JPH04130050A - Refractory material and its production - Google Patents
Refractory material and its productionInfo
- Publication number
- JPH04130050A JPH04130050A JP2246295A JP24629590A JPH04130050A JP H04130050 A JPH04130050 A JP H04130050A JP 2246295 A JP2246295 A JP 2246295A JP 24629590 A JP24629590 A JP 24629590A JP H04130050 A JPH04130050 A JP H04130050A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- alumina
- firing
- sieve
- point
- 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.)
- Pending
Links
- 239000011819 refractory material Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 60
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000010304 firing Methods 0.000 claims abstract description 22
- 230000005484 gravity Effects 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000000465 moulding Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000011109 contamination Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229920002472 Starch Polymers 0.000 abstract description 3
- 239000008107 starch Substances 0.000 abstract description 3
- 235000019698 starch Nutrition 0.000 abstract description 3
- 238000010586 diagram Methods 0.000 abstract description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 2
- 229910001679 gibbsite Inorganic materials 0.000 abstract 2
- 238000004898 kneading Methods 0.000 abstract 1
- 239000011230 binding agent Substances 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 239000012535 impurity Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910001570 bauxite Inorganic materials 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004901 spalling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明はアルミニウム及びアルミニウム合金（以下「ア
ルミニウム」と称す）等の溶湯用の炉。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a furnace for molten metal such as aluminum and aluminum alloys (hereinafter referred to as "aluminum").
樋及び湯溜まり等の装置の内張りに用いる耐火材及びそ
の製造法に関する。This invention relates to fireproof materials used for lining equipment such as gutters and hot water pools, and methods for producing the same.
［従来の技術］
例えばアルミニウム溶湯を対象とした炉、樋及び湯溜ま
り等の装置の内張り用の材料としては、アルミナの含ま
れた定形または不定形耐火材が使用されているが、溶解
炉のような場合には、溶解に先立ってアルミニウム塊が
高所から炉内に投入され、溶解後各種溶製作業を施す間
、長時間溶湯と接触する。従って、このような溶湯と接
触する装置の内張り用の材料に要求される特性としては
、１０機械的強度が大きく、アルミニウム塊の落下衝撃
で割れないこと。[Prior Art] For example, fixed or unshaped refractory materials containing alumina are used as lining materials for equipment such as furnaces, gutters, and pools for processing molten aluminum. In such cases, the aluminum ingot is introduced into the furnace from a high place prior to melting, and comes into contact with the molten metal for a long period of time during various melting operations after melting. Therefore, the characteristics required for the lining material of equipment that comes into contact with molten metal are as follows: 10. It must have high mechanical strength and not crack under the impact of falling aluminum blocks.
２、耐熱性及び耐スポーリング性を有すること。2. Must have heat resistance and spalling resistance.
３、気孔が小さく、溶湯の浸透がないこと。3. Pores are small and there is no penetration of molten metal.
４、溶融アルミニウムに対して耐食性があり、溶湯への
不純物の溶出がないこと
などが挙げられる。4. It has corrosion resistance against molten aluminum and does not elute impurities into the molten metal.
このような特性を有するものとしてアルミナ分を９８〜
９９％含有する耐火材が市販されている。As a material with such characteristics, the alumina content is 98 to 98%.
Refractory materials containing 99% are commercially available.
耐火材の緻密性（即ちかさ比重）と強度は、原料の特性
の他に、骨材の配合粒度、結合材の混合量、保形材添加
量並びに成形・焼成条件による。The density (i.e., bulk specific gravity) and strength of a refractory material depend on the characteristics of the raw material, as well as the blended particle size of the aggregate, the amount of binder mixed, the amount of shape retainer added, and the forming and firing conditions.
従って、これらの製造条件を適切に選ぶ必要がある。即
ち、高アルミナ質の市販耐火材のかさ比重は３．００〜
３．２５ｇ／ｃｍ３の範囲に、また圧縮強度と曲げ強度
は、それぞれ７５０〜１９００ｋｇ／ｃｍ２と２００〜
３８０ｋｇ／ｃｍ２の範囲にあり、−射的にはかさ比重
３．１０ ｇ ７ｃｍ３．圧縮強度１２００ ｋｇ／
ｃｍ２及び曲げ強度３００ ｋｇ／ ｃｍ２の耐火材が
使用されている。Therefore, it is necessary to appropriately select these manufacturing conditions. In other words, the bulk specific gravity of commercially available high alumina refractory materials is 3.00~
3.25g/cm3, and the compressive strength and bending strength are 750-1900kg/cm2 and 200-200kg/cm2, respectively.
