JPH01119587A - Low-thermal expansion refractories - Google Patents
Low-thermal expansion refractoriesInfo
- Publication number
- JPH01119587A JPH01119587A JP27539787A JP27539787A JPH01119587A JP H01119587 A JPH01119587 A JP H01119587A JP 27539787 A JP27539787 A JP 27539787A JP 27539787 A JP27539787 A JP 27539787A JP H01119587 A JPH01119587 A JP H01119587A
- Authority
- JP
- Japan
- Prior art keywords
- coating layer
- thermal expansion
- particles
- refractories
- thickness
- 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
- 239000011819 refractory material Substances 0.000 title abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 28
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 21
- 238000011109 contamination Methods 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 13
- 229910052681 coesite Inorganic materials 0.000 abstract description 12
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 12
- 229910052682 stishovite Inorganic materials 0.000 abstract description 12
- 229910052905 tridymite Inorganic materials 0.000 abstract description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008020 evaporation Effects 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 239000002585 base Substances 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 10
- 230000035939 shock Effects 0.000 description 10
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- -1 high speed steel Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000889 permalloy Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、低熱膨張性耐火物に係り、特にＬｉ、Ｏ・Ａ
ＪＺ、Ｏ，・ｎＳｉＯ２（ｎ＝２〜９）質低熱膨張性耐
火物の低熱膨張性（耐熱衝撃性）を損なうことなく、高
温使用時におけるＬｉ２０成分の基材からの蒸発を抑え
たＬｉ２０・Ａｕ、Ｏ，・ｎＳｉＯ２（ｎ＝２〜９）買
低熱膨張性耐火物に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to low thermal expansion refractories, particularly Li, O.A.
JZ,O,・nSiO2 (n=2-9) Li20・SiO2 (n=2-9) which suppresses evaporation of Li20 component from the base material during high temperature use without impairing the low thermal expansion property (thermal shock resistance) of the low thermal expansion refractory. This invention relates to a low thermal expansion refractory containing Au, O, .nSiO2 (n=2 to 9).
［従来の技術］
Ｌｉ２０・ＡＪ２２０．・ｎ５ｉｏ、（ｎ＋＋ｓ２〜９
）質耐火物は、その特異な低熱膨張性ゆえに、極めて大
きな熱衝撃抵抗性を有するという優れた特徴を備える。[Prior art] Li20/AJ220.・n5io, (n++s2~9
) quality refractories have the excellent feature of extremely high thermal shock resistance due to their unique low thermal expansion.
この特性は、特にその成分中のＬｉ２０成分に依るとこ
ろが大である。This characteristic largely depends on the Li20 component in the component.
［発明が解決しようとする問題点］
しかしながら、熊本工業大学研究報告第１１巻第１号及
び第１２巻第１号に報告されているように、ｒｔ、ｔ、
ｏはアルカリ元素の一般性で高温で蒸発しやすく、焼成
や溶融工程、また使用中に問題となり、組成変動や周囲
への汚染が起り得る。Ｊという欠点を有している。[Problems to be solved by the invention] However, as reported in Kumamoto Institute of Technology Research Report Vol. 11, No. 1 and Vol. 12, No. 1, rt, t,
O is a general alkali element and easily evaporates at high temperatures, which causes problems during firing, melting processes, and use, and can cause compositional fluctuations and contamination of the surrounding area. It has the disadvantage of J.
［問題点を解決するための手段］
本発明は、Ｌ ｆ ２０ ” Ａ Ｊ２２０３ ・ｎ
Ｓ ｉ Ｏ２（ｎ＝２〜９）質耐火物の最大の特徴で
ある優れた熱衝撃抵抗性を損なうことなく、蒸発したＬ
ｉ２０成分を吸収あるいは蒸発そのものを抑止させ、特
に高温熱処理治具として使用した場合における被処理物
への汚染が軽減あるいは防止される、優れた耐火物を提
供することを目的とするものである。[Means for solving the problems] The present invention provides L f 20 ” A J2203 ・n
Evaporated L without impairing the excellent thermal shock resistance, which is the greatest feature of S i O2 (n = 2 to 9) refractories.
