JP2012020895A - Insulating refractory and method of manufacturing the same - Google Patents

Insulating refractory and method of manufacturing the same Download PDF

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Publication number
JP2012020895A
JP2012020895A JP2010159206A JP2010159206A JP2012020895A JP 2012020895 A JP2012020895 A JP 2012020895A JP 2010159206 A JP2010159206 A JP 2010159206A JP 2010159206 A JP2010159206 A JP 2010159206A JP 2012020895 A JP2012020895 A JP 2012020895A
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Japan
Prior art keywords
heat
particles
insulating refractory
refractory
pore
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JP2010159206A
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JP5694695B2 (en
Inventor
Tatsumi Tsuyama
辰己 津山
Kenichiro Koga
謙一郎 古賀
Tatsuhiko Uchida
龍彦 打田
Koji Watanabe
浩二 渡邊
Mitsunobu Murashima
光宣 村島
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Priority to JP2010159206A priority Critical patent/JP5694695B2/en
Priority to PCT/JP2011/065567 priority patent/WO2012008352A1/en
Priority to CN2011800149415A priority patent/CN102811973A/en
Priority to KR1020127024461A priority patent/KR20130097059A/en
Publication of JP2012020895A publication Critical patent/JP2012020895A/en
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Abstract

PROBLEM TO BE SOLVED: To provide an insulating refractory restrained from the reaction with an alkaline component and further reduced in weight.SOLUTION: This insulating refractory comprises alumina or zirconia ceramics and contains no or, even if it contains, 1 wt.% or less silica, and has a porosity of 65-85% and a compressive strength of 2 MPa. This insulating refractory is preferably manufactured by kneading alumina particles or zirconia particles, a water-soluble polymer material, a polysaccharide, pore-forming particles capable of disappearing by sintering and a liquid medium, then by press-molding the kneaded product at a pressure not breaking the pore-forming particles, and finally by sintering the molded product in a condition in which the pore-forming particles are disappeared.

Description

本発明は、断熱耐火物及びその製造方法に関する。   The present invention relates to a heat-insulating refractory and a method for producing the same.

窯炉等の炉壁や天井には種々の耐火物が使用されている。例えば、アルカリ成分を多く含有するワーク焼成用の窯炉の炉壁や天井の断熱部材としては、アルミナの純度が７０〜９９％程度の断熱耐火物が多く使用されている。断熱耐火物におけるアルミナの純度が低い場合には、アルカリ成分による耐火物の劣化を抑えるために、該耐火物の表面に高純度のアルミナコートを施す必要が生じる場合がある。このようなアルミナコートを行うには手間がかかる。また、アルミナの純度が高い耐火物を用いた場合であってもアルカリ成分との反応は避けられず、耐火物の劣化を抑えるには十分とは言えなかった。   Various refractories are used for furnace walls and ceilings of kilns and the like. For example, as a heat insulating member for a furnace wall or ceiling of a kiln furnace for firing a workpiece containing a large amount of alkali components, a heat insulating refractory having an alumina purity of about 70 to 99% is often used. When the purity of alumina in the heat-insulating refractory is low, it may be necessary to apply a high-purity alumina coat to the surface of the refractory in order to suppress deterioration of the refractory due to the alkali component. It takes time to perform such alumina coating. Further, even when a refractory having a high alumina purity is used, a reaction with an alkali component is unavoidable, and it cannot be said to be sufficient for suppressing deterioration of the refractory.

アルカリ成分との反応に起因する劣化の防止に加え、断熱耐火物にはその軽量化が求められている。例えば、焼成後の嵩比重が１．３５〜１．６０であり、かつアルミナ含有比率が９７重量％以上である高温用高アルミナ質断熱耐火物が提案されている（特許文献１参照）。この耐火物は、高純度中空アルミナが３５〜６０重量％配合され、該中空アルミナの外径３．３６０ｍｍ以上の粒子が２．０〜７．０重量％含有される原料粉末を用いて焼成されたものである。   In addition to preventing deterioration due to reaction with alkali components, heat-insulating refractories are required to be lighter. For example, a high-alumina high-temperature insulating refractory for high temperature having a bulk specific gravity after firing of 1.35 to 1.60 and an alumina content ratio of 97% by weight or more has been proposed (see Patent Document 1). This refractory is fired using a raw material powder containing 35 to 60% by weight of high-purity hollow alumina and containing 2.0 to 7.0% by weight of particles having an outer diameter of 3.360 mm or more. It is a thing.

しかしこの耐火物は、シリカを比較的多く含み、アルミナの純度が十分に高いとは言えない。その結果、シリカと、ワークに由来するアルカリ成分との反応が進みやすく、耐火物の劣化が起こりやすい。また、気孔率が高いとは言えないので重くなってしまう。また、熱容量的にも不利になる。すなわち省エネ効率が悪い。更に、熱伝導率が高いことから断熱性にも劣る。   However, this refractory contains a relatively large amount of silica, and it cannot be said that the purity of alumina is sufficiently high. As a result, the reaction between the silica and the alkali component derived from the workpiece tends to proceed, and the refractory tends to deteriorate. Moreover, since it cannot be said that the porosity is high, it will become heavy. Moreover, it becomes disadvantageous also in terms of heat capacity. In other words, energy efficiency is poor. Furthermore, since heat conductivity is high, it is inferior to heat insulation.

特開平１０−０７２２６９号公報Japanese Patent Laid-Open No. 10-072269

本発明の課題は、前述した従来技術が有する種々の欠点を解消し得る断熱耐火物を提供することにある。   The subject of this invention is providing the heat insulation refractory which can eliminate the various fault which the prior art mentioned above has.

本発明は、アルミナセラミックス又はジルコニアセラミックスからなり、シリカを含まないか、又は含んだとしても１重量％以下であり、気孔率が６５〜８５％であり、かつ圧縮強さが２ＭＰａ以上であることを特徴とする断熱耐火物を提供するものである。   The present invention is made of alumina ceramics or zirconia ceramics, does not contain silica, or even if it contains 1% by weight or less, has a porosity of 65 to 85%, and has a compressive strength of 2 MPa or more. It provides the heat insulation refractory characterized by these.

また本発明は、前記の断熱耐火物の好適な製造方法として、
アルミナ粒子又はジルコニア粒子、水溶性高分子材料、多糖類、焼成によって消失可能な造孔粒子、及び液媒体を混練して得られた混練物を、該造孔粒子が破壊されない圧力でプレス成形して成形体を得、次いで
該造孔粒子が消失する条件下に該成形体を焼成することを特徴とする断熱耐火物の製造方法を提供するものである。 Moreover, this invention is as a suitable manufacturing method of the said heat insulation refractory,
A kneaded product obtained by kneading alumina particles or zirconia particles, a water-soluble polymer material, a polysaccharide, pore-forming particles that can be lost by firing, and a liquid medium is press-molded at a pressure at which the pore-forming particles are not destroyed. A molded product is obtained, and then the molded product is fired under conditions where the pore-forming particles disappear.

本発明によれば、アルカリ成分との反応が抑制され、かつ一層の軽量化が図られながら実使用に十分な強度を有する断熱耐火物が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the heat insulation refractory which has intensity | strength sufficient for actual use is provided, the reaction with an alkali component being suppressed and achieving further weight reduction.