It is in the range of 380 kg/cm2, and the bulk specific gravity is 3.10 g 7cm3. Compressive strength 1200 kg/
cm2 and a bending strength of 300 kg/cm2.
しかしながら、市販されている耐火材を構成する骨材等
にはＰをＰ２Ｏ５として０．８〜１．２％。However, aggregates constituting commercially available refractory materials contain P in an amount of 0.8 to 1.2% as P2O5.
ＮａをＮａ２Ｏとして０．２〜０．３％を含有する。Contains 0.2 to 0.3% Na as Na2O.
特にＰが多いのは結合材としてリン酸系の無機バインダ
ーを使用しているためと推定される。結合材として、ケ
イ酸系およびホウ酸系の無機バインダーを使用すること
もあるが、この場合には、焼成後、耐火材内にＳ ｉ
０２． Ｂ２０Ｂが残留する。このようなＰ、Ｓｉおよ
びＢ等の化合物はアルミニウム溶湯と反応してＰ、
Ｓｉ、 Ｂが溶湯中に溶出するので、溶湯が汚染され
るばかりでなく、耐火材の骨材間の結合力が弱まり強度
が低下する。It is presumed that the reason why P is particularly high is because a phosphoric acid-based inorganic binder is used as a binding material. Silicic acid-based and boric acid-based inorganic binders are sometimes used as binding materials, but in this case, Si is added to the refractory material after firing.
02. B20B remains. These compounds such as P, Si and B react with molten aluminum to form P,
Since Si and B are eluted into the molten metal, the molten metal is not only contaminated, but also the bonding force between the aggregates of the refractory material is weakened, resulting in a decrease in strength.
［発明が解決しようとする課題］
発明者らは、リン酸系、ホウ酸系及びケイ酸系無機バイ
ンダーなどアルミニウム溶湯に侵食され易い結合材を使
用しないで、高いかさ比重と強度を持ち、しかもアルミ
ニウム溶湯に対して耐食性のある耐火材の研究を進め、
微粒アルミナ特にその中でも水酸化アルミニウムを焼成
した微粒アルミナは易焼結性に優れていることに着目し
、これを結合材として用いることによって実質的にアル
ミナ質のみからなる耐火材が得られ上述の問題点を解決
できることを見出し、その製造法について研究を進め、
本発明を完成した。[Problems to be Solved by the Invention] The inventors have developed a material that has high bulk specific gravity and strength without using binders that are easily corroded by molten aluminum, such as phosphoric acid-based, boric acid-based and silicic acid-based inorganic binders. We are conducting research into fireproof materials that are resistant to corrosion against molten aluminum.
We focused on the fact that fine alumina, especially fine alumina made by calcining aluminum hydroxide, has excellent sintering properties, and by using it as a binder, we can obtain a refractory material consisting essentially of alumina. We discovered that the problem could be solved, and conducted research on the manufacturing method.
The invention has been completed.
［課題を解決するための手段］
本発明によれば、溶融アルミナと水酸化アルミニウムを
焼成した微粒アルミナの焼成体であって、該焼成体のか
さ比重が３．０以上であることを特徴とする溶湯汚染の
少ない耐火材及びその製造法が提供される。[Means for Solving the Problems] According to the present invention, there is provided a fired body of fine alumina obtained by firing molten alumina and aluminum hydroxide, characterized in that the bulk specific gravity of the fired body is 3.0 or more. Provided are a refractory material that causes less molten metal contamination, and a method for producing the same.
［作用］
主含有成分であるアルミナを表示する場合、通常全体量
を１００％とし、不純物の分析値を合計したものを全体
量から差し引いた残量で表示されるが、本発明における
「アルミナ含有量」とは、アルミナ分として分析した量
である。[Function] When displaying alumina, which is the main component, the total amount is usually 100%, and the total amount of impurity analysis values is subtracted from the total amount, and the remaining amount is displayed. "Amount" is the amount analyzed as alumina content.
