JP4459468B2 - Heat-resistant member for firing furnace and method for producing the same - Google Patents
Heat-resistant member for firing furnace and method for producing the same Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明は、膨潤性鉱物を主成分とする被膜を形成した焼成炉用耐熱性部材及びその製造方法に関する。
【0002】
【従来の技術】
電子部品の焼成炉等においては、壁体からの発塵が極力小さいことが望まれる。一方で、焼成炉に用いられる断熱材としては、耐熱性が高く低熱容量であることから、セラミックス質繊維を用いたものが採用されている。しかし、セラミックス質繊維を用いた断熱材は、発塵が比較的多いという問題があり、電子部品等のクリーン性が求められる製造環境には利用し難い。
【0003】
発塵を防止するための技術として、断熱材の表面に被膜を形成し、粉落ちを防止する技術がある。この技術に関しては、例えば特開昭57−13514号や特開平1−219083号各公報に記載されている技術が公知である。
【0004】
これらの公報に記載されている技術は、セラミックス材料表面にガラス質の被膜、またはその前駆体を形成するものである。しかし、本発明者らの知見によれば、これらの技術はガラス化のための熱処理が必要であり、また熱衝撃性が十分ではなく、更に発塵の抑制が必ずしも十分でない等の問題があり、要求される性能を満たすものではない。
【0005】
また、特公平4−24316号公報には、厚さが数百オングストローム以下になるまで劈開させた平均アスペクト比が1000以上の合成マイカ微細箔片を含有した塗料が開示されている。しかし、この塗料はマイカ粉を細かく劈開させてあるので、被膜の形成後にマイカ粉が粉落ちし易く、発塵が多いという問題がある。
【0006】
【発明が解決しようとする課題】
本発明はこのような状況に鑑みてなされたものであり、より高い耐熱性を有し、かつ表面からの発塵がより抑制された焼成炉用耐熱性部材を提供すること、並びに前記耐熱性部材を製造するための簡便な方法を提供することを目的とする。
【0007】
【課題を解決するための手段】
上記目的を達成するために、本発明は、耐熱性基材上に、水により膨潤する膨潤性鉱物をコーティング液全量の3〜10重量%、及び無機バインダーを前記膨潤性鉱物に対し固形分比で5〜45重量%含有するコーティング液を塗布し、乾燥してなる被膜が形成されていることを特徴とする焼成炉用耐熱性部材(以下、単に「耐熱性部材」という)を提供する。
【0008】
また、本発明は、耐熱性基材上に、水により膨潤する膨潤性鉱物をコーティング液全量の3〜10重量%、及び無機バインダーを前記膨潤性鉱物に対し固形分比で5〜45重量%含有するコーティング液を塗布し、前記コーティング液を乾燥させることを特徴とする耐熱性部材の製造方法を提供する。
【0009】
【発明の実施の形態】
本発明の耐熱性部材は、基材上に、水により膨潤する膨潤性鉱物を主成分として含有する被膜(以下、「膨潤性鉱物被膜」という)が成膜されている。本発明において、この膨潤性鉱物とは、層状の結晶構造を有し、さらに層間に陽イオンが介在しており、この陽イオンに水が水和することで、層間方向(層の厚み方向)に膨潤する性質を備えた鉱物のことをいう。
【0010】
具体的には、膨潤性鉱物として、合成あるいは天然のスメクタイト粘土鉱物群から選ばれたもの(この中にはベントナイトも含まれる)、あるいは層間にナトリウム等のアルカリイオンをインターカレーションさせ膨潤性を付与したマイカ(膨潤性マイカ)が挙げられる。スメクタイトやベントナイトは、特殊処理することなく、それ自身が層間にアルカリイオンを介在させ、膨潤性を有している。一方、膨潤性マイカは、タルクとケイフッ化アルカリとの混合物を加熱処理し、固相反応させることで得られる。これらの中でも、膨潤性マイカが粒子径が大きく、また個々の粒子が特にきれいな層状に並びやすく、発明の目的を最もよく実現できるので好ましい。