The object of the present invention is to provide an excellent refractory that absorbs or inhibits evaporation of the i20 component, and reduces or prevents contamination of objects to be treated, especially when used as a high-temperature heat treatment jig.
本発明は主としてＬｉ、Ｏ・ＡＪＺ２０３ ・ｎ５ｉ
ｏ２ （ｎ＝２〜９）よりなる基材の表面に、ＳｉＯ□
粒子及び／又は３Ａｊ２２０３・２ Ｓ ｔ ０２粒子
の集合体よりなる被？Ｉ層を形成させてなる低熱膨張性
耐火物であって、該被覆層のＡぶｚｏ３／ＳｉＯ２重量
比がＯ／１≦Ａｌ２Ｏ３／ＳｉＯ２≦２．５５７１で、
該被覆層の厚さが３０ａｍ未満であることを特徴とする
低熱膨張性耐火物を要旨とするものである。The present invention mainly focuses on Li, O・AJZ203・n5i
o2 (n=2 to 9) on the surface of the base material, SiO
A covering made of particles and/or an aggregate of 3Aj2203.2 S t 02 particles? A low thermal expansion refractory formed by forming an I layer, wherein the Abuzo3/SiO2 weight ratio of the coating layer is O/1≦Al2O3/SiO2≦2.5571,
The gist of the present invention is a low thermal expansion refractory characterized in that the thickness of the coating layer is less than 30 am.
このような本発明は、以下のような知見に基き完成され
たものである。The present invention was completed based on the following findings.
まず、本発明者は、ハイスやＳＫＤ及び特殊合金等の金
属の高温熱処理時（通常、最高温度１１００℃位で数時
間、真空中で加熱した後、数百℃まで不活性ガスにて急
激に冷却する。）において、Ｌ ｉ ２０−Ａ １１２
０３ ’ ｎ Ｓ ｉ Ｏ２（ｎ ＝２〜９）質耐火
物治具を使用した場合、被処理金属表面が汚染されるこ
とについての原因を調べた。その結果、治具基材中のり
、ｉ２０成分による汚染を確認し、加えて、前述の研究
報告により、Ｌｉ２Ｏ成分が高温で蒸発するとの知見を
得た。First, the present inventor discovered that during high-temperature heat treatment of metals such as high speed steel, SKD, and special alloys (usually heated in a vacuum at a maximum temperature of about 1100°C for several hours, then rapidly heated to several hundred degrees Celsius with an inert gas). ), L i 20-A 112
The reason why the surface of the metal to be treated is contaminated when a 03'n S i O2 (n = 2 to 9) refractory jig is used was investigated. As a result, contamination by glue and i20 components in the jig base material was confirmed, and in addition, from the aforementioned research report, it was found that Li2O components evaporate at high temperatures.
そこでＬ ｌ ２０ ” Ａｄｚ ０３ ’ ｎＳ １
０２（ｎ−２〜９）質耐火物表面より、蒸発したＬｉ２
０成分を吸収あるいはＬｉ２０成分そのものの高温にお
ける蒸発を低減あるいは抑止することによって、被処理
金属表面への汚染を軽減あるいは防止する方法について
、鋭意研究を重ねた。So L l 20 ” Adz 03 ' nS 1
Li2 evaporated from the surface of 02 (n-2 to 9) quality refractories
We have conducted extensive research into ways to reduce or prevent contamination on the surface of the metal to be treated by absorbing the Li20 component or reducing or inhibiting the evaporation of the Li20 component itself at high temperatures.
