012]
【発明が解決しようとする課題】この発明は、耐熱性の
基材表面に中間層として気孔率の比較的大きな中間層を
形成し、その上に表面層としてこの中間層の気孔率より
も小さい気孔率の緻密層の被膜を形成するもので、これ
によって被焼成物の焼成に当たって被焼成物の成分が道
具材の中に吸収されて被焼成物に特性異常が生じること
を少なくし、さらに中間層を設けることによって使用時
の加熱で被膜に発生する応力を緩和して表面の緻密層の
剥離が少なく耐用性の高い焼成用道具材を得ようとする
ものである。According to the present invention, an intermediate layer having a relatively high porosity is formed as an intermediate layer on the surface of a heat-resistant substrate, and a porosity lower than that of the intermediate layer is formed as a surface layer on the intermediate layer. This is to form a dense porosity film with a porosity, which reduces the occurrence of characteristic abnormalities in the fired object due to the absorption of the components of the fired object into the tool material during firing of the fired object. By providing the layer, the stress generated in the coating film due to heating during use is relieved, and the separation of the dense layer on the surface is less likely to occur, so that a firing tool material having high durability can be obtained.
【００１３】[0013]
【発明を解決するための手段】この発明は、耐熱性基材
表面に溶射被膜を形成した道具材であって、基材の表面
に気孔率が１２％以上の中間層と、さらにその表面に気
孔率が７％以下の緻密層を形成したことを特徴とする焼
成用道具材（請求項１）、基材主成分がＡｌ2Ｏ3 −Ｓ
ｉＯ2 質又はＳｉＣ質で、中間層及び緻密層の主成分が
Ａｌ2 Ｏ3 、未安定ＺｒＯ2 、ＣａＯ部分安定化ＺｒＯ
2 、Ｙ2 Ｏ3 部分安定化ＺｒＯ2 及びＣａＺｒＯ3 の中
の一種又は二種以上であることを特徴とする請求項１記
載の焼成用道具材（請求項２）及び中間層が水プラズマ
溶射法で成形され、さらにその上にガスプラズマ溶射法
で緻密層が形成されていることを特徴とする請求項１記
載の焼成用道具材（請求項３）である。SUMMARY OF THE INVENTION The present invention relates to a tool material having a heat-resistant base material having a sprayed coating formed on the surface of the base material. A firing tool material (Claim 1), wherein a dense layer having a porosity of 7% or less is formed, wherein the main component of the base material is Al 2 O 3 —S.
iO 2 or SiC, the main components of the intermediate layer and the dense layer are Al 2 O 3 , unstable ZrO 2 , and CaO partially stabilized ZrO
2, Y 2 O 3 partially calcining tool material according to claim 1, wherein the stabilizing is ZrO 2 and CaZrO one or two or more of the 3 (claim 2) and the intermediate layer is water plasma spraying The firing tool material according to claim 1, wherein the firing tool material is formed by a gas plasma spraying method, and a dense layer is formed thereon by a gas plasma spraying method.
【００１４】[0014]
【発明の実施の態様】この発明の焼成用道具材は、基材
の表面に溶射法で気孔率の比較的大きな中間層を形成
し、その上にこの中間層の気孔率よりも小さい気孔率の
緻密層を溶射法で形成した被膜層を有するものである。
この発明の道具材の基材は、基材主成分がＡｌ2 Ｏ3 −
ＳｉＯ2 質又はＳｉＣ質である。Ａｌ2 Ｏ3 −ＳｉＯ2
質の場合は、Ａｌ2 Ｏ3 が９０％以上のものが好まし
く、またＳｉＣ質の場合はＳｉＣが９８％以上のものが
好ましい。基材は予めブラスト処理などをして粗面化処
理しておくのが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The firing tool according to the present invention has an intermediate layer having a relatively large porosity formed on the surface of a substrate by thermal spraying, and a porosity smaller than the porosity of the intermediate layer formed thereon. Having a coating layer formed by spraying the dense layer.