【0011】
膨潤性鉱物被膜を形成するには、この膨潤性鉱物を水に分散させたコーティング液を被処理部材に塗布し、乾燥させればよい。それにより、膨潤性鉱物が層状をなしたフィルム状の被膜が成膜される。このとき、膨潤鉱物の結晶層間に介在する陽イオンに水が水和して膨潤する。そして膨潤することで、劈開し易くなり、コーティング液中で薄い鱗片状となる。特に、鱗片状の膨潤性鉱物は、層構造を有し、膨潤した状態において、層状に配向しやすく、鱗状の被膜構造が形成されやすい。
【0012】
また、鱗片状膨潤性鉱物は、膨潤後の平均粒子径が0.5〜10μmとなることが好ましく、この範囲にあると、コーティング液を塗布し乾燥させたときに鱗状に粒子が並びやすく、特に良好な膨潤性鉱物被膜が形成される。図1は実施例1で得られた膨潤性鉱物被膜の表面を撮影した電子顕微鏡写真であるが、鱗状に粒子が並んだ被膜が形成されているのがわかる。
【0013】
コーティング液における膨潤性鉱物の含有量は3〜10重量%の割合が好ましい。膨潤性鉱物量が3重量%より少ないと、コーティング液の粘度が低く、コーティングした際にレベリングや密着性において好ましくない。10重量%より多いと、粘度が高すぎてコーティング液の塗布性が悪くなり、均質な膨潤性鉱物被膜が形成し難くなる。
【0014】
また、コーティング液には無機バインダーを添加することが好ましく、それにより膨潤性鉱物の粒子同士の結合がより強固になり、発塵性をより低減させることができるようになる。無機バインダーとしては、コロイダルシリカ、アルミナゾル、アルカリ珪酸塩(珪酸リチウム、水ガラス、珪酸ソーダ)から選ばれた一種または複数種類が利用できる。これらの中でも、コロイダルシリカが最も高い効果が得られ好ましい。無機バインダーの添加量は、固形分換算で膨潤性鉱物に対して5〜45重量%の割合が好ましく、5重量%より少ないと無機バインダーを添加した効果が十分に発現せず、45重量%より多いと乾燥時に割れが発生しやすくなる。
【0015】
コーティング液の塗布量としては、基材の表面に0.05〜2g/cm2の面密度で塗布することが好ましく、これにより良好な膜質の膨潤性鉱物被膜が得られる。また、コーティング液を塗布し、乾燥した後に、適当な加熱処理、例えば100℃程度の温度下に数時間放置してもよく、これにより膨潤性鉱物被膜の安定化を図ることができる。
【0016】
このようにして得られる膨潤性鉱物被膜は、後述される実施例にも示すように、800℃程度までの耐熱性に加えて、優れた気密性(ガスバリア性)、低発塵性、平滑性を有している。また、成膜時や熱衝撃を受けた際に亀裂が生じたりすることがない。これは、膨潤性鉱物が、アルカリイオンが層間に介在した層構造を有するため、ミクロ的に見て、層間で微妙なズレが起こり易く、更に鱗状になった各粒子間でも微妙なズレが発生し易いので、問題となるような亀裂が発生する前にその力が吸収緩和されるからであると推察される。このことは、被膜として考えた場合に熱衝撃を受けることで、発塵し易くなったり、剥がれやすくなったりする問題を抑える点で有意なものとなる。また、無機質であるので、加熱時に発煙や臭いを発する問題がない。
【0017】
これに対し、層状構造を有する鉱物でも、水により膨潤しないもの(例えば非膨潤性マイカ)を用いた場合は、薄膜化がうまくゆかず、耐熱性、低発塵性、平滑性のいずれの点でも劣ったものとなる。
【0018】
尚、本発明において、膨潤性鉱物被膜が成膜される基材としては耐熱性基材、例えば断熱材等が適当であり、耐熱性をはじめとして、上記の優れた緒特性を付与することができる。特に、低発塵性を備えることから、電子部品の焼成炉等に好適である。
【0019】
【実施例】
以下、実施例を挙げて本発明を更に説明する。
【0020】
(実施例1)
水に膨潤性合成マイカ(平均粒径5μm)を7重量%混合し、良く攪拌した。この液100重量部に、コロイダルシリカを1.2重量%配合し、コーティング液を得た。尚、膨潤性合成マイカは、タルクとケイフッ化アルカリを混合し、蓋付き坩堝中で850℃、1時間の加熱処理を施すことで得た。