本発明の耐火材は骨材として溶融アルミナ、結合材とし
て水酸化アルミニウムを焼成した微粒アルミナを使用す
る。溶融アルミナは、アルミナまたはボーキサイトを電
気などのエネルギーを用いて溶融し、冷却後粉砕し粒度
を調整して得られる。The refractory material of the present invention uses fused alumina as an aggregate and fine alumina obtained by firing aluminum hydroxide as a binder. Fused alumina is obtained by melting alumina or bauxite using energy such as electricity, cooling it, and then crushing it to adjust the particle size.
このようにして得られた幾つかの粒度区分を持つ溶融ア
ルミナを用意し、第１図に示す範囲内においてこれらを
適切に配合することによって成形後のかさ比重及び強度
を最も高くすることができる。By preparing the molten alumina obtained in this way with several particle size classifications and appropriately blending them within the range shown in Figure 1, it is possible to maximize the bulk specific gravity and strength after molding. .
アルミナを溶融して得られる溶融アルミナは通常、アル
ミナの純度で９９％以上である。ボーキサイトを溶融し
て得られる溶融アルミナは、通常。Fused alumina obtained by melting alumina usually has an alumina purity of 99% or more. Fused alumina is usually obtained by melting bauxite.
アルミナの純度で９５％以上、不純物としてＴｉＯ□を
１〜３％含有する。従って、アルミナからの溶融アルミ
ナを使用した場合は純度が良いので、溶湯を汚染するこ
とが殆どない。一方、ボーキサイトからの溶融アルミナ
は前者と比べて不純物が多いが、以下に説明するように
結合材として微粒アルミナを使用するので溶湯を汚染す
ることが殆どない。The purity of alumina is 95% or more, and it contains 1 to 3% TiO□ as an impurity. Therefore, when molten alumina made from alumina is used, the purity is high and there is almost no contamination of the molten metal. On the other hand, molten alumina made from bauxite has more impurities than the former, but as explained below, fine alumina particles are used as a binder, so the molten metal is hardly contaminated.
即ち、微粒アルミナの混合量を骨材１００重量部に対し
て１０重量部以上含有させた場合は、成形体の骨材粒子
表面は微粒アルミナによって被覆され、それによって焼
成後溶湯が骨材と直接に接触することがなくなり溶湯の
汚染が少ないものと思われる。That is, when the mixed amount of fine alumina is 10 parts by weight or more based on 100 parts by weight of aggregate, the surface of the aggregate particles of the compact is coated with fine alumina, so that the molten metal after firing is directly connected to the aggregate. It is thought that there will be less contamination of the molten metal as there will be no contact with the molten metal.
ところで、結合材の微粒アルミナは水酸化アルミニウム
を焼成しアルミナ化したものである。このアルミナの純
度は９９％以上である。Incidentally, the fine alumina used as the binder is made by firing aluminum hydroxide to form alumina. The purity of this alumina is 99% or more.
溶融アルミナの粒度分布は、第１図に示すように、対数
目盛りの横軸を溶融アルミナ粒子径（ｍｍ）。For the particle size distribution of molten alumina, as shown in Figure 1, the horizontal axis of the logarithmic scale is the molten alumina particle diameter (mm).
等間隔目盛りの縦軸を篩上（％）とした図面において、
点 Ａ：粒子径１０ｍｍ、篩上 ０％
Ｂ：粒子径 ４ｍｍ、篩上 ０％
Ｃ：粒子径０ 、１ ｍｍ、篩上 ５０％Ｄ二粒子径０
．００１ｍｍ、篩上１００％Ｅ二粒子径０ 、１ ｍｍ
、篩上１００％で囲まれた領域ＡＢＣＤＥ内に含まれ、
がつ直線ＡＢ上の１点と直殿ＤＥ上の１点を両端とする
直線または曲線に沿う粒度分布を有するように配合する
。以下にその理由を説明する。In the drawing where the vertical axis of the evenly spaced scale is the sieve top (%), Point A: Particle size 10 mm, 0% on the sieve B: Particle size 4 mm, 0% on the sieve C: Particle size 0, 1 mm, 50 on the sieve %D2 particle size 0
．． 001mm, 100%E2 particle size on sieve 0, 1mm
, contained within the area ABCDE surrounded by 100% on the sieve,
The particles are blended so as to have a particle size distribution along a straight line or curve whose ends are one point on straight line AB and one point on straight line DE. The reason is explained below.