The base material of the tool material of the present invention is such that the main component of the base material is Al 2 O 3 −
It is SiO 2 or SiC. Al 2 O 3 —SiO 2
In the case of quality, the content of Al 2 O 3 is preferably 90% or more, and in the case of quality of SiC, the content of SiC is preferably 98% or more. It is preferable that the base material is previously subjected to a blast treatment or the like to perform a roughening treatment.
【００１５】基材表面に形成される中間層及び表面緻密
層はいずれも溶射被膜とするが、その主成分はＡｌ2 Ｏ
3 、未安定ＺｒＯ2 、ＣａＯ部分安定化ＺｒＯ2 、Ｙ2
Ｏ3部分安定化ＺｒＯ2 及びＣａＺｒＯ3 の中の一種又
は二種以上が好ましい。被膜の中間層の気孔率は１２％
以上とし、また表面緻密層の気孔率は７％以下として、
気孔率の大きな中間層の上に緻密層の表面層を形成した
ものとする。The intermediate layer and the dense surface layer formed on the surface of the substrate are both thermal spray coatings, and the main component thereof is Al 2 O.
3 , unstable ZrO 2 , CaO partially stabilized ZrO 2 , Y 2
One or more of O 3 partially stabilized ZrO 2 and CaZrO 3 are preferred. The porosity of the middle layer of the coating is 12%
And the porosity of the dense surface layer is 7% or less,
It is assumed that a surface layer of a dense layer is formed on an intermediate layer having a large porosity.
【００１６】この発明において中間層と表面緻密層の気
孔率の違い重要である。即ち、最終的に得られた道具材
表面に気孔率の小さい緻密層を有するために、被焼成物
の成分が道具材に吸収されることが少なく、これによっ
て焼成物に特性異常を生じ難くして良好な被焼成物とす
ることが可能となる。また、この表面緻密層と基材の中
間には上記緻密層よりも気孔率が大きくポーラスな溶射
層を中間層として介在したので、被焼成物処理時に道具
材の被膜に発生する応力を緩和して表面緻密層の剥離を
防ぐことが可能となるものである。In the present invention, the difference in porosity between the intermediate layer and the dense surface layer is important. That is, since the finally obtained tool material has a dense layer having a small porosity on the surface of the tool material, the components of the object to be fired are less likely to be absorbed by the tool material. It is possible to obtain a good object to be fired. In addition, since a porous sprayed layer having a higher porosity than the dense layer is interposed between the dense surface layer and the base material as an intermediate layer, the stress generated in the tool material coating during the processing of the material to be fired is reduced. Thus, it is possible to prevent peeling of the dense surface layer.
【００１７】表面緻密層の気孔率は上記の目的達成のた
めには７％以下とすることが必要である。更に好ましく
は、５％以下である。これによって焼成された製品の特
性劣化とともに製品のばらつきも防止出来て、従来のＡ
ｌ2 Ｏ3 磁器などの緻密質道具材でないと使用できなか
った特殊粉末の熱処理にも十分に使用出来るようにな
る。表面緻密層の気孔率が７％を超えると表面の緻密さ
が不足して上記目的を十分に達成することができない。The porosity of the dense surface layer needs to be 7% or less in order to achieve the above object. More preferably, it is 5% or less. As a result, it is possible to prevent the deterioration of the properties of the fired product and the variation of the product.
It can be used satisfactorily for heat treatment of special powders that could not be used unless it was a dense tool such as l 2 O 3 porcelain. If the porosity of the dense surface layer exceeds 7%, the above-mentioned object cannot be sufficiently achieved due to insufficient surface denseness.
【００１８】また、上記の中間層は気孔率が１２％以上
の溶射被膜とすることによって、加熱時に熱膨張率の差
異によって生ずる熱応力を分散、吸収して被膜の剥離を
最小限に押さえることが出来る。The thermal spray coating having a porosity of 12% or more in the intermediate layer disperses and absorbs thermal stress caused by a difference in thermal expansion coefficient during heating to minimize peeling of the coating. Can be done.