【0021】
他方で、下記の原料を混合してスラリーを得た。
アルミナ繊維 100重量部
コロイダルシリカ 8重量部(固形分換算)
有機バインダ(ポリアクリルアミド) 1重量部(固形分換算)
【0022】
上記スラリーから吸引脱水成形法により厚さが50mm、幅が300mm、長さが300mmの成形体を得、それを乾燥させて、密度が0.25g/cm3の断熱板を得た。
【0023】
そして、上記断熱板の表面に、上記コーティング液を0.25g/cm2の面密度で塗布し、110℃にて6時間自然乾燥させた。こうして、厚さ約100μmの被膜で被覆された繊維質断熱材を得た。この被膜の表面状態を走査型電子顕微鏡(SEM)で撮影した写真を図1に示す。
【0024】
(実施例2)
実施例1と同一の膨潤性合成マイカ(平均粒径5μm)を7重量%の割合で配合した液(7%液)を得た。この液100重量部に珪酸リチウムを1.2重量部配合し、コーティング液を得た。そして、他は実施例1と同様にして被膜を備えた断熱材を得た。
【0025】
(比較例1)
原料として非膨潤合成マイカ(平均粒径5μm)を水に7重量%の割合で配合し、この液100重量部に対してコロイダルシリカを固形分換算で1.2重量部配合し、コーティング液を得た。そして、他は実施例1と同様にして被膜を備えた断熱材を得た。
【0026】
(比較例2)
原料として水にEガラス粉(平均粒径7μm)を7重量%の割合で混合し、その液100重量部にコロイダルシリカを1.2重量部の割合で配合してコーティング液を得た。そして、他は実施例1と同様にして被膜を備えた断熱材を得た。
【0027】
上記各実施例及び比較例で得られた断熱材について、熱衝撃性及び気密性を評価した。尚、熱衝撃性の評価は、600℃に保持された電気炉に断熱材を投入し、30分保持した後に炉から取り出し、それを強制空冷により冷却した後に被膜表面の状態を観察し、裂等の発生がないものを「○」、亀裂等が発生しているが致命的でないものを「△」、使用に耐えないレベルの亀裂等が発生しているものを「×」、として評価した。また、気密性の評価は、JISR2115に準拠した通気率を計測し、透気度が10-13m2より小さいのものを「○」、10-13m2〜10-11m2のものを「△」、10-11m2より大きいものを「×」とした。それぞれの結果を表1に示す。
【0028】
【表1】
【0029】
表1に示すように、本発明に従う各実施例の断熱材は両評価ともに優れた結果が得られている。しかし、比較例1の断熱材では被膜の緻密性が低いため、全ての試験において不満足なものとなっている。また、比較例2は、粉落ちが多く、また緻密性がかなり低いので、実用にならない程度のものであった。
【0030】
(比較例3)
また、比較例2の断熱材を更に800℃、1時間の熱処理を施して被膜のガラス化処理を施して同様の熱衝撃性と気密性の評価を行った。結果を表1に併記したが、加熱処理を施してガラス化させることで、比較例2の断熱材でも気密性が改善されることが分かる。しかし、ガラス化させた被膜は、基材との熱膨張差の違いに起因する亀裂の発生が問題となる。
【0031】
また、上記特性上の問題に加えて、熱処理に要するコストアップも問題となり、更にはガラス化のための熱処理温度に耐え得る基材にしか適用できないという制約もある。
【0032】
【発明の効果】
以上説明したように、本発明によれば、耐熱性に優れ、表面からの発塵がより抑制された耐熱性部材を提供することができる。
【図面の簡単な説明】
【図1】実施例1で得られた耐熱性部材の表面状態を写した電子顕微鏡写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a heat-resistant member for a firing furnace in which a coating containing a swellable mineral as a main component is formed and a method for producing the same.