図１（ａ）ないし（ｃ）は、本発明の断熱耐火物の一実施形態を示す図である。Fig.1 (a) thru | or (c) are figures which show one Embodiment of the heat insulation refractory of this invention. 図２は、図１に示す断熱耐火物の積み上げ構造を示す模式図である。FIG. 2 is a schematic diagram showing a stacked structure of the heat insulating refractories shown in FIG. 図３（ａ）ないし（ｃ）は、本発明の断熱耐火物の別の実施形態を示す図である。3 (a) to 3 (c) are diagrams showing another embodiment of the heat-insulating refractory according to the present invention. 図４は、図１に示す断熱耐火物の積み上げ構造を示す模式図である。FIG. 4 is a schematic diagram showing a stacked structure of the heat-insulating refractories shown in FIG.

以下本発明を、その好ましい実施形態に基づき説明する。本発明の断熱耐火物は、高純度のアルミナセラミックス又はジルコニアセラミックスを主成分とするものである。これらのセラミックスを主成分とする本発明の断熱耐火物は耐アルカリ性に優れたものとなる。断熱耐火物におけるアルミナ又はジルコニアの割合は、アルカリ成分との反応を抑制する観点から９９重量％以上とすることが必要であり、好ましくは９９．５重量％以上である。すなわち、本発明の断熱耐火物は高純度アルミナ質又は高純度ジルコニア質のものである。アルミナ又はジルコニアの割合の上限値に特に制限はなく、高ければ高いほど、断熱耐火物とアルカリ成分との反応の抑制に効果的である。本発明の断熱耐火物におけるアルミナ又はジルコニアの純度を高めるためには、例えば断熱耐火物の原料として高純度の人工アルミナ又は人工ジルコニアを用いればよい。これに対して、粘度等の天然原料由来のアルミナ等を用いると、不純物の混入の可能性がある。断熱耐火物中のアルミナ又はジルコニア割合は、例えば光電測光式発光分光分析法によって測定することができる。   Hereinafter, the present invention will be described based on preferred embodiments thereof. The heat-insulating refractory of the present invention is mainly composed of high-purity alumina ceramics or zirconia ceramics. The heat-insulating refractory of the present invention mainly composed of these ceramics has excellent alkali resistance. The ratio of alumina or zirconia in the heat insulating refractory is required to be 99% by weight or more, preferably 99.5% by weight or more from the viewpoint of suppressing the reaction with the alkali component. That is, the heat-insulating refractory of the present invention is of high purity alumina or high purity zirconia. There is no restriction | limiting in particular in the upper limit of the ratio of an alumina or a zirconia, and it is effective in suppression of reaction with a heat insulation refractory and an alkali component, so that it is high. In order to increase the purity of alumina or zirconia in the heat insulating refractory of the present invention, for example, high-purity artificial alumina or artificial zirconia may be used as a raw material for the heat insulating refractory. On the other hand, when alumina derived from natural raw materials such as viscosity is used, impurities may be mixed. The ratio of alumina or zirconia in the heat-insulating refractory can be measured, for example, by photoelectric photometric emission spectrometry.

なお断熱耐火物がジルコニアセラミックスからなる場合、該ジルコニアセラミックスには安定化ジルコニアセラミックスも包含される。安定化ジルコニアセラミックスには、例えばＣａＯ、Ｙ2Ｏ3、ＭｇＯ等が安定化剤として含まれている。本発明においてはこれらの安定化剤もジルコニアセラミックスの一部として考え、不純物から除かれる。 When the heat insulating refractory is made of zirconia ceramics, the zirconia ceramics include stabilized zirconia ceramics. Stabilized zirconia ceramics contain, for example, CaO, Y 2 O 3 , MgO or the like as a stabilizer. In the present invention, these stabilizers are also considered as a part of zirconia ceramics and are excluded from impurities.

上述のとおり、本発明の断熱耐火物は、高純度のアルミナ質又は高純度のジルコニア質のものであることが好ましい。つまり、不純物を極力含んでいないことが好ましい。特に、断熱耐火物の劣化に影響を与える観点から、本発明の断熱耐火物は、シリカを含んでいないか、又は含んでいる場合であっても、その量はごく少ないものである。シリカはアルカリ成分と反応しやすく、それによって劣化の原因となる低融点物質が生成しやすいからである。断熱耐火物がシリカを含んでいる場合、断熱耐火物におけるシリカの割合は１重量％以下とすることが必要であり、好ましくは０．５重量％以下に抑える。   As described above, the heat-insulating refractory according to the present invention is preferably made of high-purity alumina or high-purity zirconia. That is, it is preferable that impurities are not included as much as possible. In particular, from the viewpoint of affecting the deterioration of the heat-insulating refractory, the amount of the heat-insulating refractory according to the present invention is very small even if it does not contain or contains silica. This is because silica easily reacts with an alkali component, thereby easily producing a low-melting-point substance that causes deterioration. When the heat insulating refractory contains silica, the ratio of silica in the heat insulating refractory is required to be 1% by weight or less, and preferably 0.5% by weight or less.

シリカと同様に、ナトリウムやカリウム等のアルカリ金属の酸化物も、断熱耐火物の劣化に影響を与える物質である。アルカリ金属酸化物は断熱耐火物のガラス化を促進し、断熱耐火物のクリープ性能の低下を招く。この観点から、本発明の断熱耐火物はアルカリ金属酸化物も含んでいないことが好ましい。また、断熱耐火物がアルカリ金属酸化物を含んでいる場合であってもその量は極力少ないことが有利である。具体的には、断熱耐火物におけるアルカリ金属酸化物の割合（Ｎａ2ＯやＫ2Ｏの合計量の割合）を０．３重量％以下、特に０．２重量％以下に抑えることが好ましい。 Similar to silica, oxides of alkali metals such as sodium and potassium are substances that affect the deterioration of heat-insulating refractories. Alkali metal oxides promote the vitrification of heat-insulating refractories and cause the creep performance of heat-insulating refractories to deteriorate. From this viewpoint, it is preferable that the heat insulating refractory of the present invention does not contain an alkali metal oxide. Even if the heat-insulating refractory contains an alkali metal oxide, it is advantageous that the amount is as small as possible. Specifically, it is preferable to suppress the ratio of the alkali metal oxide (the ratio of the total amount of Na 2 O and K 2 O) in the heat insulating refractory to 0.3% by weight or less, particularly 0.2% by weight or less.

また、シリカと同様に、酸化鉄も、断熱耐火物の劣化に影響を与える物質である。この観点から、本発明の断熱耐火物は酸化鉄も含んでいないことが好ましい。また、断熱耐火物が酸化鉄を含んでいる場合であってもその量は極力少ないことが有利である。具体的には、断熱耐火物における酸化鉄の割合（各種の酸化鉄の合計量の割合）を０．５重量％以下、特に０．２重量％以下に抑えることが好ましい。   Further, like silica, iron oxide is a substance that affects the deterioration of the heat insulating refractory. From this viewpoint, it is preferable that the heat-insulating refractory of the present invention does not contain iron oxide. Even if the heat-insulating refractory contains iron oxide, the amount is advantageously as small as possible. Specifically, it is preferable to keep the ratio of iron oxide in the heat insulating refractory (the ratio of the total amount of various iron oxides) to 0.5% by weight or less, particularly 0.2% by weight or less.

断熱耐火物の劣化の一層の抑制の観点から、本発明の断熱耐火物におけるシリカ、アルカリ金属酸化物及び酸化鉄の総和の割合は、１．３重量％以下、特に０．７以下に抑えることが好ましい。   From the standpoint of further suppressing deterioration of the heat-insulating refractory, the total ratio of silica, alkali metal oxide and iron oxide in the heat-insulating refractory of the present invention should be 1.3% by weight or less, particularly 0.7 or less. Is preferred.