そして、本発明者は、Ｌｉ２０成分との反応性が高いか
あるいはＬｉ２０成分を吸収しやすい成分よりなる緻密
な膜を、Ｌｉ２０−Ａｌ２Ｏ，・ｎ５ｉｏ２ （ｎ＝２
〜９）質基材表面上に形成することが、被熱処理金属表
面への汚染を防止するに有効な方法であること、形成す
る膜としては、充填性が良好で緻密な膜を形成し易くか
つ、Ｌｉ２０成分と反応性の高い５／０２粒子及び／又
はＬｉｚ Ｏ成分を吸収し易い３ＡＡｚ Ｏ３・２Ｓｉ
Ｏ２粒子の被覆層が有効であることを見出し本発明を完
成させた。Then, the present inventor created a dense film made of a component that has high reactivity with the Li20 component or easily absorbs the Li20 component.
~9) Formation on the surface of a quality base material is an effective method for preventing contamination of the surface of the metal to be heat treated, and the film to be formed has good filling properties and is easy to form a dense film. In addition, 5/02 particles that are highly reactive with the Li20 component and/or 3AAz O3.2Si that easily absorbs the Liz O component
The present invention was completed by discovering that a coating layer of O2 particles is effective.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の低熱膨張性耐火物は、Ｌｉ、Ｏ・Ａｄｚ０．−
ｎＳ ｉ Ｏ，（ｎ＝２〜９）貿基材表面に、次の■
〜■のいずれかを、３０μｍ未満の厚さに形成してなる
ものである。The low thermal expansion refractory of the present invention contains Li, O.Adz0. −
nS i O, (n = 2 to 9) The following ■
It is formed by forming any one of ~■ to a thickness of less than 30 μm.
■ ５／０２粒子の被覆層。■ Coating layer of 5/02 particles.
■ ３ Ａ Ｉｔ ２０ 、・２ＳｉＯ２粒子の被覆層
■ Ａ Ｊ！ ２０３ ／ Ｓ ｔ Ｏ２重量比が０／
１くＡ１□０３ ／ｓ ｉ ０２ ＜２．５５／ １、
好ましくは１．５／１≦Ａ ｆｌ、２０３ ／ Ｓ ｉ
０２ ＜２．５５／１（７）範囲となる、５ｉｎ２粒
子及び３Ａｆ２０Ｓ ・２ＳｉＯ２粒子よりなるン皮
覆層
本発明において、基材表面に形成させる被覆層は、上記
■〜■のうち、特に■の被覆層が好ましく、とりわけ、
ＳｉＯ□粒子層と３ＡＩＬ、０３ ・２ＳｉＯ２粒子層
との２層で構成されるものが好ましい。この場合、５／
０２粒子層を下層とし、３ＡＪ２２０３ ・２Ｓ ｉ
０２粒子層を上層とすると、表面の平滑性が十分に得ら
れない。これに対し、３ Ａ ｉ２０３・２ Ｓ ｉ
０２ 粒子ｍ’ａ’下Ｎトし、ＳｉＯ２粒子層を上層と
した場合には、表面平滑性が良好となるので、より好適
である。■ 3 A It 20 , 2SiO2 particle coating layer ■ A J! 203/S t O2 weight ratio is 0/
1kuA1□03 /s i 02 <2.55/ 1,
Preferably 1.5/1≦A fl, 203/S i
02<2.55/1 (7) A coating layer consisting of 5in2 particles and 3Af20S 2SiO2 particles In the present invention, the coating layer formed on the surface of the base material is particularly selected from the above Preferably, a coating layer of
Preferably, it is composed of two layers: a SiO□ particle layer and a 3AIL,03.2SiO2 particle layer. In this case, 5/
02 particle layer as the lower layer, 3AJ2203 ・2S i
If the 02 particle layer is used as the upper layer, sufficient surface smoothness cannot be obtained. On the other hand, 3 A i203・2 S i
02 particles m'a' and a SiO2 particle layer as the upper layer is more preferable because the surface smoothness is improved.
本発明において、このような被覆層の厚さは３０μｍ未
満、好ましくは１０μｍ未満とする。In the present invention, the thickness of such a covering layer is less than 30 μm, preferably less than 10 μm.