[0002]
[Prior art]
In a firing furnace or the like for electronic parts, it is desired that dust generation from the wall is as small as possible. On the other hand, as a heat insulating material used for a baking furnace, since heat resistance is high and it is a low heat capacity, what uses ceramic fiber is adopted. However, the heat insulating material using the ceramic fiber has a problem that the dust generation is relatively large, and is difficult to use in a manufacturing environment in which cleanliness such as electronic parts is required.
[0003]
As a technique for preventing dust generation, there is a technique for preventing powder falling by forming a film on the surface of the heat insulating material. With regard to this technique, for example, techniques described in Japanese Patent Application Laid-Open Nos. 57-13514 and 1-219083 are known.
[0004]
The techniques described in these publications form a glassy film or a precursor thereof on the surface of a ceramic material. However, according to the knowledge of the present inventors, these techniques have problems such as requiring heat treatment for vitrification, insufficient thermal shock resistance, and insufficient suppression of dust generation. Does not meet the required performance.
[0005]
Japanese Patent Publication No. 4-24316 discloses a paint containing a synthetic mica fine foil piece having an average aspect ratio of 1000 or more, which has been cleaved until the thickness becomes several hundred angstroms or less. However, since the mica powder is cleaved finely in this paint, there is a problem that the mica powder tends to fall off after the coating is formed, and there is much dust generation.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of such a situation, and provides a heat-resistant member for a firing furnace having higher heat resistance and further suppressing dust generation from the surface, and the heat resistance. It aims at providing the simple method for manufacturing a member.
[0007]
[Means for Solving the Problems]
To achieve the above object, the present invention is, on the resistance to heat resistant substrate, 3-10 wt% of the coating solution the total amount of swelling minerals that swell with water, and solids to said swelling mineral inorganic binder A heat-resistant member for a firing furnace (hereinafter simply referred to as “heat-resistant member”) is provided , in which a coating film formed by applying a coating liquid containing 5 to 45% by weight and drying is formed. .
[0008]
Further, the present invention has, on anti-heat resistant substrate, 3-10 wt% of the coating solution the total amount of swelling minerals that swell with water, and the inorganic binder in the solid content ratio relative to the swelling mineral 5-45 weight A method for producing a heat-resistant member is provided, in which a coating solution containing 1% is applied and the coating solution is dried.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the heat-resistant member of the present invention, a film containing a swellable mineral swollen by water as a main component (hereinafter referred to as “swellable mineral film”) is formed on a substrate. In the present invention, the swellable mineral has a layered crystal structure, and cations are interposed between layers, and water is hydrated by the cations, so that the direction of the layers (thickness direction of the layers). Minerals with the property of swelling.
[0010]
Specifically, the swellable mineral is selected from a group of synthetic or natural smectite clay minerals (this includes bentonite), or alkali ions such as sodium are intercalated between layers to swell. Examples thereof include mica (swelling mica). Smectite and bentonite have swelling properties by interposing alkali ions between layers without special treatment. On the other hand, swellable mica is obtained by heat-treating a mixture of talc and alkali silicofluoride to cause a solid phase reaction. Among these, swellable mica is preferable because it has a large particle diameter, and individual particles are easily arranged in a particularly beautiful layer, and the object of the invention can be best realized.
[0011]
In order to form a swellable mineral film, a coating liquid in which this swellable mineral is dispersed in water may be applied to a member to be treated and dried. Thereby, a film-like film in which the swellable mineral forms a layer is formed. At this time, water hydrates and swells to cations interposed between the crystal layers of the swollen mineral. And it becomes easy to cleave by swelling, and it becomes thin scale-like in a coating liquid. In particular, scaly swellable minerals have a layer structure, and in a swollen state, are easily oriented in layers, and a scaly film structure is easily formed.
[0012]
In addition, the scale-like swellable mineral preferably has an average particle diameter after swelling of 0.5 to 10 μm, and if it is in this range, the particles are easily arranged in a scale shape when the coating liquid is applied and dried, A particularly good swellable mineral coating is formed. FIG. 1 is an electron micrograph of the surface of the swellable mineral film obtained in Example 1, and it can be seen that a film in which particles are arranged in a scale shape is formed.
