JP4484694B2 - Castable refractories - Google Patents
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- 239000011819 refractory material Substances 0.000 title description 18
- 239000000843 powder Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 230000008595 infiltration Effects 0.000 claims description 19
- 238000001764 infiltration Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 239000005350 fused silica glass Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000004568 cement Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000464 lead oxide Inorganic materials 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- BFSPAPKTIGPYOV-BQYQJAHWSA-N (e)-1-[4-(4-hydroxyphenyl)piperazin-1-yl]-3-thiophen-2-ylprop-2-en-1-one Chemical compound C1=CC(O)=CC=C1N1CCN(C(=O)\C=C\C=2SC=CC=2)CC1 BFSPAPKTIGPYOV-BQYQJAHWSA-N 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 238000002156 mixing Methods 0.000 description 16
- 238000004901 spalling Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- -1 etc.) Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、アルミニウムや亜鉛に代表される非鉄金属の溶湯を取り扱う原料溶解工程、鋳造工程等において用いられる溶解保持炉、バスタブ、取鍋等の炉壁材、移送パイプ、ルツボ、スリーブ、鋳湯ノズル、ラドル、トラフ、樋等に好適なキャスタブル耐火物に関する。 The present invention relates to a melting and holding furnace, a furnace wall material such as a bathtub and a ladle, a transfer pipe, a crucible, a sleeve, and a cast metal used in a raw material melting process, a casting process, and the like that handle a non-ferrous metal typified by aluminum and zinc The present invention relates to a castable refractory suitable for nozzles, ladles, troughs, rods and the like.
アルミニウム等の非鉄金属の溶解、鋳造等において、溶湯が直接接触して使用される部材は、耐火物により構成される。前記耐火物は、定形レンガ、キャスタブル耐火物、繊維質耐火物（セラミックファイバー）、モルタル（コート材等）、セラミックフィルタ等の様々な態様のものが使用されている。 In the melting, casting, etc. of a non-ferrous metal such as aluminum, a member used in direct contact with the molten metal is composed of a refractory. The said refractory is used in various forms such as shaped bricks, castable refractories, fibrous refractories (ceramic fibers), mortar (coating materials, etc.), ceramic filters and the like.
前記耐火物の材質としては、溶湯の組成、形状、使用態様等の種々の条件に応じて、適宜選定して使用されている。例えば、溶湯に濡れ難いという特性を利用して、窒化珪素、炭化珪素、黒鉛等を材料とするものが、樋、溶融炉内張り材等に多く採用されている。
また、溶融シリカ質による熱膨張率が小さい鋳鉄誘導炉用ラミング材や、溶融シリカを含むアルミナ−シリカ質キャスタブル耐火物等も提案されている（例えば、特許文献１，２等参照）。
In addition, a ramming material for a cast iron induction furnace having a low coefficient of thermal expansion due to fused silica, an alumina-silica castable refractory containing fused silica, and the like have been proposed (see, for example, Patent Documents 1 and 2).
近年、アルミニウム合金やマグネシウム合金等の非鉄金属の需要が伸びており、特に、自動車関連の部材における需要が大幅に増加しており、これらの製品の素材の品質に対する要求が厳しくなってきている。 In recent years, the demand for non-ferrous metals such as aluminum alloys and magnesium alloys has increased, and in particular, the demand for automobile-related materials has greatly increased, and the demand for the quality of the materials of these products has become severe.
前記品質は、アルミニウム等の原料の溶解時に使用される上記のような様々な耐火物の特性により、大きな影響を受ける。例えば、耐火物が、熱的または機械的衝撃により剥離や欠落を生じたり、接触する溶湯により浸食されたりすると、種々の介在物やアルカリ金属を含む元素の混入により溶湯が汚染され、得られる地金の純度、品質の低下を招くこととなる。 The quality is greatly influenced by the characteristics of various refractories as described above used when a raw material such as aluminum is melted. For example, if a refractory material is peeled off or missing due to thermal or mechanical impact, or is eroded by molten metal that comes in contact with it, the molten metal is contaminated by the inclusion of various inclusions and elements containing alkali metals. The purity and quality of gold will be reduced.