被覆層の厚さは厚くなる程基材からのＬｉ、Ｏ成分の蒸
発抑制効果が高くなるが、１０μｍ以上になると被覆層
に亀甲状のワレが発生し易くなり、３０μｍ以上では被
覆層の殆どにワレが発生し、基材表面を全面被覆すると
いう点より見て好ましくない。汚染防止の効果は被覆層
厚が２〜３μｍ程度に達するころより顕著に現われるが
、１μｍ以下ではその効果は十分に満足し得るものでな
い場合がある。従って、本発明においては、通常は１μ
ｍ以上３０μｍ未満、好ましくは２〜３μｍ以上１０μ
ｍ未満の範囲で、被覆層の厚さを適宜決定する。なお、
被覆層を前述の２層構成とする場合、下層（Ｄ３Ａｆ１
２０ｓ ・２Ｓ ｉ ０２粒子層は１μｍ以上、上層の
５ｉＯ２層は２μｍ以上とするのが好適である。As the thickness of the coating layer becomes thicker, the effect of suppressing the evaporation of Li and O components from the base material increases, but when the thickness is 10 μm or more, hexagonal cracks are likely to occur in the coating layer, and when the thickness is 30 μm or more, most of the coating layer has cracks. This is not preferable from the point of view of covering the entire surface of the substrate. The effect of preventing contamination becomes more noticeable when the coating layer thickness reaches about 2 to 3 .mu.m, but the effect may not be fully satisfactory when the thickness is 1 .mu.m or less. Therefore, in the present invention, normally 1μ
m or more and less than 30 μm, preferably 2 to 3 μm or more and 10 μm
The thickness of the coating layer is determined as appropriate within a range of less than m. In addition,
When the coating layer has the above-mentioned two-layer structure, the lower layer (D3Af1
It is preferable that the 20s.2S i 02 particle layer has a thickness of 1 μm or more, and the upper 5iO2 layer has a thickness of 2 μm or more.
本発明において、このような被覆層を形成する基材とな
るＬｉ２ｏ−ＡｆＬ２０３ ・ｎ５ｉｏ２（ｎ＝２〜９
）貿基材とは、Ｌ ｉ２０−ＡＩＬｘ Ｏｓ ”ｎ５
ｉｏ２ （ｎ＝２〜９）よりなるもの、あるいはこれを
主体とし、必要に応じて、カオリン、蛙目粘上等の通常
の耐火物原料を少量配合したものなどが挙げられる。In the present invention, Li2o-AfL203 ・n5io2 (n=2 to 9
) Trading base materials are Li20-AILx Os”n5
io2 (n=2 to 9), or those mainly composed of io2 and, if necessary, a small amount of ordinary refractory materials such as kaolin and kaolin are mixed therein.
このような本発明の低熱膨張性耐火物は、Ｌｉ２０−Ａ
ＩＬ２０３ ・ｎＳｉＯ２（ｎ＝２〜９）質基材の表面
に、前述の被覆層を形成することにより容易に製造する
ことができるが、この場合、焼成後の被覆強度及び密着
性を考慮すると、未焼成のＬｉ２Ｏ・Ａｊ！２０．
・ｎ５ｉＯ，（ｎ＝２〜９）質基材上に、５ｉＯ２粒子
及び／又は３ＡＩ１２０３ ・２ＳｉＯ２粒子を含有す
る塗布液を塗布して基材表面を被覆した後、同時焼成し
て、基材と被覆層とを強固に反応させることが好ましい
。Such a low thermal expansion refractory of the present invention is Li20-A
IL203 can be easily manufactured by forming the above-mentioned coating layer on the surface of an nSiO2 (n=2 to 9) base material, but in this case, considering the coating strength and adhesion after firing, Unfired Li2O・Aj! 20.