[0013]
The content of the swellable mineral in the coating solution is preferably 3 to 10% by weight. When the amount of swellable mineral is less than 3% by weight, the viscosity of the coating solution is low, which is not preferable in leveling and adhesion when coated. When the amount is more than 10% by weight, the viscosity is too high, the coating property of the coating liquid is deteriorated, and it becomes difficult to form a homogeneous swellable mineral film.
[0014]
Further, it is preferable to add an inorganic binder to the coating liquid, whereby the bond between the particles of the swellable mineral becomes stronger and the dust generation property can be further reduced. As the inorganic binder, one or more kinds selected from colloidal silica, alumina sol, and alkali silicate (lithium silicate, water glass, sodium silicate) can be used. Among these, colloidal silica is preferable because the highest effect is obtained. The added amount of the inorganic binder is preferably 5 to 45% by weight with respect to the swellable mineral in terms of solid content, and if it is less than 5% by weight, the effect of adding the inorganic binder is not sufficiently exhibited, and more than 45% by weight. If it is too much, cracks are likely to occur during drying.
[0015]
The coating amount of the coating liquid is preferably applied to the surface of the substrate with an areal density of 0.05 to 2 g / cm 2 , whereby a swellable mineral film with good film quality is obtained. In addition, after the coating liquid is applied and dried, it may be allowed to stand for several hours under a suitable heat treatment, for example, at a temperature of about 100 ° C., thereby stabilizing the swellable mineral film.
[0016]
The swellable mineral coating thus obtained has excellent airtightness (gas barrier properties), low dust generation, and smoothness in addition to heat resistance up to about 800 ° C., as shown in Examples described later. have. In addition, no cracks occur during film formation or when subjected to thermal shock. This is because the swellable mineral has a layer structure in which alkali ions are interposed between the layers, so that it is easy for microscopic displacement to occur between the microscopically, and there is also subtle displacement between each of the scaly particles. This is presumed to be because the force is absorbed and relaxed before the problematic crack occurs. This is significant in that it suppresses the problem that when it is considered as a coating film, it is subject to thermal shock and is likely to generate dust or easily peel off. Moreover, since it is inorganic, there is no problem of generating smoke or odor during heating.
[0017]
In contrast, when minerals with a layered structure that do not swell with water (for example, non-swellable mica) are used, thinning is not successful, and any of heat resistance, low dust generation, and smoothness But it is inferior.
[0018]
In the present invention, as the substrate on which the swellable mineral film is formed, a heat-resistant substrate such as a heat insulating material is suitable, and the above excellent characteristics can be imparted including heat resistance. it can. In particular, since it has low dust generation properties, it is suitable for a firing furnace for electronic parts.
[0019]
【Example】
Hereinafter, the present invention will be further described with reference to examples.
[0020]
Example 1
7% by weight of swellable synthetic mica (average particle size 5 μm) was mixed with water and stirred well. To 100 parts by weight of this liquid, 1.2% by weight of colloidal silica was blended to obtain a coating liquid. In addition, the swellable synthetic mica was obtained by mixing talc and alkali fluorosilicate and performing heat treatment at 850 ° C. for 1 hour in a crucible with a lid.
[0021]
On the other hand, the following raw materials were mixed to obtain a slurry.
Alumina fiber 100 parts by weight Colloidal silica 8 parts by weight (solid content conversion)
1 part by weight of organic binder (polyacrylamide) (solid content conversion)
[0022]
A molded body having a thickness of 50 mm, a width of 300 mm, and a length of 300 mm was obtained from the slurry by a suction dehydration molding method, and dried to obtain a heat insulating plate having a density of 0.25 g / cm 3 .
[0023]
And the said coating liquid was apply | coated to the surface of the said heat insulation board with the surface density of 0.25 g / cm < 2 >, and it naturally dried at 110 degreeC for 6 hours. Thus, a fibrous heat insulating material coated with a coating having a thickness of about 100 μm was obtained. The photograph which image | photographed the surface state of this film with the scanning electron microscope (SEM) is shown in FIG.