このため、高品質の地金を得るためには、金属原料の品質のみならず、その製造工程のうち、特に、原料溶解工程、鋳造工程等において、溶湯と直接接触して使用される耐火物の材質の選択、品質の向上も重要な要素となる。
したがって、前記耐火物においては、耐熱衝撃性および機械的強度に優れ、しかも、溶湯への不純物の混入を防止するため、溶湯と接触する耐火物の浸食、反応が抑制されることが求められている。
For this reason, in order to obtain high-quality bullion, not only the quality of the metal raw material, but also the refractory used in direct contact with the molten metal, particularly in the raw material melting step, casting step, etc. Material selection and quality improvement are also important factors.
Therefore, the refractory is required to be excellent in thermal shock resistance and mechanical strength, and to suppress the erosion and reaction of the refractory in contact with the molten metal in order to prevent contamination of the molten metal. Yes.
そこで、本発明者らは、従来から耐火物材料の一つとして用いられている溶融シリカに着目して、施工が容易であり、応用範囲が広いキャスタブル耐火物において、従来の高アルミナ質等の耐火物では十分とは言えなかった上記特性の要求に応えられるものを得るべく検討を重ねた結果、本発明を完成するに至った。 Therefore, the present inventors have focused on fused silica that has been conventionally used as one of refractory materials, and in castable refractories that are easy to construct and have a wide range of applications. As a result of repeated investigations to obtain a material that can meet the above-mentioned requirements for refractories, the present invention has been completed.
すなわち、本発明は、上記技術的課題を解決するためになされたものであり、断熱性、耐スポーリング性、強度特性に優れ、アルミニウム等の溶湯の浸透を抑制することができ、アルミニウム等の非鉄金属の溶解、鋳造等において好適に用いることができるキャスタブル耐火物を提供することを目的とするものである。 That is, the present invention has been made to solve the above technical problem, and is excellent in heat insulation, spalling resistance and strength properties, and can suppress the penetration of molten metal such as aluminum. An object of the present invention is to provide a castable refractory material that can be suitably used in melting, casting, etc. of non-ferrous metals.
本発明に係るキャスタブル耐火物は、非鉄金属の溶湯を取り扱う部材に用いられるキャスタブル耐火物であって、９５％以上のＳｉＯ2を含有する粒径２０ｍｍ以下の溶融シリカからなる骨材に、粒径１０μｍ以上１００μｍ以下のアルミナ微粉、粒径１μｍ以下のシリカ微粉および７０％以上のＡｌ 2 Ｏ 3 純度を有する粒径２０μｍ以上１００μｍ以下のアルミナセメントからなる粉末原料と、酸化鉛、酸化バリウム、硫酸バリウム、酸化ゲルマニウム、酸化鉄から選ばれた少なくとも１種の粉末からなる浸潤抑制剤と、縮合リン酸ナトリウム、ナフタレンスルホン酸系またはポリカルボン酸系から選ばれた少なくとも１種の分散剤とが配合され、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、前記骨材が６０重量％以上８５重量％以下、前記粉末原料が１４重量％以上２０重量％以下配合されていることを特徴とする。
キャスタブル耐火物において、溶融シリカを骨材として、上記のような配合とすることにより、断熱性、耐スポーリング性、強度特性に優れ、アルミニウム等の非鉄金属の溶湯の浸透を抑制することができる。
The castable refractory according to the present invention is a castable refractory used for a member that handles a non-ferrous metal melt, and is composed of an aggregate made of fused silica containing 95% or more of SiO 2 and having a particle size of 20 mm or less. Powder raw material comprising alumina fine powder of 10 μm or more and 100 μm or less, silica fine powder of particle diameter of 1 μm or less, and alumina cement having a particle size of 20 μm or more and 100 μm or less having an Al 2 O 3 purity of 70% or more , lead oxide, barium oxide, barium sulfate , An infiltration suppressor comprising at least one powder selected from germanium oxide and iron oxide, and at least one dispersant selected from condensed sodium phosphate, naphthalene sulfonic acid or polycarboxylic acid. , the total amount of the aggregate powder raw material infiltration inhibitor, wherein the aggregate is 60 wt% or more 85 wt% or less Wherein the powder material is blended 20 wt% 14 wt% or more.