・A coating liquid containing 5iO2 particles and/or 3AI1203 ・2SiO2 particles is applied onto the n5iO, (n=2-9) base material to coat the surface of the base material, and then co-fired to coat the base material. It is preferable to cause a strong reaction with the coating layer.
原料のＳ ｉ ０２粒子としては、緻密な層を形成する
ために、焼成径粒径１μｍ未満になるようなものが好ま
しく、そのために、５〜５０ｎｍ（ナノメータ）程度の
粒子径を有する市販のコロイダルシリカを使用するのが
好ましい。また、３ ＡＪＺ、 Ｏ５・２ Ｓ、 ｉ
０２ ニツイテも同様な粒径のものが望ましく、市販の
アルミナゾルを使用するのが好ましい。In order to form a dense layer, the raw material S i 02 particles are preferably those having a fired particle size of less than 1 μm, and for this purpose commercially available colloidal particles having a particle size of about 5 to 50 nm (nanometers) are used. Preference is given to using silica. Also, 3 AJZ, O5・2 S, i
02 It is desirable that the particles have a similar particle size, and it is preferable to use commercially available alumina sol.
これらの原料粒子は適当な濃度の水溶液とし、これをＬ
ｉ２０・Ａｊ！２０３ ・ｎ５ｔ０２ （ｎ＝２〜９
）質基材表面に塗布する。塗布方法としては、スプレー
、はけ塗り、含浸法等の一般的な方法を採用することが
できる。These raw material particles are made into an aqueous solution with an appropriate concentration, and this is
i20・Aj! 203 ・n5t02 (n=2~9
) on the surface of the substrate. As a coating method, general methods such as spraying, brushing, and impregnating methods can be employed.
［作 用］
ＳｉＯ２は充填性が良好で緻密な膜を形成することがで
きるので、Ｌｉ２Ｏ・ＡＪ２２０３ ・ｎＳｉＯ２
（ｎ＝２〜９）質基材からのｔ、ｔ、 ０成分の蒸発
を抑制することができる。しかも、Ｓｉｎ、はＬｉ２Ｏ
成分との反応性が高いので、Ｌｉ２０−Ａλ、Ｏ，・ｎ
５ｉＯ，（ｎ＝２〜９）買基材から蒸発したＬｉ２Ｏ成
分を捕捉することができる。また、３Ａ１，０３ ・２
ＳｉＯ。[Function] SiO2 has good filling properties and can form a dense film, so Li2O・AJ2203・nSiO2
Evaporation of the t, t, and 0 components from the base material (n=2 to 9) can be suppressed. Moreover, Sin is Li2O
Since it has high reactivity with the components, Li20-Aλ,O,・n
5iO, (n=2 to 9) It is possible to capture the Li2O component evaporated from the substrate. Also, 3A1,03 ・2
SiO.
もＬｉ、Ｏ成分を吸収し易いため、該基材から蒸発する
Ｌｉ、Ｏ成分を捕捉することができる。Since it also easily absorbs Li and O components, it is possible to capture the Li and O components that evaporate from the base material.
このため、本発明の低熱膨張性耐火物では、ＳｉＯ２及
び／又は３ ＡＩＬｔ Ｏｓ ・２ Ｓ ｉ ０２ （
７）被覆層により、基材からのＬｉ２０成分の放出が有
効に防止される。Therefore, in the low thermal expansion refractory of the present invention, SiO2 and/or 3 AILt Os 2 Si 02 (
7) The coating layer effectively prevents release of the Li20 component from the base material.
［実施例］
以下実施例及び比較例を挙げて本発明をより具体的に説
明するが、本発明はその要旨を超えない限り、以下の実
施例に限定されるものではない。[Examples] The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
実施例１．２
焼成後、Ｌｉ２０’Ａｊ１２０ｓ ’ｎＳｉＯ２（ｎ＝
約４）質となる未焼成の板状熱処理用トレイ（２００ｍ
ｍｘ２００ｍｍｘ５ｍｍ厚さ）にＳ ｉ Ｏ２の被覆層
を形成した。Example 1.2 After firing, Li20'Aj120s'nSiO2 (n=
Approximately 4) Unfired plate-shaped heat treatment tray (200 m
A coating layer of SiO2 was formed on the substrate (mx200mmx5mm thick).