上記図形の点Ａは粒子径１０ｍｍ、点Ｂは粒子径４ｍｍ
の点で、最大粒子径としては、４ｍｍから１０ｍｍの範
囲の骨材が適当である。最大絞が４ｍｍより小さいと成
形体の焼成時収縮してヒビ割れを発生し、また１０ｍｍ
より大きいと、製品強度が低下する傾向にある。次に、
点Ｅは粒子径０ 、１ ｍｍ、点りはＯ，ＯＯｌｍｍ（
１μｍ）の点で、最小粒としては０ 、１ ｍｍ以下に
する必要がある。これは粒子間隙を微粉で充填すること
により気孔を減らし耐火材の緻密性を高めるためであり
、最小粒が０ 、１ ｍｍより大きいと十分に高いかさ
比重が得られない。また０、００１ｍｍの点りはその量
が僅かで、殆ど影響を及ぼさないので粒子径の下限とし
たものである。Point A in the above figure has a particle diameter of 10 mm, and point B has a particle diameter of 4 mm.
In this respect, aggregates with a maximum particle diameter in the range of 4 mm to 10 mm are appropriate. If the maximum drawing area is smaller than 4mm, the compact will shrink during firing and cracks will occur, and
If it is larger, the strength of the product tends to decrease. next,
At point E, the particle size is 0, 1 mm, and the point is O, OOlmm (
1 μm), the minimum grain size needs to be 0.1 mm or less. This is to reduce pores and improve the density of the refractory material by filling the gaps between particles with fine powder, and if the minimum particle size is larger than 0.1 mm, a sufficiently high bulk specific gravity cannot be obtained. In addition, since the amount of speckles of 0,001 mm is so small that it has almost no effect, it is set as the lower limit of the particle size.
また、点Ｃは粒子径０ 、１ ｍｍ、篩上５０％の点で
、この点を規定した理由は、０ 、１ ｍｍ以上の骨材
が骨材全体の５０％以上を占める必要があり、５０％以
下であると製品のかさ比重及び強度が十分に得られない
からである。好ましくは６０〜９０％である。In addition, point C is the point where the particle size is 0.1 mm and 50% on the sieve.The reason for specifying this point is that aggregates with a diameter of 0.1 mm or more must account for 50% or more of the total aggregate. This is because if it is less than 50%, the product will not have sufficient bulk specific gravity and strength. Preferably it is 60-90%.
以上の骨材は全体を幾つかの粒度範囲に分けて、それら
を全体の粒度分布が前記ＡＢＣＤＥの領域内に含まれ直
線ＡＢ及び直線ＤＥを両端に持つ直線または曲線に沿う
ように配合することにより、最密充填が得られる。The above aggregates should be divided into several particle size ranges and mixed so that the entire particle size distribution falls within the ABCDE area and follows a straight line or curved line with straight line AB and straight line DE at both ends. Close packing is obtained.
結合材には水酸化アルミニウムを焼成して得られた易焼
結性の微粒アルミナを用いる。これは骨材のアルミナと
異なり、加熱により容易に融着して骨材同士を結合させ
る機能を持つと共に、一部は粒間を埋めるのに役立つ。As the binder, easily sinterable fine alumina obtained by firing aluminum hydroxide is used. Unlike alumina, which is an aggregate, it easily fuses when heated and has the function of bonding aggregates together, and some of it also helps fill in the gaps between grains.
微粒アルミナの平均粒径は０．１μｍ〜１０μｍ１ 好
ましくは０．５μｍ〜２μｍであって、０．１μｍ未満
では凝集により分散し難く取扱上不都合であり、１０μ
ｍを超えると焼成時に完全には融着せず、結合が不十分
となる場合があって、耐火材の強度を低下させる虞があ
る。成分はＡｌ２Ｏ３として９９％以上で、不純物が少
ないものが好ましい。The average particle diameter of the fine alumina is 0.1 μm to 10 μm, preferably 0.5 μm to 2 μm, and if it is less than 0.1 μm, it will be difficult to disperse due to agglomeration and it will be difficult to handle.
If it exceeds m, complete fusion may not occur during firing, resulting in insufficient bonding, which may reduce the strength of the refractory material. The component is preferably 99% or more as Al2O3 and contains few impurities.