断熱耐火物に含まれるシリカやアルカリ金属酸化物の割合は、例えば光電測光式発光分光分析法によって測定することができる。   The proportion of silica or alkali metal oxide contained in the heat-insulating refractory can be measured, for example, by photoelectric photometric emission spectroscopic analysis.

本発明の断熱耐火物は、気孔率が高いことによって特徴付けられる。具体的には、本発明の断熱耐火物の気孔率は６５〜８５％という非常に高いものであり、好ましくは７０〜８０％である。断熱耐火物の気孔率が６５％に満たない場合には、該耐火物が重くなってしまう。また熱容量や熱伝導率の点からも不利になってしまう。断熱耐火物の気孔率の上限値は、該耐火物の軽量化及び断熱化と強度とのバランスを考慮して決定される。この観点から、本発明においては断熱耐火物の気孔率の上限値を８５％に設定している。断熱耐火物の気孔率は、例えば
（１−嵩比重／見掛比重）×１００の計算式から算出することができる。 The adiabatic refractory of the present invention is characterized by a high porosity. Specifically, the heat-insulating refractory of the present invention has a very high porosity of 65 to 85%, preferably 70 to 80%. When the porosity of the heat insulating refractory is less than 65%, the refractory becomes heavy. Further, it is disadvantageous from the viewpoint of heat capacity and thermal conductivity. The upper limit value of the porosity of the heat-insulating refractory is determined in consideration of the weight reduction of the refractory and the balance between heat insulation and strength. From this viewpoint, in the present invention, the upper limit value of the porosity of the heat insulating refractory is set to 85%. The porosity of the heat insulating refractory can be calculated from, for example, a formula of (1−bulk specific gravity / apparent specific gravity) × 100.

前記の式における嵩比重は、断熱耐火物の重量を測定し、また断熱耐火物の寸法の測定から得られた体積で除すことで算出される。また、見掛比重は、断熱耐火物の質量を、その見掛容積と同じ容積を持つ４℃の水の質量で割った値であり（ＪＩＳ Ｒ２００１）、アルキメデス法によって測定される。   The bulk specific gravity in the above formula is calculated by measuring the weight of the heat insulating refractory and dividing by the volume obtained from the measurement of the size of the heat insulating refractory. The apparent specific gravity is a value obtained by dividing the mass of the heat insulating refractory by the mass of water at 4 ° C. having the same volume as the apparent volume (JIS R2001), and is measured by the Archimedes method.

本発明の断熱耐火物の気孔率を上述した範囲内にするためには、例えば該耐火物の製造において、原料として焼成によって消失可能な造孔粒子を用いたり、中空粒子を用いたりすればよい。特に、後述する製造方法によれば、中空粒子を用いなくても（つまり中実粒子を用いても）、気孔率を上述した範囲内にすることができる。   In order to make the porosity of the heat-insulating refractory of the present invention within the above-mentioned range, for example, in the production of the refractory, pore-forming particles that can be lost by firing may be used as raw materials, or hollow particles may be used. . In particular, according to the production method described later, the porosity can be within the above-described range without using hollow particles (that is, even when solid particles are used).

本発明の断熱耐火物は、気孔率が高いにもかかわらず、実使用に十分な強度を有することによっても特徴付けられる。具体的には、ＪＩＳ Ｒ２６１５に準じて測定された、断熱耐火物の圧縮強さが２ＭＰａ以上であり、好ましくは３ＭＰａ以上である。つまり本発明の断熱耐火物は、高気孔率と高圧縮強さという二律背反の要求を同時に満たすものである。断熱耐火物の圧縮強さが２ＭＰａ以上あれば、該断熱圧縮物を積み上げて、後述する積み上げ構造を形成した場合に、各断熱圧縮物に圧潰等の不都合が生じることを効果的に防止することができる。   The adiabatic refractory of the present invention is also characterized by having sufficient strength for practical use despite its high porosity. Specifically, the compressive strength of the heat insulating refractory measured in accordance with JIS R2615 is 2 MPa or more, preferably 3 MPa or more. That is, the heat-insulating refractory of the present invention satisfies the contradictory requirements of high porosity and high compressive strength at the same time. If the compressive strength of the heat insulating refractory is 2 MPa or more, effectively preventing the occurrence of inconvenience such as crushing in each heat insulating compressed material when the heat insulating compressed material is stacked to form a stacked structure described later. Can do.

前記の圧縮強さと同様の観点から、本発明の断熱耐火物は、ＪＩＳ Ｒ２６１９に準じて測定された断熱耐火物の曲げ強さが０．５ＭＰａ以上であり、特に１ＭＰａ以上であることが好ましい。断熱耐火物の曲げ強さが０．５ＭＰａ以上であれば、前記の積み上げ構造において、各断熱耐火物の破損等の不都合が生じることを効果的に防止することができる。   From the same viewpoint as the compressive strength, the heat insulating refractory of the present invention has a bending strength of the heat insulating refractory measured according to JIS R2619 of 0.5 MPa or more, and particularly preferably 1 MPa or more. If the bending strength of the heat insulating refractories is 0.5 MPa or more, it is possible to effectively prevent inconveniences such as breakage of the respective heat insulating refractories in the stacked structure.

前記の圧縮強さや曲げ強さを有する断熱耐火物を得るためには、例えば後述する方法を採用して断熱耐火物を製造すればよい。   In order to obtain the heat insulating refractory having the compressive strength and the bending strength, for example, a heat insulating refractory may be manufactured by adopting a method described later.

本発明の断熱耐火物は、一般に所定の三次元形状をしている。本発明の断熱耐火物を各種の炉の内張りや裏張りに用いる場合には、所定の三次元形状を有する該耐火物を複数個組み上げていくことが好ましい。具体的な形状としては、例えばＪＩＳ Ｒ２１０１に規定された標準形れんが形状である並形、標準横ぜり形、標準縦ぜり形、標準ばち形等を始めとする多面体形状を採用することができる。また、継ぎ手に用いられる異形の形状を採用することもできる。そのような形状としては、例えば相欠継、実継、ほぞ継、太ほぞ継、大入継などが挙げられる。更に、アーチ構造用の形状を採用することもできる。そのような形状としては、例えば横ぜり、縦ぜり、ばち形（扇形）、長手抱き、小口抱き、胴付抱きなどが挙げられる。以上の各種形状の詳細は、例えば耐火物技術協会発行の「窯炉工学」（第１版、１９８３年４月発行）に記載されている。   The heat insulating refractory of the present invention generally has a predetermined three-dimensional shape. When the heat-insulating refractory according to the present invention is used for the lining or backing of various furnaces, it is preferable to assemble a plurality of the refractories having a predetermined three-dimensional shape. As specific shapes, for example, polyhedral shapes such as standard shape, standard horizontal edge shape, standard vertical edge shape, standard edge shape, etc. which are standard brick shapes defined in JIS R2101 shall be adopted. Can do. Moreover, the irregular shape used for a joint can also be employ | adopted. Examples of such a shape include phase succession, real succession, tenon joint, thick tenon joint, large joint, and the like. Furthermore, the shape for an arch structure can also be employ | adopted. As such a shape, for example, a horizontal hull, a vertical hull, a drum shape (fan shape), a longitudinal hug, a forehead hug, a body hug, and the like can be mentioned. Details of the various shapes described above are described in, for example, “Kiln Furnace Engineering” (first edition, issued in April 1983) issued by the Refractory Technology Association.