In castable refractories, by using fused silica as an aggregate and blending as described above, heat insulation, spalling resistance, strength properties are excellent, and penetration of molten metal of non-ferrous metals such as aluminum can be suppressed. .
前記キャスタブル耐火物は、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、前記浸潤抑制剤が１重量％以上２５重量％以下、前記分散剤が外率で０．０１重量％以上０．２重量％以下配合されていることが好ましい。
前記キャスタブル耐火物において、上記のような優れた特性を発揮させるためには、このような配合組成とすることが好ましい。
In the castable refractory , the infiltration inhibitor is 1% by weight or more and 25% by weight or less, and the dispersant is 0.01% by weight or more based on the total amount of the aggregate, the powder raw material, and the infiltration inhibitor. It is preferable that 0.2% by weight or less is blended.
In the castable refractory, in order to exhibit the above excellent characteristics, it is preferable to have such a composition.
上述したとおり、本発明によれば、断熱性、耐スポーリング性に優れ、アルミニウム等の非鉄金属の溶湯の浸透を抑制することができるキャスタブル耐火物が提供される。
また、本発明に係るキャスタブル耐火物は、比較的かさ比重が小さく、強度特性にも優れていることから、予めブロック化して焼成処理を施すことにより、樋、パイプ、ラドル等に用いられる軽量材とする等、様々な用途に応用可能である。
As described above, according to the present invention, there is provided a castable refractory that has excellent heat insulation and spalling resistance and can suppress the penetration of a molten metal such as aluminum.
In addition, the castable refractory according to the present invention has a relatively small bulk specific gravity and is excellent in strength characteristics. Therefore, a light weight material used for firewood, pipes, ladles, etc. by blocking and firing in advance. It can be applied to various uses.
以下、本発明について、より詳細に説明する。
本発明に係るキャスタブル耐火物は、溶融シリカ骨材に、アルミナ微粉、シリカ微粉およびアルミナセメントからなる粉末原料と、浸潤抑制剤と、分散剤とが配合されているものである。
すなわち、本発明は、キャスタブル耐火物の骨材として溶融シリカを用いることを特徴とするものである。
溶融シリカは、熱膨張率が非常に小さく、骨材として用いることにより、得られるキャスタブル耐火物の耐熱衝撃性が大きく向上する。また、溶融シリカ骨材自体が、他の配合成分に比べて、溶湯に濡れ難いという特徴を有している。
さらに、上記のような溶融シリカ質のキャスタブル耐火物は、従来の高アルミナ質のキャスタブル耐火物よりも、熱伝導率が小さく、優れた断熱性が得られる。
Hereinafter, the present invention will be described in more detail.
The castable refractory according to the present invention is obtained by blending a fused silica aggregate with a powder raw material composed of alumina fine powder, silica fine powder and alumina cement, an infiltration inhibitor, and a dispersant.
That is, the present invention is characterized by using fused silica as an aggregate of castable refractories.
Fused silica has a very small coefficient of thermal expansion, and when used as an aggregate, the thermal shock resistance of the castable refractory obtained is greatly improved. Further, the fused silica aggregate itself has a feature that it is difficult to get wet with the molten metal as compared with other blending components.
Further, the above-described fused siliceous castable refractories have a lower thermal conductivity and superior heat insulation than conventional high alumina castable refractories.