前記の溶融アルミナ１００重量部に対し、微粒アルミナ
１０〜７５重量部及び保形材０．１〜５重量部と水を加
えて混練し、成形する。溶融アルミナに対し微粒アルミ
ナが１０重量部未満では耐火材のかさ比重及び強度が低
く不十分であり、また７５重量部を超えると全体的に微
粉量が多い組成となり焼成時に収縮してヒビ割れを発生
してかさ比重及び強度が低下する傾向にある。To 100 parts by weight of the molten alumina, 10 to 75 parts by weight of fine alumina, 0.1 to 5 parts by weight of a shape retaining material, and water are added, kneaded, and molded. If the amount of fine alumina is less than 10 parts by weight relative to molten alumina, the bulk specific gravity and strength of the refractory material will be low and insufficient, and if it exceeds 75 parts by weight, the composition will have a large amount of fine powder overall, causing shrinkage and cracking during firing. This tends to cause the bulk specific gravity and strength to decrease.
さらに、焼成前の成形品形状を保持するために保形材を
用いる。保形材は焼成によって消失するものであり、例
えば澱粉、ＰＶＡ（ポリビニルアルコール）、ＭＣ（メ
チルセルロース）などが用いられる。混合割合は溶融ア
ルミナ１００重量部に対して０．１〜５重量部で、０．
１重量部未満では保形力が不足し、５重量部を超えると
焼成時に炭化物として気孔中に残存する虞れがある。使
用に当って保形材は濃度調整した水溶液として用いられ
る。Furthermore, a shape retaining material is used to maintain the shape of the molded product before firing. The shape-retaining material disappears by firing, and examples of the shape-retaining material used include starch, PVA (polyvinyl alcohol), and MC (methyl cellulose). The mixing ratio is 0.1 to 5 parts by weight with respect to 100 parts by weight of molten alumina.
If it is less than 1 part by weight, the shape retention power is insufficient, and if it exceeds 5 parts by weight, it may remain in the pores as carbide during firing. In use, the shape retaining material is used as an aqueous solution with adjusted concentration.
成形は常法に従って１００〜１０００ｋｇ／ｃｍ２で加
圧成形し、骨材間の充填を密にする。加重１００ ｋｇ
／ ｃｍ２以下では耐火材は充分ながさ比重が得られず
、また１ ０００ ｋｇ／ ｃｍ２以上では骨材粒が破
壊される危険がある。このようにして得られた成形体を
十分に乾燥した後、１３００℃以上、好ましくは１３５
０℃〜１８００℃の温度で焼成する。The molding is carried out under pressure of 100 to 1000 kg/cm2 according to a conventional method, and the filling between the aggregates is made dense. Weight 100 kg
/cm2 or less, the refractory material will not have a sufficient bulk specific gravity, and if it is more than 1,000 kg/cm2, there is a risk that the aggregate particles will be destroyed. After sufficiently drying the molded product thus obtained, the temperature is 1300°C or higher, preferably 135°C.
Calcinate at a temperature of 0°C to 1800°C.
焼成温度が１３００℃未満では微粒アルミナの融着が不
十分な場合がある。また１８００℃以上では汎用の工業
炉は使用できず、黒鉛発熱体を用いた高価な特殊炉を用
いる必要がある。If the firing temperature is less than 1300°C, the fusion of the fine alumina particles may be insufficient. Further, at temperatures above 1800° C., a general-purpose industrial furnace cannot be used, and an expensive special furnace using a graphite heating element must be used.
本発明に係る耐火材においては、骨材及び結合材ともに
高純度のアルミナを使用し、アルミニウム溶湯の侵食に
対して十分な耐久性を確保し、また結合材に水酸化アル
ミニウムから得られた易焼結性の微粒アルミナを使用し
ているので、低い焼成温度でも十分な結合力が得られる
。In the fireproof material according to the present invention, high-purity alumina is used for both the aggregate and the binder to ensure sufficient durability against the erosion of molten aluminum, and the binder is made of aluminum hydroxide. Since sinterable fine-grain alumina is used, sufficient bonding strength can be obtained even at low firing temperatures.
結合材の混合量が比較的多いので、微粒アルミナは骨材
を完全に被覆するとともに骨材粒子間にも充填され、耐
火材のかさ比重及び強度を向上させている。Since the amount of the binder mixed is relatively large, the fine alumina completely covers the aggregate and is also filled between the aggregate particles, improving the bulk specific gravity and strength of the refractory material.