上述の各種の形状を有する本発明の断熱耐火物を組み上げる場合、該耐火物に、へこみ、ザグリ、穴等の凹陥部を形成することが、一層の軽量化及び断熱化の観点から好ましい。例えば図１（ａ）に示すように、断熱耐火物１０を直六面体（直方体）の形状となし、組み上げ状態において隣り合う他の断熱耐火物との対向面、例えば組み上げ状態における上面１１及び下面１２に相当する面に１又は２以上の凹陥部２１，２２を形成することができる。この断熱耐火物１０は、その上面１１及び下面１２が長手方向Ｘとそれに直交する幅方向Ｙを有し、長手方向Ｘの長さが、幅方向Ｙの長さの概ね２倍になっている。   When assembling the heat-insulating refractory of the present invention having the above-described various shapes, it is preferable from the viewpoints of further weight reduction and heat insulation to form concave portions such as dents, counterbores, and holes in the refractory. For example, as shown in FIG. 1A, the heat-insulating refractory 10 has a rectangular parallelepiped (cuboid) shape, and faces opposite to other heat-insulating refractories adjacent in the assembled state, for example, the upper surface 11 and the lower surface 12 in the assembled state. One or two or more recessed portions 21 and 22 can be formed on the surface corresponding to. This heat-insulating refractory 10 has an upper surface 11 and a lower surface 12 having a longitudinal direction X and a width direction Y orthogonal thereto, and the length in the longitudinal direction X is approximately twice the length in the width direction Y. .

各凹陥部２１，２２はそれが形成されている面と反対側の面までは貫通していない。各凹陥部２１，２２の深さは、断熱耐火物１０の厚みＴの１／２未満になっている。各凹陥部２１，２２はいずれも同形であり、円柱状の形状をしている。尤も、各凹陥部２１，２２は同じ形状であることを要せず、断熱耐火物の具体的な用途や、炉内での組み上げ位置に応じて種々の異なる形状を採用してもよい。   Each of the recessed portions 21 and 22 does not penetrate to the surface opposite to the surface where the recessed portions 21 and 22 are formed. The depth of each recessed part 21, 22 is less than ½ of the thickness T of the heat insulating refractory 10. Each of the recessed portions 21 and 22 has the same shape and has a cylindrical shape. However, the recessed portions 21 and 22 do not need to have the same shape, and various different shapes may be employed depending on the specific use of the heat-insulating refractory and the assembly position in the furnace.

上面１１に形成されている凹陥部２１と、下面１２に形成されている凹陥部２２とは、断熱耐火物１０の平面視において、該凹陥部２１，２２の位置が重ならないように配置されている。つまり、上面１１における凹陥部２１が形成されている位置に対応する下面１２の位置には凹陥部が形成されておらず、かつ下面１２における凹陥部２２が形成されている位置に対応する上面１１の位置にも凹陥部が形成されていない。   The recessed portion 21 formed on the upper surface 11 and the recessed portion 22 formed on the lower surface 12 are arranged so that the positions of the recessed portions 21 and 22 do not overlap in the plan view of the heat-insulating refractory 10. Yes. That is, the upper surface 11 corresponding to the position where the recessed portion 22 is formed on the lower surface 12 and the recessed portion 22 is not formed at the position of the lower surface 12 corresponding to the position where the recessed portion 21 is formed on the upper surface 11. No recess is formed at the position of.

断熱耐火物１０の上面１１及び下面１２における凹陥部２１，２２の具体的な形成位置は次のとおりである。すなわち、図１に示すように、断熱耐火物１０の上面１１（下面１２）を幅方向Ｙに沿って左右に二等分する中心線Ｌによって仮想的に上面１１（下面１２）を左右に二等分して形成される左半部の四角形１１ａと、右半部の四角形１１ｂを考えた場合、各四角形１１ａ，１１ｂの一の対角線（図示せず）上に凹陥部２１の中心が位置しており、他の対角線（図示せず）上に凹陥部２２の中心が位置している。   The specific formation positions of the recessed portions 21 and 22 on the upper surface 11 and the lower surface 12 of the heat insulating refractory 10 are as follows. That is, as shown in FIG. 1, the upper surface 11 (lower surface 12) is virtually divided into left and right by a center line L that bisects the upper surface 11 (lower surface 12) of the heat insulating refractory 10 in the width direction Y. Considering the left half quadrangle 11a and the right half quadrangle 11b formed by equally dividing, the center of the recess 21 is located on one diagonal line (not shown) of each quadrangle 11a, 11b. The center of the recessed portion 22 is located on another diagonal line (not shown).

軽量化及び断熱化と強度とのバランスの点から、断熱耐火物１０においては、それに形成されている凹陥部２１，２２の体積の総和は、断熱耐火物１０の見かけの体積の１０〜４０％、特に２０〜３０％であることが好ましい。また、同様の観点から、個々の凹陥部２１，２２の体積は、断熱耐火物１０の見かけの体積の２〜４０％、特に５〜４０％であることが好ましい。   In terms of the balance between weight reduction, heat insulation, and strength, in the heat insulating refractory 10, the total volume of the recessed portions 21 and 22 formed in the heat insulating refractory 10 is 10 to 40% of the apparent volume of the heat insulating refractory 10. In particular, it is preferably 20 to 30%. Further, from the same viewpoint, the volume of each of the recessed portions 21 and 22 is preferably 2 to 40%, particularly 5 to 40%, of the apparent volume of the heat insulating refractory 10.

図１に示す断熱耐火物１０を積み上げる場合には、例えば図２に示すような積み上げ構造を採用することができる。すなわち、断熱耐火物１０を、その長手方向Ｘに沿って列をなすように並べて第１段３１を形成し、その上に、同様の並べ方で第２段３２を形成する。この場合、第２段３２は、第１段３１に対して、断熱耐火物１０の配置が１／２ピッチずれるようにする。本図に示す積み上げ構造においては、各断熱耐火物１０における凹陥部２１，２２は、上下で隣り合う断熱耐火物１０における凹陥部２１，２２と対向していない状態になっている。   When the heat insulating refractories 10 shown in FIG. 1 are stacked, for example, a stacked structure as shown in FIG. 2 can be adopted. That is, the heat insulating refractories 10 are arranged in a row along the longitudinal direction X to form the first stage 31, and the second stage 32 is formed thereon in the same manner. In this case, the second stage 32 is arranged such that the arrangement of the heat insulating refractory 10 is shifted by 1/2 pitch with respect to the first stage 31. In the stacked structure shown in the figure, the recessed portions 21 and 22 in each heat insulating refractory 10 are not opposed to the recessed portions 21 and 22 in the heat insulating refractory 10 adjacent in the vertical direction.