キャスタブル耐火物が多量に不純物を含有することは、上記のような優れた特性を損なわせる原因となるため、骨材として用いられる溶融シリカは、ＳｉＯ2純度ができるだけ高いものであることが好ましい。
本発明に係るキャスタブル耐火物においては、骨材として用いられる溶融シリカの特徴であるそのガラス質により発揮される効果を、他の成分の混入により阻害されないようにするため、ＳｉＯ2が９５％以上含まれた溶融シリカを用いることが好ましい。
Since the castable refractory contains a large amount of impurities causes the above-described excellent characteristics to be impaired, it is preferable that the fused silica used as the aggregate has a SiO 2 purity as high as possible.
In the castable refractory according to the present invention, SiO 2 is 95% or more so that the effect exhibited by the vitreous material, which is a feature of fused silica used as an aggregate, is not hindered by the mixing of other components. It is preferable to use the fused silica contained.
前記溶融シリカ骨材の粒径は２０ｍｍ以下であることが好ましく、より好ましくは、８ｍｍ以下のものが使用される。
前記粒径が２０ｍｍを超える場合は、小型や薄型状の製品の成形が困難となり、また、現場での施工が制約され好ましくない。また、得られるキャスタブル耐火物が、アルミニウム等の溶湯により浸食されやすくなる。
The particle size of the fused silica aggregate is preferably 20 mm or less, more preferably 8 mm or less.
When the particle diameter exceeds 20 mm, it is difficult to form a small or thin product, and construction on site is restricted, which is not preferable. Moreover, the castable refractory obtained is easily eroded by a molten metal such as aluminum.
前記溶融シリカ骨材の配合量は、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、６０重量％以上８５重量％以下とする。
前記配合量が６０重量％未満である場合は、キャスタブル耐火物の耐熱衝撃性および耐濡れ性が著しく低下する。
一方、前記配合量が８５重量％を超える場合は、キャスタブルの流動性が低下し、施工時の作業性が劣る。
The amount of the fused silica aggregate is 60% by weight or more and 85% by weight or less based on the total amount of the aggregate, the powder raw material, and the infiltration inhibitor.
When the blending amount is less than 60% by weight, the thermal shock resistance and wettability of the castable refractory are significantly lowered.
On the other hand, when the said compounding quantity exceeds 85 weight%, the fluidity | liquidity of castable falls and the workability | operativity at the time of construction is inferior.
前記溶融シリカ骨材に配合されるアルミナ微粉、シリカ微粉およびアルミナセメントからなる粉末原料は、混合時にそれぞれ添加してもよく、あるいはまた、予めこれら３種を混合したものを投入してもよい。
アルミナ微粉およびシリカ微粉は、キャスタブルの流動性を向上させる作用を有する。また、アルミナセメントは、キャスタブル耐火物の強度を向上させる作用を有する。
The powder raw material consisting of alumina fine powder, silica fine powder and alumina cement to be blended in the fused silica aggregate may be added at the time of mixing, or alternatively, a mixture of these three kinds in advance may be added.
Alumina fine powder and silica fine powder have the effect of improving the flowability of castable. Alumina cement has the effect of improving the strength of the castable refractory.
前記アルミナ微粉は、粒径１０μｍ以上１００μｍ以下のものを用い、また、前記アルミナセメントは、粒径２０μｍ以上１００μｍ以下のものを用いる。
前記粒径が大きすぎる場合は、キャスタブルの流動性が低下する。一方、前記粒径が小さすぎる場合には、使用時に加熱焼結し、熱スポーリング性が低下する。
前記アルミナ微粉の粒径は、５０μｍ程度であることが好ましく、また、前記アルミナセメントの粒径は、３０μｍ以上６０μｍ以下であることが好ましい。
The alumina fine powder has a particle size of 10 μm to 100 μm, and the alumina cement has a particle size of 20 μm to 100 μm.
If the particle size is too large, the flowability of the castable is lowered. On the other hand, when the particle size is too small, it is heated and sintered at the time of use, and the thermal spalling property is lowered.