【００１９】特に、水プラズマ溶射法を用いて溶射した
組織は、気孔率が１０〜１８％程度の適度な空隙をもっ
て溶融した粒子が複雑に絡み合った組織となっており、
被膜の耐剥離性に非常に有効に作用する。しかし、中間
層のみであると被焼成物の焼成に際してこの被膜の中に
被焼成物成分が進入し被膜成分と反応して体積変化を起
こして被膜が膨れ上がり剥離する場合があるが、この発
明ではこの上に緻密層を溶射層で形成するので、こうし
たことによる被膜の剥離は大幅に回避出来るようにな
る。In particular, the structure sprayed by the water plasma spraying method is a structure in which particles fused with moderate voids having a porosity of about 10 to 18% are intricately intertwined.
It has a very effective effect on the peel resistance of the coating. However, when only the intermediate layer is used, when the object to be fired is fired, the component of the object to be fired enters the film and reacts with the component of the film to cause a change in volume, whereby the film may swell and peel off. Then, since a dense layer is formed thereon by a thermal spraying layer, peeling of the coating film due to such a situation can be largely avoided.
【００２０】さらに、中間溶射層の表面は凹凸が激し
く、そのためにこの表面に表面緻密層を形成すると、中
間層と表面緻密層の界面の面積が大きく、中間溶射層と
表面緻密層がアンカー効果で強固に結合され、基材に直
接緻密層を形成した場合と比べて表面緻密層の耐剥離性
はさらに向上する。Further, the surface of the intermediate sprayed layer is highly uneven, and if a dense surface layer is formed on this surface, the area of the interface between the intermediate layer and the dense surface layer is large, and the intermediate spray layer and the dense surface layer are anchored. And the peel resistance of the dense surface layer is further improved as compared with the case where the dense layer is directly formed on the substrate.
【００２１】表面緻密層の形成方法としては、ガスプラ
ズマ溶射法がコスト、量産性などから好ましい。表面層
をさらに緻密にするにはＣＶＤ法を用いてもよい。中間
層と表面緻密層の厚さは、被膜層の材質、使用条件によ
って任意に選択すればよいが、被膜層の厚さを厚くすれ
ばする程、熱膨張により発生する応力が大きくなるの
で、あまり厚くしないのが好ましい。例えば、中間層を
水プラズマ溶射膜とし、表面緻密層をガスプラズマ溶射
膜とする場合、中間層は１００μｍ、表面緻密層は５０
μｍまで薄くすることが可能であるが、基材の形状、表
面状態によっては被膜の厚さがばらつくこともあるの
で、これらを考慮すると中間層の厚さは１００〜３００
μｍ、表面緻密層は５０〜２００μｍが好ましいが、被
焼成物の種類によってはこの範囲を外れる厚さとするこ
ともある。As a method for forming the dense surface layer, a gas plasma spraying method is preferable from the viewpoint of cost, mass productivity and the like. In order to further densify the surface layer, a CVD method may be used. The thickness of the intermediate layer and the surface dense layer may be arbitrarily selected depending on the material of the coating layer and the conditions of use, but as the thickness of the coating layer increases, the stress generated by thermal expansion increases. It is preferred not to be too thick. For example, when the intermediate layer is a water plasma sprayed film and the dense surface layer is a gas plasma sprayed film, the intermediate layer is 100 μm and the dense surface layer is 50 μm.
Although it is possible to reduce the thickness of the intermediate layer to 100 μm, the thickness of the coating may vary depending on the shape and surface condition of the base material.
The thickness of the surface dense layer is preferably 50 to 200 μm, but the thickness may be outside this range depending on the type of the object to be fired.
【００２２】[0022]
【実施例】（実施例１）Ａｌ2 Ｏ3 含有量が９０重量％
のＡｌ2 Ｏ3 −ＳｉＯ2 質で、形状が１５０ｍｍ×１５
０ｍｍ×５０ｍｍ（外形）のトレー状基材の表面を、Ａ
ｌ2 Ｏ3 砥粒（２２０）ブラストを用いて処理した後、
水プラズマ溶射法で厚さ１５０μｍのＡｌ2 Ｏ3 溶射膜
（Ａｌ2 Ｏ3 純度９９％）の中間層を形成した。さら
に、この表面にガスプラズマ溶射法を用いて厚さ１５０
μｍのＡｌ2 Ｏ3 溶射膜（Ａｌ2Ｏ3 純度９９％）を形
成した（表面緻密層）。EXAMPLES (Example 1) The content of Al 2 O 3 is 90% by weight.