［実施例］
次に本発明を実施例及び比較例により具体的に説明する
。[Examples] Next, the present invention will be specifically explained using Examples and Comparative Examples.
ボーキサイトを原料として作られた溶融アルミナ骨材Ａ
、及びアルミナを原料として作られた溶融アルミナ骨材
Ａ２の各１００重量部に、水酸化アルミニウムを焼成し
て得られた微粒アルミナ結合材Ｂ、の平均粒径１．０μ
ｍのものを５０重量部混合して試料Ｎｏ、 １及び平均
粒径０，７μｍのものを３０重量部混合して試料Ｎｏ、
２を作成した。Ｎｏ、 １及びＮｏ、 ２の骨材の最
大粒は６ｒｎｍ及び８ｍｍで、また０、１ｍｍ以上の粒
子を８０％及び６５％含む。Fused alumina aggregate A made from bauxite as raw material
, and 100 parts by weight each of molten alumina aggregate A2 made from alumina as a raw material, and fine alumina binder B obtained by firing aluminum hydroxide, with an average particle size of 1.0 μm.
Sample No. 1 was prepared by mixing 50 parts by weight of 0.7 μm particles, and Sample No. 1 was prepared by mixing 30 parts by weight of particles with an average particle size of 0.7 μm.
2 was created. The largest grains of No. 1 and No. 2 aggregates were 6rnm and 8mm, and contained 80% and 65% of particles larger than 0.1mm.
試料Ｎｏ、 １及びＮｏ、 ２に用いた骨材の粒度分布
を第１図に粒度分布１及び粒度分布２として示す。The particle size distributions of the aggregates used for samples No. 1 and No. 2 are shown in FIG. 1 as particle size distribution 1 and particle size distribution 2.
比較例として粒度分布を変えた骨材Ａ２と試料Ｎｏ、
２と同じ平均粒径の結合材Ｂ、とて試料Ｎｏ、 ３とＮ
ｏ、 ４を作成した。試料Ｎｏ、 ３は最大粒径１４ｍ
ｍ、０゜１ｍｍ以上の粒子が８０％、Ｎｏ、４は最大粒
２ ｍｍ、最小粒０．２ｍｍ（従って０ 、１ ｍｍ以
上の骨材が１００％）で、いずれも第１図に粒度分布３
及び粒度分布４として示される分布を持つ骨材を使用し
た。As a comparative example, aggregate A2 with different particle size distribution and sample No.
Binder B with the same average particle size as 2, sample No. 3 and N
o, 4 was created. Sample No. 3 has a maximum particle size of 14 m
For No. 4, the maximum particle size is 2 mm and the minimum particle size is 0.2 mm (therefore, 100% of aggregate is 0.1 mm or larger), and the particle size distribution is shown in Figure 1. 3
and particle size distribution 4 was used.
試料Ｎｏ、 １及びＮｏ、 ２は領域ＡＢＣＤＥ内に含
まれるが、試料Ｎｏ、 ３及びＮｏ、 ４は一部がこの
領域から外れている。Samples No. 1 and No. 2 are included in the area ABCDE, but samples No. 3 and No. 4 are partially outside this area.
また、粒度分布１で示される骨材Ａ２と市販の結合材Ｂ
２（日本琺瑯釉薬（株）製フリット）を使用し試料Ｎｏ
、 ５を作成した。なお、結合材Ｂ２の組成はＡｌ２Ｏ
３１１，２％、５ｉ０２３３．６％、ＣａＯ３，７％、
ＭｇＯ１８，６％、Ｂ２０，１７．７％。In addition, aggregate A2 having a particle size distribution of 1 and commercially available binder B
2 (frit made by Nippon Enamel Glaze Co., Ltd.) and sample No.
, 5 was created. Note that the composition of the binder B2 is Al2O
311.2%, 5i0233.6%, CaO3.7%,
MgO 18.6%, B20, 17.7%.
Ｂａ０ １３−５％及びＮａ２Ｏ０，３％である。Ba0 13-5% and Na2O 0.3%.
これらの配合割合等をまとめて第１表に示す。Table 1 summarizes these blending ratios.