The particle size of the alumina fine powder is preferably about 50 μm, and the particle size of the alumina cement is preferably 30 μm or more and 60 μm or less.
また、前記アルミナセメントは、Ａｌ2Ｏ3純度が低いものは、ＣａＯ分が多くなり、アルミニウム溶湯の汚染につながるため、Ａｌ2Ｏ3純度が７０％以上のものを用いることが好ましい。 The alumina cement having a low Al 2 O 3 purity has a high CaO content and leads to contamination of the molten aluminum. Therefore, it is preferable to use an alumina cement having an Al 2 O 3 purity of 70% or more.
また、前記シリカ微粉は、粒径１μｍ以下、好ましくは、０．１μｍ以上１μｍ以下のものを用いる。
前記粒径が１μｍを超える場合は、キャスタブルの流動性が低下する。
The silica fine powder has a particle size of 1 μm or less, preferably 0.1 μm or more and 1 μm or less.
When the particle size exceeds 1 μm, the castable fluidity is lowered.
また、前記キャスタブル耐火物には、浸潤抑制剤として、酸化鉛、酸化バリウム、硫酸バリウム、酸化ゲルマニウム、酸化鉄から選ばれた少なくとも１種の粉末が配合される。
溶融アルミニウムの表面張力は、６８０℃において５５０ｄｙｎｅ／ｃｍであり、上記浸潤抑制剤はいずれも、溶融アルミニウムよりも表面張力が低い。このため、上記のような表面張力が小さい浸潤抑制剤を添加することにより、アルミニウム、アルミニウム合金、その他の非鉄金属の溶湯が耐火物内に浸透することを防止し、また、該耐火物の浸食、剥離や欠落による前記溶湯の汚染を防止することができる。
The castable refractory is mixed with at least one powder selected from lead oxide, barium oxide, barium sulfate, germanium oxide, and iron oxide as an infiltration suppressor.
The surface tension of molten aluminum is 550 dyne / cm at 680 ° C., and any of the above infiltration inhibitors has a surface tension lower than that of molten aluminum. For this reason, by adding an infiltration suppressor having a small surface tension as described above, it is possible to prevent the molten metal of aluminum, aluminum alloy, or other non-ferrous metal from penetrating into the refractory, and to erode the refractory. Further, contamination of the molten metal due to peeling or missing can be prevented.
前記キャスタブル耐火物における好ましい配合組成は、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、前記骨材が６０重量％以上８５重量％以下、前記粉末原料が１４重量％以上２０重量％以下、前記浸潤抑制剤が１重量％以上２５重量％以下、前記分散剤が外率で０．０１重量％以上０．２重量％以下である。 A preferable blending composition in the castable refractory is such that the aggregate is 60 wt% or more and 85 wt% or less, and the powder raw material is 14 wt% or more and 20 wt% with respect to the total amount of the aggregate, the powder raw material, and the infiltration suppressor. % Or less, the infiltration inhibitor is 1% by weight or more and 25% by weight or less, and the dispersant is 0.01% by weight or more and 0.2% by weight or less in terms of external ratio.
前記粉末原料の配合量は、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、アルミナ微粉、シリカ微粉およびアルミナセメントの３種混合にて１４重量％以上２０重量％以下であることが好ましい。特に、キャスタブルの優れた流動性、硬化特性および強度特性等を発揮させるためには、前記３種の粉末原料は、それぞれほぼ等量ずつ配合されることがより好ましい。
前記配合量が１４重量％未満である場合は、キャスタブルの流動性、硬化特性および強度特性のいずれもが低下する。
一方、前記配合量が２０重量％を超える場合は、キャスタブル耐火物の耐食性が低下し、該耐火物からＣａＯ、Ａｌ2Ｏ3等の成分が溶出し、アルミニウム等の溶湯を汚染することとなる。
The blending amount of the powder raw material is 14% by weight or more and 20% by weight or less by mixing three kinds of alumina fine powder, silica fine powder and alumina cement with respect to the total amount of the aggregate, the powder raw material and the infiltration suppressor. Is preferred. In particular, in order to exhibit excellent fluidity, curing characteristics, strength characteristics, and the like of castable, it is more preferable that the three powder raw materials are blended in approximately equal amounts.