図３には、断熱耐火物１０の別の形態が示されている。なお、同図に示す断熱耐火物１０に関して特に説明しない点については、図１に示す断熱耐火物１０に関する説明が適宜適用される。上面１１に形成されている凹陥部２１と、下面１２に形成されている凹陥部２２とは、断熱耐火物１０の平面視において、該凹陥部２１，２２の位置が重ならないように配置されている。具体的には、中心線Ｌによって仮想的に上面１１（下面１２）を左右に二等分して形成される左半部の四角形１１ａと、右半部の四角形１１ｂを考えた場合、左半部の四角形１１ａに対応する上面１１に凹陥部２１が形成されており、右半部の四角形１１ｂに対応する下面１２に凹陥部２２が形成されている。各半部の四角形１１ａ，１１ｂにおいては、２本の対角線それぞれの上に２個の凹陥部２１（２２）の中心が位置しており、かつ２本の対角線の交点に更に１個の凹陥部２１（２２）の中心が位置している。つまり、各半部の四角形１１ａ（１１ｂ）においては、合計５個の凹陥部２１（２２）が形成されている。   FIG. 3 shows another form of the heat insulating refractory 10. In addition, about the point which is not demonstrated especially regarding the heat insulation refractory 10 shown to the same figure, the description regarding the heat insulation refractory 10 shown in FIG. 1 is applied suitably. The recessed portion 21 formed on the upper surface 11 and the recessed portion 22 formed on the lower surface 12 are arranged so that the positions of the recessed portions 21 and 22 do not overlap in the plan view of the heat-insulating refractory 10. Yes. Specifically, when a left half quadrangle 11a and a right half quadrangle 11b formed by virtually dividing the upper surface 11 (lower surface 12) into left and right by a center line L are considered, A concave portion 21 is formed on the upper surface 11 corresponding to the quadrangle 11a, and a concave portion 22 is formed on the lower surface 12 corresponding to the right half quadrilateral 11b. In each half quadrilateral 11a, 11b, the centers of the two recesses 21 (22) are positioned on each of the two diagonals, and one more recess at the intersection of the two diagonals. The center of 21 (22) is located. That is, a total of five recessed portions 21 (22) are formed in each half quadrilateral 11a (11b).

図３に示す断熱耐火物１０を積み上げる場合には、例えば図４に示すような積み上げ構造を採用することができる。この積み上げ構造は、先に説明した図２に示す積み上げ構造と同様である。図４に示す積み上げ構造においては、第２段３２は、第１段３１に対して、断熱耐火物１０の配置が１／２ピッチずれている。したがって、各断熱耐火物１０における凹陥部２１，２２は、上下で隣り合う断熱耐火物１０における凹陥部２１，２２と対向していない状態になっている。   When the heat insulating refractories 10 shown in FIG. 3 are stacked, for example, a stacked structure as shown in FIG. 4 can be adopted. This stacked structure is the same as the stacked structure shown in FIG. 2 described above. In the stacked structure shown in FIG. 4, the arrangement of the heat insulating refractory 10 in the second stage 32 is shifted from the first stage 31 by 1/2 pitch. Therefore, the recessed portions 21 and 22 in each heat insulating refractory 10 are not opposed to the recessed portions 21 and 22 in the heat insulating refractory 10 adjacent in the vertical direction.

次に、本発明の断熱耐火物の好ましい製造方法について説明する。本製造方法は、（イ）アルミナ粒子又はジルコニア粒子を含む混練物を用いて成形体を得る工程と、（ロ）該成形体を焼成して目的とする耐火物を得る工程とに大別される。以下、それぞれの工程について説明する。   Next, the preferable manufacturing method of the heat insulation refractory of this invention is demonstrated. This production method is roughly divided into (i) a step of obtaining a molded body using a kneaded product containing alumina particles or zirconia particles, and (b) a step of firing the molded body to obtain a target refractory. The Hereinafter, each process will be described.

先ず（イ）の工程においては、アルミナ粒又はジルコニア粒子、水溶性高分子材料、多糖類、焼成によって消失可能な造孔粒子、及び液媒体を混練して混練物を得る。この混練物を構成する成分であるアルミナ粒子又はジルコニア粒子としては高純度のものを用いることが好ましい。安定化ジルコニア粒子を用いる場合には、ジルコニア粒子の純度は、ジルコニア粒子と安定化剤との合計値とする。具体的には、純度９８．５重量％以上、特に９９．０重量％以上のものを用いることが好ましい。そのような高純度のアルミナ粒子又はジルコニア粒子は商業的に容易に入手可能である。   First, in the step (a), alumina particles or zirconia particles, a water-soluble polymer material, a polysaccharide, pore-forming particles that can be lost by firing, and a liquid medium are kneaded to obtain a kneaded product. It is preferable to use high-purity alumina particles or zirconia particles as components constituting the kneaded product. When the stabilized zirconia particles are used, the purity of the zirconia particles is the total value of the zirconia particles and the stabilizer. Specifically, it is preferable to use those having a purity of 98.5% by weight or more, particularly 99.0% by weight or more. Such high purity alumina particles or zirconia particles are readily available commercially.

アルミナ粒子又はジルコニア粒子としては、骨材原料としての比較的大粒径のものと、ボンドとしての比較的小粒径のものとを併用することが好ましい。骨材原料としてのアルミナ粒子又はジルコニア粒子は、その粒径が３０〜５００μｍ、特に４５〜３００μｍであることが、気孔率及び強度の維持の点から好ましい。一方、ボンドとしてのアルミナ粒子又はジルコニア粒子は、その粒径が０．１〜３０μｍ、特に１〜２５μｍであることが好ましい。アルミナ粒子又はジルコニア粒子の粒径は、マイクロトラックやレーザー式粒度分布測定器によって測定される。   As the alumina particles or zirconia particles, it is preferable to use a particle having a relatively large particle size as an aggregate material and a particle having a relatively small particle size as a bond. Alumina particles or zirconia particles as an aggregate raw material preferably have a particle size of 30 to 500 μm, particularly 45 to 300 μm from the viewpoint of maintaining porosity and strength. On the other hand, the alumina particles or zirconia particles as a bond preferably have a particle size of 0.1 to 30 μm, particularly 1 to 25 μm. The particle size of the alumina particles or zirconia particles is measured by a microtrack or a laser type particle size distribution analyzer.

混練物中の骨材原料とボンドとの割合は、気孔率を高める観点及び断熱耐火物の強度の維持の観点から、骨材５０〜９０重量％／ボンド５０〜１０重量％、特に骨材６０〜８０重量％／ボンド４０〜２０重量％とすることが好ましい。   The ratio between the aggregate raw material and the bond in the kneaded product is 50 to 90% by weight of the aggregate / 50 to 10% by weight of the bond, particularly the aggregate 60 from the viewpoint of increasing the porosity and maintaining the strength of the heat insulating refractory. It is preferable to set it to -80 weight% / bond 40-20 weight%.

アルミナ粒子又はジルコニア粒子の形状は本製造方法において特に臨界的でなく、商業的に入手可能な種々の形状のものを用いることができる。   The shape of the alumina particles or zirconia particles is not particularly critical in the present production method, and various commercially available shapes can be used.

アルミナ粒子又はジルコニア粒子には、中実のものと中空のものがあることが知られている。一般的には、中実の粒子よりも中空のものを用いることで、気孔率の高い断熱耐火物を得ることができる。しかし、それよりも更に高い気孔率を得るためには、中空のアルミナ粒子又はジルコニア粒子の使用では、限界がある。本製造方法においては、後述する水溶性高分子材料、多糖類及び造孔粒子を用いることで、中空のアルミナ系粒子又はジルコニア系粒子を使用せずに、先に述べた範囲の高い気孔率を達成する断熱耐火物を得ることができる。   It is known that there are solid and hollow alumina particles or zirconia particles. In general, a heat-insulating refractory having a high porosity can be obtained by using hollow particles rather than solid particles. However, there is a limit to the use of hollow alumina particles or zirconia particles in order to obtain a higher porosity. In this production method, by using the water-soluble polymer material, polysaccharides and pore-forming particles described later, a high porosity in the above-mentioned range can be obtained without using hollow alumina-based particles or zirconia-based particles. An adiabatic refractory to achieve can be obtained.