Al 2 O 3 —SiO 2 , 150 mm × 15
The surface of the tray-shaped substrate of 0 mm × 50 mm (outer shape) is
After treatment using l 2 O 3 abrasive (220) blast,
An intermediate layer of an Al 2 O 3 sprayed film (Al 2 O 3 purity: 99%) having a thickness of 150 μm was formed by water plasma spraying. Further, the surface is coated with a thickness of 150 using a gas plasma spraying method.
A μm Al 2 O 3 sprayed film (Al 2 O 3 purity: 99%) was formed (surface dense layer).
【００２３】ここに得られたトレーの一部を切断して研
磨し断面を顕微鏡で観察し、画像解析により被膜の気孔
率を算出したところ、中間層が１３％、表面緻密層が６
％であった。この表面層の断面顕微鏡写真を図１に示し
た。A part of the obtained tray was cut and polished, the cross section was observed with a microscope, and the porosity of the coating was calculated by image analysis. The porosity of the intermediate layer was 13%, and that of the surface dense layer was 6%.
%Met. FIG. 1 shows a cross-sectional micrograph of this surface layer.
【００２４】また、トレーの耐熱衝撃性を評価するため
の試験として、３００℃に保持した電気炉内にＡｌ2 Ｏ
3 粉末を充填した状態でトレーを挿入し、炉内温度が設
定温度に復帰した後６０分後にトレーを炉内より取出し
室温で冷却した。このものについてトレーの割れ、被膜
の剥離などの不具合が無いか観察した。不具合が発生し
た場合は、その時の温度をＮＧ温度とした。不具合が生
じなかった場合は、設定温度を５０℃上げて同様の操作
を行ない、この操作を繰り返し行ったところ、設定温度
が６００℃のときにトレー底部にクラックが発生した。
またＡｌ2 Ｏ3被膜はクラックの発生部分でやや剥離が
みられたものの大きな剥離には至らなかった。As a test for evaluating the thermal shock resistance of the tray, Al 2 O was placed in an electric furnace maintained at 300 ° C.
The tray was inserted in a state where the powder was filled, and the tray was taken out of the furnace and cooled at room temperature 60 minutes after the furnace temperature returned to the set temperature. This was observed for defects such as cracking of the tray and peeling of the coating. When a failure occurred, the temperature at that time was regarded as the NG temperature. When no trouble occurred, the same operation was performed by increasing the set temperature by 50 ° C., and this operation was repeated. When the set temperature was 600 ° C., cracks occurred at the bottom of the tray.
Further, the Al 2 O 3 film was slightly peeled off at the portion where cracks occurred, but did not lead to large peeling.
【００２５】更に、このものの被膜と被焼成物との反応
性を評価するため、ＴｉＯ2 、ＢａＯ、ＰｂＯをそれぞ
れ主成分とする誘電体原料をプレス成形して作製したテ
ストピースを用いて焼成試験を行った。即ち、上記トレ
ーから切出した円板（φ５０ｍｍ×１０ｍｍ）の上で図
２に示すようにして上記テストピースを焼成し、焼成前
後の道具材表面（図２のＡ面）を蛍光Ｘ線で半定量分析
を行い焼成前後での成分量を比較した。この実験では成
分量の差（以下、成分変化量とい。）が大きい程被焼成
体の成分が吸収し易いと言える。Further, in order to evaluate the reactivity between the coating film and the material to be fired, a firing test was performed using a test piece produced by press-molding a dielectric material containing TiO 2 , BaO, and PbO as main components. Was done. That is, the test piece was fired on a disk (φ50 mm × 10 mm) cut out from the tray as shown in FIG. 2, and the surface of the tool material before and after firing (A surface in FIG. 2) was half-cut with fluorescent X-rays. Quantitative analysis was performed to compare the amounts of components before and after firing. In this experiment, it can be said that the larger the difference between the component amounts (hereinafter, referred to as component change amount), the more easily the components of the fired body are absorbed.