When the blending amount is less than 14% by weight, all of castable fluidity, curing characteristics, and strength characteristics are deteriorated.
On the other hand, when the blending amount exceeds 20% by weight, the corrosion resistance of the castable refractory decreases, and components such as CaO and Al 2 O 3 are eluted from the refractory and contaminate the molten metal such as aluminum. .
また、前記浸潤抑制剤の配合量は、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、１重量％以上２５重量％以下であることが好ましい。
前記配合量が１重量％未満である場合は、上述したような溶湯の耐火物内への浸透防止効果が十分に得られない。
一方、前記配合量が２５重量％を超える場合は、配合量の増加に伴う量的な添加効果は認められず、しかも、コスト高となる。
Moreover, it is preferable that the compounding quantity of the said infiltration suppressor is 1 to 25 weight% with respect to the total amount of the said aggregate, a powder raw material, and an infiltration suppressor.
When the blending amount is less than 1% by weight, the effect of preventing the penetration of the molten metal into the refractory as described above cannot be obtained sufficiently.
On the other hand, when the blending amount exceeds 25% by weight, the quantitative addition effect accompanying the increase in the blending amount is not recognized, and the cost increases.
さらに、本発明に係るキャスタブル耐火物には、有機または無機の分散剤が配合される。
キャスタブルの流動性、ブロック（成形体）における緻密な組織形成、耐火物における優れた強度特性を得るためには、充填性の向上、すなわち、原料混練時の水分量の低減化が求められる。そのため、低水分で良好な流動性を得るため、少なくとも１種の分散剤（混和剤）が配合される。
Furthermore, an organic or inorganic dispersant is blended in the castable refractory according to the present invention.
In order to obtain castable fluidity, formation of a dense structure in the block (molded body), and excellent strength characteristics in the refractory, it is required to improve the filling property, that is, to reduce the water content during raw material kneading. Therefore, in order to obtain good fluidity with low moisture, at least one dispersant (admixture) is blended.
有機系の分散剤の場合には、ナフタレンスルホン酸系（例えば、花王株式会社製マイティー等）またはポリカルボン酸系（例えば、日本純薬株式会社製ジュリマー等）のものが用いられ、無機系の分散剤の場合には、縮合リン酸ナトリウムを用いることができる。
これらの分散剤は、１種のみでもよく、あるいはまた、２種以上を混合して配合してもよい。
In the case of organic dispersants, naphthalene sulfonic acid type (for example, Mighty manufactured by Kao Corporation) or polycarboxylic acid type (for example, Jurimer manufactured by Nippon Pure Chemical Co., Ltd.) is used. In the case of a dispersant, condensed sodium phosphate can be used.
These dispersants may be used alone or in combination of two or more.
前記分散剤は、前記骨材と粉末原料と浸潤抑制剤の合計量に対して、外率で０．０１重量％以上０．２重量％以下配合されることが好ましい。
前記配合量が０．０１重量％未満である場合は、キャスタブルの良好な流動性が得られ難い。
一方、０．２重量％よりも多く配合した場合であっても、配合量の増加に伴う量的な添加効果は得られない。
The dispersant is preferably blended in an external ratio of 0.01% by weight or more and 0.2% by weight or less with respect to the total amount of the aggregate, the powder raw material, and the infiltration inhibitor.
When the blending amount is less than 0.01% by weight, it is difficult to obtain good castable fluidity.
On the other hand, even if it is a case where it mix | blends more than 0.2 weight%, the quantitative addition effect accompanying the increase in a compounding quantity is not acquired.