焼成によって消失可能な造孔粒子は、目的とする断熱耐火物の気孔率を高くするために用いられる。この造孔粒子は、空気中で加熱することによって消失が可能なものである。例えば、加熱温度１５０℃以上で、少なくとも消失が始まるものを用いることが好ましい。そのような粒子は、例えばアクリル酸エステル、ポリイミド、ポリスチレン、ポリエチレン、ポリプロピレン、エチレンビニルアセテートなどの有機高分子化合物から構成されている。ここで言う「消失」とは、加熱による酸化で分解し、残存物が何も残らない状態になることである。   The pore-forming particles that can disappear by firing are used to increase the porosity of the intended heat-insulating refractory. The pore-forming particles can be lost by heating in air. For example, it is preferable to use one at which the disappearance begins at least at a heating temperature of 150 ° C. Such particles are composed of organic polymer compounds such as acrylic acid ester, polyimide, polystyrene, polyethylene, polypropylene, and ethylene vinyl acetate. The term “disappearance” as used herein means that the residue is decomposed by oxidation by heating, and no residue remains.

造孔粒子の粒径は、目的とする断熱耐火物の気孔率や強度に影響を及ぼす。この観点から、造孔粒子の粒径は０．５〜５ｍｍ、特に１〜４ｍｍであることが好ましい。造孔粒子の粒径、上述したアルミナ粒子又はジルコニア粒子の粒径の測定方法と同様の方法で測定される。造孔粒子の形状も、目的とする断熱耐火物の嵩比重や気孔率に影響を及ぼす。この観点から、形状がより真球に近い造孔粒子を用いることが好ましい。   The particle diameter of the pore-forming particles affects the porosity and strength of the intended heat insulating refractory. From this viewpoint, the particle diameter of the pore-forming particles is preferably 0.5 to 5 mm, particularly 1 to 4 mm. It is measured by the same method as the method for measuring the particle diameter of the pore-forming particles and the above-mentioned alumina particles or zirconia particles. The shape of the pore-forming particles also affects the bulk specific gravity and porosity of the intended heat-insulating refractory. From this viewpoint, it is preferable to use pore-forming particles whose shape is closer to a true sphere.

混練物中に含まれる造孔粒子の割合は、目的とする断熱耐火物の気孔率と強度とのバランスの観点から、アルミナ粒子又はジルコニア粒子１００ｇに対し１００〜３００ｃｍ3特に１５０〜２５０ｃｍ3とすることが好ましい。 The proportion of pore-forming particles contained in the kneaded material, from the point of view of balance between the porosity and strength of the heat-insulating refractories of interest, and 100～300Cm 3 particularly 150～250Cm 3 to alumina particles or zirconia particles 100g It is preferable.

混練物中に含まれる水溶性高分子材料及び多糖類は、該混練物から成形される成形体の保形性を高めるために用いられる。詳細には、気孔率が高い断熱耐火物を得るためには、混練物中に含まれる造孔粒子の割合を高くすることが有利である。しかし、造孔粒子の割合を高くすると、混練物から成形体を成形する場合の保形性が低下して、目的とする形状の成形体が得られにくい。また、プレス圧を低くした場合においても、成形体の保形性が低下して目的の成形体が得られにくくなる。これに対して、水溶性高分子材料及び多糖類を結合剤として用いることで成形体の保形性が高まるので、混練物中に含まれる造孔粒子の割合が高くなっても、成形体を首尾良く成形することができ、また、プレス圧が低くても成形体を首尾よく成形できる。更に、後述する（ロ）の焼成工程も首尾良く行うことができる。   The water-soluble polymer material and polysaccharide contained in the kneaded product are used for enhancing the shape retention of a molded product formed from the kneaded product. Specifically, in order to obtain a heat-insulating refractory having a high porosity, it is advantageous to increase the ratio of the pore-forming particles contained in the kneaded product. However, if the ratio of the pore-forming particles is increased, the shape retention in the case of molding a molded body from the kneaded product is lowered, and it is difficult to obtain a molded body having a desired shape. Further, even when the press pressure is lowered, the shape retention of the molded body is lowered and it is difficult to obtain the desired molded body. On the other hand, since the shape retention of the molded body is enhanced by using a water-soluble polymer material and a polysaccharide as a binder, the molded body can be produced even if the ratio of the pore-forming particles contained in the kneaded product is increased. It can be molded successfully, and the molded body can be molded successfully even when the press pressure is low. Furthermore, the firing step (b) described later can be carried out successfully.

前記の観点から、水溶性高分子材料としては少量の使用でも高い結合力を発現するものを用いることが好ましい。例えば、ポリビニルアルコール、セルロース、寒天、ゼラチンなどを用いることができる。   From the above viewpoint, it is preferable to use a water-soluble polymer material that exhibits a high binding force even when used in a small amount. For example, polyvinyl alcohol, cellulose, agar, gelatin or the like can be used.

多糖類も、水溶性高分子材料と同様の観点から好適な材料が選定される。例えば、デンプン、グリコーゲンなどを用いることができる。   As the polysaccharide, a suitable material is selected from the same viewpoint as the water-soluble polymer material. For example, starch, glycogen, etc. can be used.

水溶性高分子材料は、極力少ない使用量で、必要かつ十分な結合力が発揮されることが好ましい。多糖類に関しても同様である。この観点から、混練物中に含まれる水溶性高分子材料の割合は、５〜１５重量％、特に８〜１２重量％とすることが好ましい。また、混練物中に含まれる多糖類の割合は、０．１〜３重量％、特に０．５〜２重量％とすることが好ましい。   It is preferable that the water-soluble polymer material exhibits a necessary and sufficient binding force with a minimal amount of use. The same applies to polysaccharides. From this viewpoint, the proportion of the water-soluble polymer material contained in the kneaded product is preferably 5 to 15% by weight, particularly 8 to 12% by weight. Moreover, it is preferable that the ratio of the polysaccharide contained in a kneaded material shall be 0.1 to 3 weight%, especially 0.5 to 2 weight%.

混練物に含まれる液媒体としては基本的には水を用いる。   As a liquid medium contained in the kneaded product, water is basically used.

上述した各成分を均一に混合して目的とする混練物を得る。混合の方法に特に制限はなく、当該技術分野において用いられている方法と同様の方法を用いることができる。このようにして得られた混練物を用いて、所定の形状を有する成形体を得る。成形には例えば、所定形状の金型内に混練物を充填し、該混練物を所定の圧力でプレスするプレス成形を用いることができる。プレス成形は、混練物に含まれる造孔粒子が破壊されないことを上限値とする圧力で行われることが好ましい。この圧力は、造孔粒子の種類や粒径等に依存する。一般的な範囲としては５０〜５００ｋｇ／ｃｍ2を採用することが好ましい。 The above-described components are uniformly mixed to obtain a desired kneaded product. There is no restriction | limiting in particular in the method of mixing, The method similar to the method used in the said technical field can be used. Using the kneaded product thus obtained, a molded body having a predetermined shape is obtained. For example, press molding in which a kneaded product is filled in a mold having a predetermined shape and the kneaded product is pressed at a predetermined pressure can be used. The press molding is preferably performed at a pressure with an upper limit that the pore-forming particles contained in the kneaded product are not destroyed. This pressure depends on the type and particle size of the pore-forming particles. As a general range, it is preferable to employ 50 to 500 kg / cm 2 .