上記骨材と結合材を用い、保形材として澱粉を水に溶解
して２０％水溶液として用い、骨材１００重量部に対し
て５重量部添加した。Using the above aggregate and binder, starch was dissolved in water as a shape retaining material to form a 20% aqueous solution, and 5 parts by weight was added to 100 parts by weight of the aggregate.
成形は、骨材、結合材および保形材をよく混合して、圧
カフ ５０ ｋｇ／ ｃｍ２の型込め法で行い、乾燥後
、電気炉を用いて約１４００℃で１時間焼成を行った。The molding was carried out by mixing the aggregate, binder and shape retaining material thoroughly and using a molding method using a pressure cuff of 50 kg/cm2. After drying, the molding was performed at about 1400° C. for 1 hour using an electric furnace.
（１）物性試験
焼成後の試料について、組成分析、かさ比重、圧縮強度
及び曲げ強度の測定を行った。また市販の耐火材２種類
（試料Ｎｏ、 ６及びＮｏ、 ７ ）についても、同様
の測定を行った。結果を第１表に示す。(1) Physical property test For the sample after firing, compositional analysis, bulk specific gravity, compressive strength and bending strength were measured. Similar measurements were also performed on two types of commercially available refractory materials (Samples No. 6 and No. 7). The results are shown in Table 1.
この結果、本発明は、かさ比重及び機械的強度ともに十
分な値を示しているのに対し、本発明条件から外れる試
料Ｎｏ、 ３及びＮｏ、 ４はかさ比重、圧縮強度及び
曲げ強度のいずれかにおいて低い値を示すことが判る。As a result, the present invention shows sufficient values for both bulk specific gravity and mechanical strength, whereas samples No. 3 and No. 4, which deviate from the present invention conditions, have either bulk specific gravity, compressive strength, or bending strength. It can be seen that this shows a low value.
（２）溶出試験
試料Ｎｏ、２（本発明材）及び試料Ｎｏ、 ５ 、Ｎｏ
、 ６゜Ｎｏ、７（比較材）について、るつぼ法（耐火
材に５０φＸ５０ｍｍの穴を開け、この中にアルミニウ
ム溶湯を入れて、一定時間保持後、アルミニウム溶湯中
の不純物の増加量を測る）により、耐火材成分のメタル
への溶出量を測定した。アルミニウム溶湯としては９９
．９９％Ａ１とＡ１−４％Ｍｇ合金を使用し、８５０℃
で４８時間保持して試験を行った。結果を第２表に示す
。(2) Elution test sample No. 2 (invention material) and sample No. 5, No.
, 6゜No. and 7 (comparative materials) were tested using the crucible method (drill a hole of 50φ x 50mm in the refractory material, pour the molten aluminum into the hole, and measure the increase in impurities in the molten aluminum after holding it for a certain period of time). The amount of elution of refractory components into metal was measured. 99 as molten aluminum
．． Using 99% A1 and A1-4% Mg alloy, 850℃
The test was carried out by holding it for 48 hours. The results are shown in Table 2.
この結果、本発明の耐火材はＳｉ、Ｂ、Ｐの溶出がない
ことが判る。また試料Ｎｏ、 ５及び市販品Ｎｏ、 ６
及びＮｏ、 ７は結合材成分であるこれらの溶出が認め
られることが判る。As a result, it can be seen that the refractory material of the present invention does not elute Si, B, and P. In addition, sample No. 5 and commercial product No. 6
It can be seen that in No. 7 and No. 7, elution of binder components was observed.
また、本発明材はるつぼの側壁が剥がれることなく、耐
スポーリング性のあることが判る。Furthermore, it can be seen that the material of the present invention has spalling resistance without peeling of the side wall of the crucible.
４゜
［発明の効果］
本発明に係る耐火材はかさ比重及び強度に優れ、しかも
該耐火材をアルミニウム溶湯用炉材に使用した場合、溶
湯への微量不純物の溶出がなく、従って品質が安定する
。4゜[Effect of the invention] The refractory material according to the present invention has excellent bulk specific gravity and strength, and when the refractory material is used as a furnace material for molten aluminum, there is no elution of trace impurities into the molten metal, so the quality is stable. do.
さらに、耐スポーリング性があり、結合材が溶湯によっ
て侵食を受は難いので、長期間の使用が可能であり、工
業上その効果の大きい発明である。Furthermore, it has spalling resistance and the binding material is not easily corroded by molten metal, so it can be used for a long period of time, making this invention highly effective industrially.