まず、市販のコロイダルシリカ（日産化学製「スノーテ
ックス」）水溶液（２０重量％濃度）、及びこの水溶液
を更に５倍程度に希釈した水溶液を調製し、これら２種
の水溶液を用い、上記トレイを浸漬、乾燥した後、１１
００〜１３００℃にて１時間焼成して、それぞれ、厚さ
３μｍ（実施例１）及び７μｍ（実施例２）の５ｉｎ２
被覆層を形成した。First, a commercially available colloidal silica (Snowtex manufactured by Nissan Chemical) aqueous solution (concentration 20% by weight) and an aqueous solution obtained by further diluting this aqueous solution to about 5 times were prepared. Using these two types of aqueous solutions, the above tray was prepared. After soaking and drying, 11
Baked at 00 to 1300°C for 1 hour, 5in2 with a thickness of 3 μm (Example 1) and 7 μm (Example 2), respectively.
A coating layer was formed.
この被覆層形成トレイにパーマロイ合金テストピースを
載せ【真空中１１００℃で２時間熱処理した後、Ｎ２ガ
スで急冷し、この時のテストピースの汚染（変色）の程
度を観察した。また、２５〜１０００℃における熱膨張
係数を測定すると共に、被覆層のワレの発生の有無から
熱衝撃性を調べた。A permalloy alloy test piece was placed on this coating layer forming tray and heat treated in vacuum at 1100° C. for 2 hours, then rapidly cooled with N2 gas, and the degree of contamination (discoloration) of the test piece at this time was observed. In addition, the thermal expansion coefficient at 25 to 1000° C. was measured, and the thermal shock resistance was examined based on the presence or absence of cracking in the coating layer.
結果を第１表に示す。The results are shown in Table 1.
実施例３．４
Ａｌｌｘ Ｏｓ ／ Ｓ ｉ Ｏｘ −２，５５／ １
となるように、市販のアルミナゾル及びコロイダルシリ
カ（共に８産化学製）を混合して調製した水溶液を用い
、それぞれ、厚さ２μｍ（実施例３）及び５μｍ（実施
例４） の３ＡｊＺｚ Ｏｓ ・２Ｓ ｉ ０２被覆層
を形成したこと以外は実施例１と同様にして被覆層形成
トレイを得、同様に汚染の程度、熱膨張係数及び熱衝撃
性を調べた。Example 3.4 AllxOs/SiOx-2,55/1
Using an aqueous solution prepared by mixing commercially available alumina sol and colloidal silica (both manufactured by Yasan Kagaku), 3AjZz Os 2S with a thickness of 2 μm (Example 3) and 5 μm (Example 4) were prepared. A coating layer-formed tray was obtained in the same manner as in Example 1 except that the i02 coating layer was formed, and the degree of contamination, coefficient of thermal expansion, and thermal shock property were similarly examined.
結果を第１表に示す。The results are shown in Table 1.
実施例５．６
Ａｌ２２０ｓ ／Ｓ ｉ０２が第１表に示す値トナル水
溶液を調製し、厚さ５μｍの（３Ａｉ２０３ ・２Ｓｉ
０２ ＋ＳｉＯ２ ）被覆層を形成したこと以外は実施
例４と同様にして被覆層形成トレイを得、同様に汚染の
程度、熱膨張係数及び熱衝撃性を調べた。Example 5.6 A tonal aqueous solution with Al220s /S i02 having the value shown in Table 1 was prepared, and a 5 μm thick (3Ai203 ・2Si
02 +SiO2) A coating layer-formed tray was obtained in the same manner as in Example 4 except that the coating layer was formed, and the degree of contamination, coefficient of thermal expansion, and thermal shock resistance were similarly examined.