このようにして得られた成形体は、金型内で又は金型から取り出されて乾燥工程に付される。乾燥工程においては、加熱や赤外線の照射等の手段によって液媒体が除去される。乾燥は、成形体に含まれる液媒体の割合が好ましくは１重量％、より好ましくは０．５重量％以下になるまで行われる。   The molded body thus obtained is taken out of the mold or from the mold and subjected to a drying process. In the drying step, the liquid medium is removed by means such as heating or infrared irradiation. Drying is performed until the ratio of the liquid medium contained in the molded body is preferably 1% by weight, more preferably 0.5% by weight or less.

乾燥された後の成形体は、（ロ）の焼成工程に付される。焼成は、空気中で行うことができる。また焼成は、成形体に含まれている造孔粒子が消失する条件下に行われる。この焼成条件は造孔粒子の種類や粒径等に依存するが、一般的な条件として、１４００〜１８００℃の温度を１〜１０時間保持することで、造孔粒子が消失し、かつアルミナ粒子又はジルコニア粒子が十分に焼結する。   The molded body after being dried is subjected to the firing step (b). Firing can be performed in air. Firing is performed under conditions where pore-forming particles contained in the molded body disappear. This firing condition depends on the type and particle size of the pore-forming particles, but as a general condition, the pore-forming particles disappear by holding the temperature of 1400 to 1800 ° C. for 1 to 10 hours, and the alumina particles Alternatively, the zirconia particles are sufficiently sintered.

このようにして目的とする断熱耐火物が得られる。この耐火物はアルミナ又はジルコニアの純度が高く、かつ耐火物の劣化の原因となるシリカやアルカリ金属酸化物等の不純物の含有量が少ないので、アルカリを含むワークを焼成するための窯炉の内張り断熱耐火物として特に好適に用いられる。例えば、アルカリイオン電池材料を焼成するための窯炉に好適に用いられる。この用途以外にも、電子部品用焼成炉等にも好適に用いられる。   In this way, the intended heat insulating refractory is obtained. This refractory has a high purity of alumina or zirconia and has a low content of impurities such as silica and alkali metal oxides that cause deterioration of the refractory. It is particularly preferably used as an adiabatic refractory. For example, it is suitably used in a kiln for firing alkaline ion battery materials. In addition to this application, it is also suitably used in electronic component firing furnaces and the like.

以下、実施例により本発明を更に詳細に説明する。しかしながら本発明の範囲は、かかる実施例に制限されない。特に断らない限り、「％」及び「部」はそれぞれ「重量％」及び「重量部」を意味する。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to such examples. Unless otherwise specified, “%” and “part” mean “% by weight” and “part by weight”, respectively.

〔実施例１〕
（１）混練物の調製
骨材原料として平均粒径１００μｍの中実アルミナ粒子（純度９９．７％）を７０部用いた。また、ボンドとして平均粒径５μｍの中実アルミナ粒子（純度９９．８％）を３０部用いた。水溶性高分子材料としてポリビニルアルコールを１部用いた。多糖類としてデンプンを２部用いた。造孔粒子として平均粒径３ｍｍのスチレンビーズをアルミナ粒子１００ｇに対して１５０ｃｍ3用いた。これらを１０部の水と均一に混合して混練物を得た。 [Example 1]
(1) Preparation of kneaded material As an aggregate raw material, 70 parts of solid alumina particles (purity 99.7%) having an average particle diameter of 100 μm were used. Further, 30 parts of solid alumina particles (purity 99.8%) having an average particle diameter of 5 μm were used as bonds. One part of polyvinyl alcohol was used as the water-soluble polymer material. Two parts of starch was used as the polysaccharide. Styrene beads having an average particle size of 3mm as the pore-forming particles were used 150 cm 3 with respect to the alumina particles 100 g. These were uniformly mixed with 10 parts of water to obtain a kneaded product.

（２）成形体の成形
得られた混練物を金型内に充填し、１００ｋｇ／ｃｍ2の圧力でプレス成形し、成形体を得た。この金型は図１に示す断熱耐火物に対応する形状を有していた。得られた成形体を１００℃に加熱して水分含有率が０．５％以下になるまで乾燥を行った。成形体を観察したところ、造孔粒子の破壊は観察されなかった。 (2) Molding of molded body The obtained kneaded material was filled in a mold and press molded at a pressure of 100 kg / cm 2 to obtain a molded body. This mold had a shape corresponding to the heat insulating refractory shown in FIG. The obtained molded body was heated to 100 ° C. and dried until the water content became 0.5% or less. When the molded body was observed, no destruction of the pore-forming particles was observed.

（３）成形体の焼成
乾燥後の成形体を、空気中、１６００℃で、５時間焼成し、図１に示す形状の耐火物を得た。この耐火物は、長さ２３０ｍｍ、幅１１５ｍｍ、厚さ６５ｍｍであった。 (3) Firing of the molded body The dried molded body was fired in the air at 1600 ° C. for 5 hours to obtain a refractory having the shape shown in FIG. This refractory had a length of 230 mm, a width of 115 mm, and a thickness of 65 mm.

〔実施例２〕
以下の表１に示す条件を用いて実施例１と同様にして、図１に示す形状の断熱耐火物を得た。 [Example 2]
A heat-insulating refractory having the shape shown in FIG. 1 was obtained in the same manner as in Example 1 using the conditions shown in Table 1 below.

〔実施例３〕
骨材原料として平均粒径１５０μｍの中実のＣａＯ安定化ジルコニア粒子（純度：ＺｒＯ2９５．６％、ＣａＯ３．７％）を６０部、ボンドとして中実の平均粒径２μｍのＣａＯ安定化ジルコニア粒子（純度：ＺｒＯ2９５．６％、ＣａＯ３．７％）を４０部、多糖類としてデンプンを２部、造孔粒子として平均粒径３ｍｍのスチレンビーズ粒子をジルコニア粒子１００ｇに対して１００ｃｍ3用い、８０ｋｇ／ｃｍ2の圧力でプレス成形した以外は実施例１と同様にして、図１に示す形状の断熱耐火物を得た。 Example 3
60 parts of solid CaO-stabilized zirconia particles (purity: ZrO 2 95.6%, CaO 3.7%) as an aggregate raw material with an average particle diameter of 150 μm, and CaO-stabilized zirconia with a solid average particle diameter of 2 μm as a bond particles (purity: ZrO 2 95.6%, CaO3.7% ) 100cm 3 using 40 parts, 2 parts starch as polysaccharide, a styrene bead particles having an average particle size of 3mm as the pore-forming particles with respect to the zirconia particles 100g A heat-insulating refractory having the shape shown in FIG. 1 was obtained in the same manner as in Example 1 except that press molding was performed at a pressure of 80 kg / cm 2 .

〔比較例１及び２〕
以下の表１に示す条件を用いて実施例１と同様にして、図１に示す形状の断熱耐火物を得た。 [Comparative Examples 1 and 2]
A heat-insulating refractory having the shape shown in FIG. 1 was obtained in the same manner as in Example 1 using the conditions shown in Table 1 below.

〔比較例３〕
イソライト工業株式会社製のアルミナ質耐火断熱レンガＬＢＫ−２８（商品名）を比較例３とした。 [Comparative Example 3]
Alumina refractory insulating brick LBK-28 (trade name) manufactured by Isolite Industry Co., Ltd. was used as Comparative Example 3.