第１図は、粒子径（対数目盛り）−篩上３図における本
発明に係る溶融アルミナ骨材の粒度分布の適用領域を示
す図面である。FIG. 1 is a drawing showing the applicable range of the particle size distribution of the fused alumina aggregate according to the present invention in particle size (logarithmic scale) - 3 sieve diagrams.
Claims (2)
アルミナの焼成体であって、該焼成体のかさ比重が３．
０以上であることを特徴とする溶湯汚染の少ない耐火材
。1. A fired body of fine alumina obtained by firing molten alumina and aluminum hydroxide, the fired body having a bulk specific gravity of 3.
A refractory material with little molten metal contamination, characterized in that the temperature is 0 or more.
粒子径（ｍｍ），等間隔目盛りの縦軸を篩上（％）とし
た第１図に示す図面において、 点Ａ：粒子径１０ｍｍ，篩上０％ Ｂ：粒子径４ｍｍ，篩上０％ Ｃ：粒子径０．１ｍｍ，篩上５０％ Ｄ：粒子径０．００１ｍｍ，篩上１００％ Ｅ：粒子径０．１ｍｍ，篩上１００％ で囲まれた領域ＡＢＣＤＥ内に含まれ、かつ直線ＡＢ上
の１点と直線ＤＥ上の１点を両端とする直線または曲線
に沿う粒度分布を有するものであって、該溶融アルミナ
１００重量部に対し、水酸化アルミニウムを焼成した平
均粒径０．１〜１０μｍの微粒アルミナ１０〜７５重量
部を保形材及び水とともに混練し、成形後１３００℃以
上の温度で焼成することを特徴とする請求項１記載の耐
火材の製造法。2. In the drawing shown in Figure 1, where the horizontal axis of the logarithmic scale is the molten alumina particle size (mm) and the vertical axis of the evenly spaced scale is the sieve size (%), point A: particle size 10 mm, sieve size 0. % B: Particle size 4 mm, 0% on the sieve C: Particle size 0.1 mm, 50% on the sieve D: Particle size 0.001 mm, 100% on the sieve E: Particle size 0.1 mm, 100% on the sieve Surrounded by It is included in the area ABCDE and has a particle size distribution along a straight line or a curved line with one point on the straight line AB and one point on the straight line DE as both ends. 10. 10 to 75 parts by weight of fine alumina having an average particle diameter of 0.1 to 10 μm obtained by firing aluminum oxide is kneaded with a shape retaining material and water, and after molding, the mixture is fired at a temperature of 1300° C. or higher. manufacturing method for refractory materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246295A JPH04130050A (en) | 1990-09-18 | 1990-09-18 | Refractory material and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2246295A JPH04130050A (en) | 1990-09-18 | 1990-09-18 | Refractory material and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04130050A true JPH04130050A (en) | 1992-05-01 |
Family
ID=17146430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2246295A Pending JPH04130050A (en) | 1990-09-18 | 1990-09-18 | Refractory material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04130050A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037806A (en) * | 1973-06-27 | 1975-04-08 | ||
| JPS5116442A (en) * | 1974-07-31 | 1976-02-09 | Akiko Hirata | Chikudenchino denkaiekijohatsuboshihoho |
| JPS5978926A (en) * | 1982-10-29 | 1984-05-08 | Mitsubishi Chem Ind Ltd | Manufacture of easily sinterable alumina |
| JPS61132513A (en) * | 1984-11-28 | 1986-06-20 | Asahi Chem Ind Co Ltd | Alpha-alumina powder and its production |
-
1990
- 1990-09-18 JP JP2246295A patent/JPH04130050A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037806A (en) * | 1973-06-27 | 1975-04-08 | ||
| JPS5116442A (en) * | 1974-07-31 | 1976-02-09 | Akiko Hirata | Chikudenchino denkaiekijohatsuboshihoho |
| JPS5978926A (en) * | 1982-10-29 | 1984-05-08 | Mitsubishi Chem Ind Ltd | Manufacture of easily sinterable alumina |
| JPS61132513A (en) * | 1984-11-28 | 1986-06-20 | Asahi Chem Ind Co Ltd | Alpha-alumina powder and its production |
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