結果を第１表に示す。The results are shown in Table 1.
実施例７．８ 実施例３で調製した３Ａλ２０３ ・２ＳｉＯ。Example 7.8 3Aλ203·2SiO prepared in Example 3.
水溶液を用いてまず第１表に示す厚さの３Ａ１２ｏ３
・２Ｓｉ０２の下層を形成し、次いで実施例１で調製し
たＳｉＯ２水溶液を用いて第１表に示す厚さのＳｉｎ、
の上層を形成したこと以外は、実施例１と同様にして被
覆層形成トレイを得こ同様に汚染の程度、熱膨張係数及
び熱衝撃性を調べた。First, using an aqueous solution, 3A12o3 of the thickness shown in Table 1 was prepared.
- Form a lower layer of 2SiO2, and then use the SiO2 aqueous solution prepared in Example 1 to form a Si layer with the thickness shown in Table 1,
A coating layer-forming tray was obtained in the same manner as in Example 1, except that the upper layer was formed, and the degree of contamination, coefficient of thermal expansion, and thermal shock resistance were examined in the same manner.
結果を第１表に示す。The results are shown in Table 1.
比較例１〜３
実施例１と同様の未焼成トレイをｔｔｏｏ’ｅ〜１３０
０℃にて１時間焼成したもの（比較例１）、および実施
例１と同様の未焼成トレイを市販のアルミナゾル（８産
化学製）水溶液を希釈したものに浸漬・乾燥後ｔｔｏｏ
℃〜１３００’ｔｌ：にて１時間焼成して、それぞれ厚
さ２μｍ（比較例２）、５μｍ（比較例３）のＡｌ１２
０３被覆層を形成したものについて、実施例１と同様に
して汚染の程度、熱膨張係数及び熱衝撃性を調べた。Comparative Examples 1 to 3 Unfired trays similar to those in Example 1 were heated to ttoo'e~130
The one baked at 0°C for 1 hour (Comparative Example 1) and the same unfired tray as in Example 1 were immersed in a diluted aqueous solution of commercially available alumina sol (manufactured by Yasan Kagaku) and dried.
℃~1300'tl: for 1 hour to obtain Al12 with a thickness of 2 μm (Comparative Example 2) and 5 μm (Comparative Example 3), respectively.
The degree of contamination, coefficient of thermal expansion, and thermal shock properties were examined in the same manner as in Example 1 for the samples on which the 03 coating layer was formed.
結果を第１表に示す。The results are shown in Table 1.
第１表より、本発明の低熱膨張性耐火物は、熱膨張係数
が良好で、熱衝撃性は著しく高い上に、Ｌｉ２０成分の
放出が殆どなく、汚染性が著しく改善されていることが
認められる。From Table 1, it can be seen that the low thermal expansion refractory of the present invention has a good coefficient of thermal expansion, extremely high thermal shock resistance, almost no release of Li20 components, and significantly improved staining properties. It will be done.
［発明の効果］
以上詳述した通り、本発明の低熱膨張性耐火物は、Ｓ
ｉ Ｏ２及び／又は３ＡｊＬｚＯ５・２ＳｔＯ２よりな
る特定組成、特定層厚の被覆層をＬｉ、０−Ａｌｚ ０
３ ・ｎＳｉＯ２（ｎ＝２〜９）質耐火物の表面に形成
することによって、その優れた熱衝撃性を損なうことな
く、蒸発したＬｉ２Ｏ成分を吸収あるいは蒸発そのもの
を抑止させたものであって、特に高温熱処理時において
被処理物への汚染を軽減あるいは防止することができる
ことから、極めて優れた高温熱処理用治具を提供するこ
とができる。[Effect of the invention] As detailed above, the low thermal expansion refractory of the present invention has S
i A coating layer of a specific composition and a specific layer thickness consisting of O2 and/or 3AjLzO5・2StO2 is formed by Li, 0-Alz 0
3. By forming it on the surface of nSiO2 (n=2-9) refractory, it absorbs evaporated Li2O components or inhibits evaporation itself without impairing its excellent thermal shock properties, In particular, since contamination of the object to be treated can be reduced or prevented during high-temperature heat treatment, an extremely excellent jig for high-temperature heat treatment can be provided.