Figure 2012020895
Figure 2012020895

〔性能評価〕
実施例及び比較例の断熱耐火物について、上述の方法で気孔率を測定した。また、耐熱耐火物の化学分析を行った。これらに加えて断熱耐火物の圧縮強さ及び曲げ強さをＪＩＳ Ｒ２６１５及びＪＩＳ Ｒ２６１９に準じて測定した。更に耐アルカリ性を、下記の方法により評価した。その結果を以下の表２に示す。 [Performance evaluation]
About the heat insulation refractories of an Example and a comparative example, the porosity was measured by the above-mentioned method. In addition, chemical analysis of heat and refractories was conducted. In addition to these, the compressive strength and bending strength of the heat insulating refractory were measured according to JIS R2615 and JIS R2619. Furthermore, alkali resistance was evaluated by the following method. The results are shown in Table 2 below.

〔耐アルカリ性〕
坩堝に炭酸リチウム（Ｌｉ2ＣＯ3）を入れ、実施例及び比較例で得られた断熱耐火物により蓋をした。坩堝を１０００℃で１０時間加熱した。その後、室温まで冷却し、断熱耐火物を坩堝から取り外した。取り外した断熱耐火物の炭酸リチウムと対向していた面の状態を観察し、該断熱耐火物の耐アルカリ性を評価した。評価基準は以下のとおりである。
○：断熱耐火物の表面の変化が観察されない
△：断熱耐火物の表面にボロツキは観察されないが、変色は観察される
×：断熱耐火物の表面にボロツキが観察される [Alkali resistance]
Lithium carbonate (Li 2 CO 3 ) was placed in the crucible, and the crucible was covered with the heat insulating refractories obtained in the examples and comparative examples. The crucible was heated at 1000 ° C. for 10 hours. Then, it cooled to room temperature and removed the heat insulation refractory from the crucible. The state of the surface of the heat-insulating refractory removed from the surface facing the lithium carbonate was observed, and the alkali resistance of the heat-insulating refractory was evaluated. The evaluation criteria are as follows.
○: No change in the surface of the heat-insulating refractory is observed △: No battering is observed on the surface of the heat-insulating refractory, but discoloration is observed ×: Blasting is observed on the surface of the heat-insulating refractory

Figure 2012020895
Figure 2012020895

表２に示す結果から明らかなように、各実施例の断熱耐火物は、比較例１及び２の断熱耐火物に比べて、気孔率が高いものであることが判る。強度に関しては、各実施例の断熱耐火物は、比較例１及び２の断熱耐火物よりも低い値を示しているが、実使用に差し支えのない強度は有している。比較例３の断熱耐火物は、気孔率は比較的高く、また圧縮強さや曲げ強さの値も大きいが、アルミナの純度が低く、シリカ等の不純物の量が多いことから、実施例１〜３の断熱耐火物に比べて、耐アルカリ性が劣るものであった。   As is clear from the results shown in Table 2, it can be seen that the heat-insulating refractories of each Example have a higher porosity than the heat-insulating refractories of Comparative Examples 1 and 2. Regarding the strength, the heat-insulating refractory of each example shows a lower value than the heat-insulating refractories of Comparative Examples 1 and 2, but has strength that does not interfere with actual use. The heat insulating refractory of Comparative Example 3 has a relatively high porosity and a large value of compressive strength and bending strength, but the purity of alumina is low and the amount of impurities such as silica is large. Compared with the heat insulation refractory material 3, the alkali resistance was inferior.

１０ 断熱耐火物
１１ 上面
１２ 下面
２１，２２ 凹陥部 10 Insulating refractory 11 Upper surface 12 Lower surface 21, 22 Recessed portion

Claims (9)

アルミナセラミックス又はジルコニアセラミックスからなり、シリカを含まないか、又は含んだとしても１重量％以下であり、気孔率が６５〜８５％であり、かつ圧縮強さが２ＭＰａ以上であることを特徴とする断熱耐火物。   It is made of alumina ceramics or zirconia ceramics, does not contain silica, or even if it contains 1% by weight or less, has a porosity of 65 to 85%, and has a compressive strength of 2 MPa or more. Insulated refractory. アルカリ金属酸化物を含まないか又は含んだとしても０．３重量％以下である請求項１記載の断熱耐火物。   The heat-insulating refractory according to claim 1, which does not contain an alkali metal oxide or contains 0.3% by weight or less. セラミックス粒子として中実のもののみが用いられている請求項１又は２に記載の断熱耐火物。   The heat-insulating refractory according to claim 1 or 2, wherein only solid particles are used as ceramic particles. アルカリイオン電池材料焼成用窯炉の内張り断熱耐火物として用いられる請求項１ないし３のいずれか一項に記載の断熱耐火物。   The heat-insulating refractory according to any one of claims 1 to 3, wherein the heat-insulating refractory is used as a lining heat-insulating refractory for a furnace for firing an alkaline ion battery material. 複数個が組み上げられて使用され、組み上げ状態における隣り合う耐火物の対向面に、１又は２以上の凹陥部を有する請求項１ないし４のいずれか一項に記載の断熱耐火物。   The heat-insulating refractory according to any one of claims 1 to 4, wherein a plurality of the refractories are assembled and used, and have one or two or more recessed portions on opposing surfaces of adjacent refractories in the assembled state. 組み上げ状態において上下に隣り合う前記耐火物における上面及び下面の双方に凹陥部を有し、
上面における凹陥部が形成されている位置に対応する下面の位置には凹陥部が形成されておらず、かつ下面における凹陥部が形成されている位置に対応する上面の位置にも凹陥部が形成されていない請求項５記載の断熱耐火物。 In the assembled state, it has a recessed portion on both the upper surface and the lower surface of the refractory adjacent to the top and bottom,
No recess is formed at the position of the lower surface corresponding to the position where the recess is formed on the upper surface, and a recess is also formed at the position of the upper surface corresponding to the position where the recess is formed on the lower surface. The heat-insulating refractory according to claim 5, which is not used. 請求項１記載の断熱耐火物の製造方法であって、
アルミナ粒子又はジルコニア粒子、水溶性高分子材料、多糖類、焼成によって消失可能な造孔粒子、及び液媒体を混練して得られた混練物を、該造孔粒子が破壊されない圧力でプレス成形して成形体を得、次いで
該造孔粒子が消失する条件下に該成形体を焼成することを特徴とする断熱耐火物の製造方法。 It is a manufacturing method of the heat insulation refractory according to claim 1,
A kneaded product obtained by kneading alumina particles or zirconia particles, a water-soluble polymer material, a polysaccharide, pore-forming particles that can be lost by firing, and a liquid medium is press-molded at a pressure at which the pore-forming particles are not destroyed. A method for producing a heat-insulating refractory, characterized in that a molded body is obtained and then the molded body is fired under conditions where the pore-forming particles disappear. 前記造孔粒子を、アルミナ粒子又はジルコニア粒子１００ｇに対して１００〜３００ｃｍ3用いる請求項７記載の製造方法。 The manufacturing method according to claim 7, wherein the pore-forming particles are used in an amount of 100 to 300 cm 3 with respect to 100 g of alumina particles or zirconia particles. 前記造孔粒子の粒径が０．５〜５ｍｍである請求項７又は８記載の製造方法。   The manufacturing method according to claim 7 or 8, wherein the pore-forming particles have a particle size of 0.5 to 5 mm.
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CN103206862A (en) * 2013-04-22 2013-07-17 五力机电科技（昆山）有限公司 Lower high pressure laminate
JP2015157724A (en) * 2014-02-24 2015-09-03 イソライト工業株式会社 Light weight alkali resistant fire resistant thermal insulating brick and manufacturing method therefor
DE112019006604T5 (en) 2019-01-09 2021-11-11 Mitsubishi Electric Corporation CONTROL DEVICE AND CONTROL PROCEDURE

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