上記のような本発明に係るキャスタブル耐火物は、断熱性、耐スポーリング性に優れ、アルミニウム、アルミニウム合金、亜鉛、マグネシウム合金等の非鉄金属を溶解する際に使用される溶解保持炉、バスタブ、取鍋等の炉壁材、移送パイプ、ルツボ、スリーブ、鋳湯ノズル、ラドル、トラフ、樋等の非鉄金属の溶湯や蒸気に直接触れる箇所に好適に用いることができる。 Castable refractories according to the present invention as described above are excellent in heat insulation, spalling resistance, melting holding furnace used when melting non-ferrous metals such as aluminum, aluminum alloy, zinc, magnesium alloy, bathtub, It can be suitably used in places where it comes into direct contact with molten metal or steam of non-ferrous metals such as ladle walls such as ladle, transfer pipes, crucibles, sleeves, cast metal nozzles, ladles, troughs and troughs.
また、本発明に係るキャスタブル耐火物は、比較的かさ比重が小さく、強度特性にも優れていることから、予めブロック化して焼成処理を施して、樋、パイプ、ラドル等の様々な用途の軽量材として応用することができる。 In addition, the castable refractory according to the present invention has a relatively small bulk specific gravity and excellent strength characteristics. Therefore, the castable refractory is blocked and fired in advance, and is lightweight for various uses such as firewood, pipes, and ladles. It can be applied as a material.
以下、本発明を実施例に基づきさらに具体的に説明するが、本発明は下記の実施例により制限されるものではない。
［実施例１〜６］
表１の実施例１〜６に示すような配合組成で混練し、１１０℃で２４時間、または、９００℃で３時間処理したキャスタブル耐火物を作製した。
得られたキャスタブル耐火物について、線変形率、かさ比重、曲げ強度、圧縮強度を測定した。
また、アルミニウム溶湯浸漬試験として、各キャスタブル耐火物を６６０℃のアルミニウム合金（ＡＤＣ１２）の溶湯に３５０時間浸漬させ、浸食量により評価を行った。
さらに、スポーリング試験として、各キャスタブル耐火物を１０００℃の炉内で１５分間加熱後、３分間水冷し、１２分間空冷するというサイクルを繰り返し、３０回まで行い、試料片の剥離や欠落が発生するまでの回数により評価を行った。
これらの結果を表１に示す。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited by the following Example.
[Examples 1 to 6]
Castable refractories were prepared by kneading with the composition shown in Examples 1 to 6 in Table 1 and treating at 110 ° C. for 24 hours or 900 ° C. for 3 hours.
About the obtained castable refractory, the linear deformation rate, bulk specific gravity, bending strength, and compressive strength were measured.
In addition, as a molten aluminum immersion test, each castable refractory was immersed in a molten aluminum alloy (ADC12) at 660 ° C. for 350 hours and evaluated by the amount of erosion.
Furthermore, as a spalling test, each castable refractory was heated in a 1000 ° C. furnace for 15 minutes, then water-cooled for 3 minutes, and then air-cooled for 12 minutes. The evaluation was performed according to the number of times until.
These results are shown in Table 1.
［比較例１〜４］
表２の比較例１〜４に示すような配合組成で混練し、１１０℃で２４時間、または、９００℃で３時間処理したキャスタブル耐火物を作製した。
得られたキャスタブル耐火物について、実施例１と同様にして、線変形率、かさ比重、曲げ強度、圧縮強度を測定し、また、アルミニウム溶湯浸漬試験およびスポーリング試験を行った。
これらの結果を表２に示す。
[Comparative Examples 1-4]
Castable refractories were prepared by kneading with the blending compositions as shown in Comparative Examples 1 to 4 in Table 2 and treating at 110 ° C. for 24 hours or 900 ° C. for 3 hours.
About the obtained castable refractory material, the linear deformation rate, the bulk specific gravity, the bending strength, and the compressive strength were measured in the same manner as in Example 1, and the molten aluminum immersion test and the spalling test were performed.
These results are shown in Table 2.