代理人 弁理士 重 野 剛Agent: Patent attorney Tsuyoshi Shigeno
Claims (5)
＿２（ｎ＝２〜９）よりなる基材の表面に、ＳｉＯ＿２
粒子及び／又は３Ａｌ＿２Ｏ＿３・２ＳｉＯ＿２粒子の
集合体よりなる被覆層を形成させてなる低熱膨張性耐火
物であって、該被覆層のＡｌ＿２Ｏ＿３／ＳｉＯ＿２重
量比が０／１≦Ａｌ＿２Ｏ＿３／ＳｉＯ＿２≦２．５５
／１で、該被覆層の厚さが３０μｍ未満であることを特
徴とする低熱膨張性耐火物。(1) Mainly Li_2O・Al_2O_3・nSiO
SiO_2 on the surface of the base material made of _2 (n=2 to 9)
A low thermal expansion refractory formed by forming a coating layer consisting of an aggregate of particles and/or 3Al_2O_3.2SiO_2 particles, the coating layer having an Al_2O_3/SiO_2 weight ratio of 0/1≦Al_2O_3/SiO_2≦2.55.
/1, and the thickness of the coating layer is less than 30 μm.
とする特許請求の範囲第１項に記載の低熱膨張性耐火物
。(2) The low thermal expansion refractory according to claim 1, wherein the coating layer has a thickness of less than 10 μm.
子よりなる下層と、ＳｉＯ＿２粒子よりなる上層とで構
成されることを特徴とする特許請求の範囲第１項又は第
２項に記載の低熱膨張性耐火物。(3) The coating layer is composed of a lower layer made of 3Al_2O_3.2SiO_2 particles and an upper layer made of SiO_2 particles. thing.
層の厚さが１μｍ以上、ＳｉＯ＿２粒子よりなる上層の
厚さが２μｍ以上であることを特徴とする特許請求の範
囲第３項に記載の低熱膨張性耐火物。(4) The low thermal expansion refractory according to claim 3, characterized in that the thickness of the lower layer made of 3Al_2O_3.2SiO_2 particles is 1 μm or more, and the thickness of the upper layer made of SiO_2 particles is 2 μm or more. .
１．５／１≦Ａｌ＿２Ｏ＿３／ＳｉＯ＿２≦２．５５／
１であることを特徴とする特許請求の範囲第１項ないし
第４項のいずれか１項に記載の低熱膨張性耐火物。(5) The Al_2O_3/SiO_2 weight ratio of the coating layer is 1.5/1≦Al_2O_3/SiO_2≦2.55/
1. The low thermal expansion refractory according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27539787A JPH0714839B2 (en) | 1987-10-30 | 1987-10-30 | Low thermal expansion refractory |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27539787A JPH0714839B2 (en) | 1987-10-30 | 1987-10-30 | Low thermal expansion refractory |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01119587A true JPH01119587A (en) | 1989-05-11 |
| JPH0714839B2 JPH0714839B2 (en) | 1995-02-22 |
Family
ID=17554928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27539787A Expired - Fee Related JPH0714839B2 (en) | 1987-10-30 | 1987-10-30 | Low thermal expansion refractory |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0714839B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015024945A (en) * | 2013-07-29 | 2015-02-05 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Inorganic filler, and insulating resin composition, insulating film, prepreg and printed circuit board including the same |
-
1987
- 1987-10-30 JP JP27539787A patent/JPH0714839B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015024945A (en) * | 2013-07-29 | 2015-02-05 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Inorganic filler, and insulating resin composition, insulating film, prepreg and printed circuit board including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0714839B2 (en) | 1995-02-22 |
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