【００２６】表１には、被膜のない基材（Ａｌ2 Ｏ3 −
ＳｉＯ2 質、Ａｌ2 Ｏ3 質９０％）表面の成分変化量を
１００としたときの相対量で表した。焼成温度はＴｉＯ
2 、ＢａＯが１４００℃、ＰｂＯの場合は１２００℃で
行った。その結果、それぞれの成分変化量は、ＴｉＯ2
が９、ＢａＯが３８、ＰｂＯが１１であった。Table 1 shows that the base material without the coating (Al 2 O 3-
(SiO 2 quality, Al 2 O 3 quality 90%) The relative amount is expressed assuming that the component change amount on the surface is 100. The firing temperature is TiO
2 , BaO was performed at 1400 ° C., and PbO was performed at 1200 ° C. As a result, each component change amount is TiO 2
Was 9, BaO was 38 and PbO was 11.
【００２７】実際の熱処理条件に近づけた状態での耐用
性を評価する試験として、上記トレーに誘電体の主成分
であるＴｉＯ2 、ＢａＣＯ3 、ＰｂＯ、ＺｒＯ2 の場合
の割合が１：１：１：１（モル比）になるように秤量
し、ボールミルで湿式混合し乾燥した後上記のトレーに
充填し、これにふたをした状態で電気炉を用いてサイク
ル加熱を行った。サイクル加熱は３００℃〜１３００℃
の間で、サヤを３段重ねた状態で行い、５回毎にサヤの
外観を観察し割れ、被膜の剥離等の不具合が無いかを確
認した。昇降の速度は２００℃〜４００℃／時間で行っ
た。その結果、３５回目で１個、４５回目で２個のサヤ
の底部に亀裂が発生した。以上の実施例１については表
１にまとめて示した。As a test for evaluating the durability under conditions close to the actual heat treatment conditions, the ratio of the case where TiO 2 , BaCO 3 , PbO, and ZrO 2 , which are the main components of the dielectric material, are 1: 1: The mixture was weighed so as to be 1: 1 (molar ratio), wet-mixed in a ball mill, dried, filled in the tray, and cycle-heated using an electric furnace while the tray was covered. Cycle heating is 300 ℃ ～ 1300 ℃
During the period, the sheaths were stacked in three stages, and the appearance of the sheaths was observed every five times, and it was confirmed whether there were any defects such as cracks and peeling of the coating. The elevating speed was 200 to 400 ° C./hour. As a result, a crack was generated at the bottom of one sheath at the 35th and two at the 45th. Example 1 described above is summarized in Table 1.
【００２８】（実施例２〜４）実施例２〜６は、基材を
Ａｌ2 Ｏ3 −ＳｉＯ2 質とし、中間層を水プラズマ層溶
射、表面緻密層をガスプラズマ溶射で形成し、それぞれ
の表面被膜層の材質を表１に記載したように変化させた
事例である。いずれも急熱急冷試験、サイクル試験とも
にＡｌ2 Ｏ3 磁器より高かった。また、反応試験の結果
もＡｌ2 Ｏ3 磁器とほぼ同レベルの結果であった。特
に、ＣａＺｒＯ3 を用いたものは反応性、耐久性ともに
非常に良好であった。(Examples 2 to 4) In Examples 2 to 6, the base material was made of Al 2 O 3 —SiO 2 , the intermediate layer was formed by water plasma layer spraying, and the dense surface layer was formed by gas plasma spraying. This is an example in which the material of the surface coating layer was changed as described in Table 1. In both cases, both the rapid heat quenching test and the cycle test were higher than the Al 2 O 3 porcelain. The results of the reaction test were almost the same as those of the Al 2 O 3 porcelain. In particular, those using CaZrO 3 were very good in both reactivity and durability.