表１に示したように、実施例１〜６のキャスタブルは、比較的低水分での流し込み施工が可能であり、流動性が良好であることが認められた。
また、得られた耐火物の線変化率、強度特性にも優れており、アルミニウム溶湯浸漬試験においては、溶湯の耐火物内への浸透は認められなかった。
さらに、水冷法によるスポーリング試験でも、３０回繰り返した後も、試料片の剥離や欠落は認められなかった。
As shown in Table 1, it was confirmed that the castables of Examples 1 to 6 can be cast with relatively low moisture and have good fluidity.
Further, the obtained refractory was excellent in linear change rate and strength characteristics, and in the molten aluminum immersion test, the penetration of the molten metal into the refractory was not recognized.
Further, even in the spalling test by the water cooling method, no peeling or missing of the sample piece was observed even after repeating 30 times.
一方、表２に示したように、比較例１，３，４のキャスタブル耐火物は、線変化率が大きく、また、十分な強度特性は認められなかった。また、アルミニウム溶湯浸漬試験においては、浸食されてしまい、さらに、スポーリング試験においても、２０回目までには試料が剥離または欠落した。
比較例２については、線変化率、強度特性、耐スポーリング性は、実施例と同等であったが、アルミニウム溶湯浸漬試験においては、浸食されてしまった。
On the other hand, as shown in Table 2, the castable refractories of Comparative Examples 1, 3, and 4 had a large linear change rate, and sufficient strength characteristics were not recognized. Moreover, in the molten aluminum immersion test, it was eroded, and in the spalling test, the sample was peeled off or lost by the 20th time.
In Comparative Example 2, the linear change rate, strength characteristics, and spalling resistance were the same as those in the example, but in the molten aluminum immersion test, they were eroded.
Claims (2)
９５％以上のＳｉＯ2を含有する粒径２０ｍｍ以下の溶融シリカからなる骨材に、粒径１０μｍ以上１００μｍ以下のアルミナ微粉、粒径１μｍ以下のシリカ微粉および７０％以上のＡｌ 2 Ｏ 3 純度を有する粒径２０μｍ以上１００μｍ以下のアルミナセメントからなる粉末原料と、酸化鉛、酸化バリウム、硫酸バリウム、酸化ゲルマニウム、酸化鉄から選ばれた少なくとも１種の粉末からなる浸潤抑制剤と、縮合リン酸ナトリウム、ナフタレンスルホン酸系またはポリカルボン酸系から選ばれた少なくとも１種の分散剤とが配合され、
前記骨材と粉末原料と浸潤抑制剤の合計量に対して、前記骨材が６０重量％以上８５重量％以下、前記粉末原料が１４重量％以上２０重量％以下配合されていることを特徴とするキャスタブル耐火物。 It is a castable refractory used for members that handle non-ferrous metal melts,
Aggregate composed of fused silica having a particle size of 20 mm or less, containing 95% or more of SiO 2, and alumina fine powder having a particle size of 10 μm or more and 100 μm or less, silica fine powder having a particle size of 1 μm or less, and Al 2 O 3 purity of 70% or more. A powder raw material comprising an alumina cement having a particle size of 20 μm to 100 μm, an infiltration inhibitor comprising at least one powder selected from lead oxide, barium oxide, barium sulfate, germanium oxide, and iron oxide, and condensed sodium phosphate , With at least one dispersant selected from naphthalene sulfonic acid or polycarboxylic acid,
60 to 85% by weight of the aggregate and 14 to 20% by weight of the powder material are blended with respect to the total amount of the aggregate, the powder material and the infiltration suppressor. Castable refractory.
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| CN103319186A (en) * | 2013-05-24 | 2013-09-25 | 霍山县新裕炉窑模具有限公司 | Aluminum melting furnace cast refractory material and preparation method thereof |
| CN104311088A (en) * | 2014-10-28 | 2015-01-28 | 宁夏天纵泓光余热发电技术有限公司 | Silica fume-free refractory castable |
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