[0024]
(Example 2)
A liquid (7% liquid) containing 7% by weight of the same swellable synthetic mica (average particle size 5 μm) as in Example 1 was obtained. 1.2 parts by weight of lithium silicate was added to 100 parts by weight of this liquid to obtain a coating liquid. And others obtained the heat insulating material provided with the film like Example 1.
[0025]
(Comparative Example 1)
Non-swelling synthetic mica (average particle size 5 μm) was blended in water at a ratio of 7% by weight as a raw material, and 1.2 parts by weight of colloidal silica in terms of solid content was blended with 100 parts by weight of this liquid to obtain a coating liquid. . And others obtained the heat insulating material provided with the film like Example 1.
[0026]
(Comparative Example 2)
As a raw material, E glass powder (average particle size 7 μm) was mixed with water at a ratio of 7% by weight, and 100 parts by weight of the liquid was mixed with 1.2 parts by weight of colloidal silica to obtain a coating liquid. And others obtained the heat insulating material provided with the film like Example 1.
[0027]
About the heat insulating material obtained by said each Example and comparative example, thermal shock property and airtightness were evaluated. The thermal shock resistance was evaluated by placing a heat insulating material in an electric furnace maintained at 600 ° C., holding it for 30 minutes, removing it from the furnace, cooling it by forced air cooling, and observing the state of the coating surface, Evaluated as “○” for those with no cracks, “△” for cracks but not fatal, and “x” for cracks that could not be used. . In addition, the airtightness is evaluated by measuring the air permeability in accordance with JISR2115. If the air permeability is less than 10 −13 m 2 , “○” is used, and 10 −13 m 2 to 10 −11 m 2 . “Δ” and those larger than 10 −11 m 2 were defined as “x”. The results are shown in Table 1.
[0028]
[Table 1]
[0029]
As shown in Table 1, the heat insulating material of each example according to the present invention has excellent results in both evaluations. However, the heat insulating material of Comparative Example 1 is unsatisfactory in all tests because of the low density of the coating. Further, Comparative Example 2 was not practical because it had a lot of powder falling and the density was quite low.
[0030]
(Comparative Example 3)
Further, the heat insulating material of Comparative Example 2 was further subjected to a heat treatment at 800 ° C. for 1 hour to vitrify the coating, and the same thermal shock property and airtightness were evaluated. Although the result was written together in Table 1, it turns out that airtightness is improved also with the heat insulating material of the comparative example 2 by heat-processing and making it vitrify. However, the vitrified film has a problem of cracking due to a difference in thermal expansion difference from the substrate.
[0031]
Further, in addition to the above-mentioned problems in the characteristics, the cost increase required for the heat treatment becomes a problem, and there is a restriction that it can be applied only to a substrate that can withstand the heat treatment temperature for vitrification.
[0032]
【The invention's effect】
As described above, according to the present invention, it is possible to provide a heat-resistant member that is excellent in heat resistance and in which dust generation from the surface is further suppressed.
[Brief description of the drawings]
1 is an electron micrograph showing the surface state of a heat-resistant member obtained in Example 1. FIG.
Claims (7)
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| JP2001090370A JP4459468B2 (en) | 2001-03-27 | 2001-03-27 | Heat-resistant member for firing furnace and method for producing the same |
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| JP2001090370A JP4459468B2 (en) | 2001-03-27 | 2001-03-27 | Heat-resistant member for firing furnace and method for producing the same |
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| JP2009012195A (en) * | 2007-06-29 | 2009-01-22 | Nippon Sheet Glass Co Ltd | Heat-resistant cushioning sheet material for hot press and hot press molding method |
| JP5956721B2 (en) * | 2010-04-01 | 2016-07-27 | 日鉄住金鋼板株式会社 | Painted metal plate and architectural panel |
| JP2016128368A (en) * | 2015-01-09 | 2016-07-14 | 日立造船株式会社 | Refractory coating method and refractory |
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