【００２９】（実施例５及び６）実施例５及び６は、基
材をＳｉＣ質とし、中間層を水プラズマ層溶射、表面緻
密層をガスプラズマ溶射で形成し、それぞれの材質を表
１に記載したように変化させた事例である。これらは耐
熱衝撃性はＡｌ2 Ｏ3 −ＳｉＯ2 質基材を用いたものよ
り良好であった。サイクル加熱試験ではいずれも基材／
中間層界面では３５〜４５回の試験で剥離が生じた。(Examples 5 and 6) In Examples 5 and 6, the base material was made of SiC, the intermediate layer was formed by spraying a water plasma layer, and the dense surface layer was formed by gas plasma spraying. This is an example in which it is changed as described. These had better thermal shock resistance than those using the Al 2 O 3 —SiO 2 base material. In the cycle heating test,
At the interface of the intermediate layer, peeling occurred after 35 to 45 tests.
【００３０】[0030]
【表１】 [Table 1]
【００３１】（比較例１〜５）これに対して、比較例の
方はいずれも満足すべき状態でない。即ち、比較例１は
Ａｌ2 Ｏ3 磁器で反応性は良好であるが、急熱急冷試験
では４００℃で割れ、サイクル加熱試験でも１つのサヤ
は３回の試験で割れ、その割れ方も激しく、真二つ割れ
た。比較例２は、Ａｌ2 Ｏ3 −ＳｉＯ2 質の道具材で急
熱急冷には強いが、反応性が激しくサイクル試験でも反
応に起因すると考えられるクラックが内面底面から発生
していた。(Comparative Examples 1 to 5) In contrast, none of the comparative examples is in a satisfactory state. That is, Comparative Example 1 had good reactivity with Al 2 O 3 porcelain, but cracked at 400 ° C. in the rapid heating and quenching test, and one sheath was cracked in the cycle heating test in three tests, and the cracking was also severe. , Two were split. Comparative Example 2 was an Al 2 O 3 —SiO 2 tool, which was resistant to rapid heating and quenching, but had high reactivity and cracks, which were considered to be caused by the reaction even in the cycle test, were generated from the inner bottom surface.
【００３２】比較例３は、Ａｌ2 Ｏ3 −ＳｉＯ2 の基材
にＡｌ2 Ｏ3 を水プラズマ溶射したものであるが、これ
は表面層を溶射しない比較例２と比較すると反応性は改
善されているが、Ａｌ2 Ｏ3 磁器と比較すると不十分で
ある。さらに、サイクル加熱での耐用性は長くなってい
るが、これによる不具合の状況は比較例２とよく似て、
溶射膜を通過した成分が基材と反応し組織変化が起こっ
ていた。また、被膜も細かいひび割れが内面前面にわた
って発生していた。これは被焼成物成分の影響でＡｌ2
Ｏ3 被膜を収縮したためと考えられた。[0032] Comparative Example 3 is an Al 2 O 3 to the base material of Al 2 O 3 -SiO 2 is obtained by water plasma spraying, which is reactive with the comparison with Comparative Example 2 without spraying the surface layer is improved However, it is insufficient when compared with Al 2 O 3 porcelain. Furthermore, although the durability in the cycle heating is longer, the situation of the trouble due to this is very similar to Comparative Example 2,
The components that passed through the sprayed film reacted with the base material, causing a structural change. In addition, the coating also had fine cracks on the inner front surface. This is because Al 2
It is considered that the O 3 film shrank.
【００３３】比較例４は、Ａｌ2 Ｏ3 −ＳｉＯ2 の基材
にＣａＯ部分安定化ジルコニアを水プラズマ溶射したも
のであるが、これはＢａＯ、ＰｂＯに対する反応性は向
上したが、それも磁器に比べると不十分である。サイク
ル加熱では回数を重ねるうちに被膜が膨れ上がり剥離が
生じた。比較例５は、Ａｌ2 Ｏ3 −ＳｉＯ2 の基材にＡ
ｌ2 Ｏ3 をガスプラズマ溶射したものであるが、反応性
は磁器質に近いレベルに達したが、サイクル加熱試験で
は使用初期に剥離が発生した。Comparative Example 4 was obtained by spraying CaO partially stabilized zirconia on a substrate of Al 2 O 3 —SiO 2 by water plasma spraying. The reactivity with BaO and PbO was improved. Is insufficient compared to In the cycle heating, the coating swelled and peeled as the number of cycles increased. Comparative Example 5, A to a substrate Al 2 O 3 -SiO 2
Although l 2 O 3 was obtained by gas plasma spraying, the reactivity reached a level close to that of porcelain, but peeling occurred in the early stage of use in the cycle heating test.
【００３４】[0034]
【表２】 [Table 2]
【００３５】なお、本発明の変形例としては、表面層に
被焼成物成分を混合して溶射した焼成用道具材としても
よい。このようにすると被焼成物の組成と表面層の組成
が近づき被焼成物と被膜間での成分の移動が起こりにく
くなり被焼成物の特性面で有効となる。また、基材は、
耐熱性に優れたものであるならば金属であってもよい。As a modification of the present invention, a firing tool material obtained by mixing and spraying a component to be fired on a surface layer may be used. In this way, the composition of the object to be fired and the composition of the surface layer are close to each other, and the movement of components between the object to be fired and the coating film is less likely to occur, which is effective in the characteristics of the object to be fired. The base material is
Metals may be used as long as they are excellent in heat resistance.
【００３６】[0036]
【発明の効果】以上の通り、この発明によると表面に緻
密な被膜層を有するために、焼成用道具材に被焼成物の
成分が吸収されることが少なくて被焼成物の特性異常が
生じ難い。また、被膜自体の変質劣化による剥離がな
く、しかも中間層に設けられたポーラスな溶射層が熱処
理時に被膜に発生する応力を緩和するため表面が緻密層
でありながら剥離し難く耐用性の高い道具材とすること
が出来る。As described above, according to the present invention, since a dense coating layer is formed on the surface, the components of the object to be fired are hardly absorbed by the firing tool material, resulting in an abnormal characteristic of the object to be fired. hard. In addition, there is no peeling due to deterioration of the coating itself, and the porous sprayed layer provided in the intermediate layer relieves stress generated in the coating during heat treatment. Material.
【図１】本発明の一実施例になる焼成用道具材の基材表
面に形成されたＡｌ2 Ｏ3 の水プラズマ溶射層と、その
表面に形成されたＡｌ2 Ｏ3 のガスプラズマ溶射層の状
態を示すセラミック材料の組織を示す写真である。FIG. 1 is a water plasma sprayed layer of Al 2 O 3 formed on a substrate surface of a firing tool material according to an embodiment of the present invention, and a gas plasma sprayed layer of Al 2 O 3 formed on the surface thereof 5 is a photograph showing the structure of a ceramic material showing the state of FIG.
【図２】この発明の焼成用道具材と被焼成物との反応性
を試験するための試験方法を示す説明図。FIG. 2 is an explanatory view showing a test method for testing the reactivity between the firing tool material of the present invention and an object to be fired.
Claims (3)
具材であって、基材の表面に気孔率が１２％以上の中間
層と、さらにその表面に気孔率が７％以下の緻密層を形
成したことを特徴とする焼成用道具材。1. A tool material comprising a heat-resistant base material having a sprayed coating formed on a surface thereof, wherein the intermediate layer has a porosity of 12% or more on the surface of the base material and a dense layer having a porosity of 7% or less on the surface. A firing tool material having a layer formed thereon.
ＳｉＣ質で、中間層及び緻密層の主成分がＡｌ2 Ｏ3 、
未安定ＺｒＯ2 、ＣａＯ部分安定化ＺｒＯ2、Ｙ2 Ｏ3
部分安定化ＺｒＯ2 及びＣａＺｒＯ3 の中の一種又は二
種以上であることを特徴とする請求項１記載の焼成用道
具材。2. The main component of the base material is Al 2 O 3 —SiO 2 or SiC, and the main components of the intermediate layer and the dense layer are Al 2 O 3 ,
Unstable ZrO 2 , CaO partially stabilized ZrO 2 , Y 2 O 3
Calcining tool material according to claim 1, characterized in that partially stabilized ZrO 2 and CaZrO one or two or more of the three.
らにその上にガスプラズマ溶射法で緻密層が形成されて
いることを特徴とする請求項１記載の焼成用道具材。3. The firing tool according to claim 1, wherein the intermediate layer is formed by a water plasma spraying method, and a dense layer is further formed thereon by a gas plasma spraying method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06277498A JP3653388B2 (en) | 1998-03-13 | 1998-03-13 | Baking tool material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06277498A JP3653388B2 (en) | 1998-03-13 | 1998-03-13 | Baking tool material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11263671A true JPH11263671A (en) | 1999-09-28 |
| JP3653388B2 JP3653388B2 (en) | 2005-05-25 |
Family
ID=13210068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06277498A Expired - Fee Related JP3653388B2 (en) | 1998-03-13 | 1998-03-13 | Baking tool material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3653388B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278685A (en) * | 2000-01-24 | 2001-10-10 | Toshiba Ceramics Co Ltd | Silicon carbide material and its manufacturing method |
| JP2002060287A (en) * | 2000-06-07 | 2002-02-26 | Toshiba Ceramics Co Ltd | Firing vessel |
| JP2002356387A (en) * | 2001-03-30 | 2002-12-13 | Toshiba Ceramics Co Ltd | Plasma proof member |
| JP2004262712A (en) * | 2003-02-28 | 2004-09-24 | Toshiba Ceramics Co Ltd | Burning tool |
| JP2007045641A (en) * | 2005-08-08 | 2007-02-22 | Toshiba Ceramics Co Ltd | Container for firing |
| KR100787077B1 (en) | 2004-12-28 | 2007-12-21 | 니뽄 가이시 가부시키가이샤 | Firing jig for electronic element |
| JP2013199011A (en) * | 2012-03-23 | 2013-10-03 | Yoshikawa Kogyo Co Ltd | Wear resistant and heat resistant fiber-reinforced composite material and method for producing the same |
| EP2821382A4 (en) * | 2012-02-27 | 2015-11-04 | Ngk Insulators Ltd | Heat-insulating member and engine combustion chamber structure |
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1998
- 1998-03-13 JP JP06277498A patent/JP3653388B2/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278685A (en) * | 2000-01-24 | 2001-10-10 | Toshiba Ceramics Co Ltd | Silicon carbide material and its manufacturing method |
| JP4743973B2 (en) * | 2000-01-24 | 2011-08-10 | コバレントマテリアル株式会社 | Silicon carbide members for firing electronic components |
| JP2002060287A (en) * | 2000-06-07 | 2002-02-26 | Toshiba Ceramics Co Ltd | Firing vessel |
| JP2002356387A (en) * | 2001-03-30 | 2002-12-13 | Toshiba Ceramics Co Ltd | Plasma proof member |
| JP2004262712A (en) * | 2003-02-28 | 2004-09-24 | Toshiba Ceramics Co Ltd | Burning tool |
| KR100787077B1 (en) | 2004-12-28 | 2007-12-21 | 니뽄 가이시 가부시키가이샤 | Firing jig for electronic element |
| CN100406413C (en) * | 2004-12-28 | 2008-07-30 | 日本碍子株式会社 | Clamp for electron component |
| JP2007045641A (en) * | 2005-08-08 | 2007-02-22 | Toshiba Ceramics Co Ltd | Container for firing |
| JP4713981B2 (en) * | 2005-08-08 | 2011-06-29 | コバレントマテリアル株式会社 | Ceramic electronic component firing container |
| EP2821382A4 (en) * | 2012-02-27 | 2015-11-04 | Ngk Insulators Ltd | Heat-insulating member and engine combustion chamber structure |
| JP2013199011A (en) * | 2012-03-23 | 2013-10-03 | Yoshikawa Kogyo Co Ltd | Wear resistant and heat resistant fiber-reinforced composite material and method for producing the same |
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