JP2007260703A - Heat-resistant coating material and member of casting device for low-melting metal - Google Patents
Heat-resistant coating material and member of casting device for low-melting metal Download PDFInfo
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本発明は、アルミニウム、マグネシウム、亜鉛、スズ、鉛、あるいはこれらの合金等のように概ね融点が８００℃以下である比較的低融点の金属を鋳造する鋳造装置において、これら金属の溶湯と接触する部材を被覆する耐熱性コーティング材、並びに耐熱性コーティング材で被覆された低融点金属鋳造装置用部材に関する。 The present invention is in contact with a molten metal of a metal such as aluminum, magnesium, zinc, tin, lead, or an alloy thereof, which casts a relatively low melting point metal having a melting point of about 800 ° C. or less. The present invention relates to a heat-resistant coating material that covers a member, and a member for a low-melting-point metal casting apparatus that is coated with a heat-resistant coating material.
鋳造装置において、上述のような金属の溶湯の移送や給湯、保持等を行う注湯ボックスや樋、保持炉等の内張り材、あるいはフロートやスパウト、ホット・トップリング、トランジションプレート等の付属部材として、種々の耐熱材料を加工したものが使用されるが、中でも耐熱性が良好で、軽量でありながらも強度が高く、更に加工性に優れることなどから、けい酸カルシウム質を炭素繊維で補強した耐熱材料が広く利用されている（例えば、特許文献１及び特許文献２参照）。 In casting equipment, as a lining material such as a pouring box, slag, and holding furnace for transferring, supplying and holding molten metal as described above, or as an accessory for floats, spouts, hot top rings, transition plates, etc. Processed from various heat-resistant materials are used. Among them, calcium silicate is reinforced with carbon fiber because of its good heat resistance, light weight, high strength, and excellent workability. Heat resistant materials are widely used (see, for example, Patent Document 1 and Patent Document 2).
一方で、デジタルカメラやデジタルビデオカメラ、携帯電話、ノート型コンピュータ等のモバイル機器、あるいは自動車等の高重量物においても、軽量化のために、フレームや筐体をマグネシウム合金で形成する傾向にある。しかし、マグネシウムやマグネシウムを含む合金は活性が非常に高く、これらの溶湯と接触する材料を浸食する作用が極めて強い。そのため、従来のけい酸カルシウム質、またはアルミナ・シリカ系等からなる部品は数回使用しただけで、場合によっては１回の使用で交換しなけばならないという問題があった。 On the other hand, in mobile devices such as digital cameras, digital video cameras, mobile phones, notebook computers, and heavy objects such as automobiles, frames and housings tend to be made of magnesium alloy for weight reduction. . However, magnesium and magnesium-containing alloys have very high activity and have an extremely strong action of eroding materials that come into contact with these molten metals. Therefore, there has been a problem that the conventional parts made of calcium silicate or alumina / silica are used several times, and in some cases must be replaced after one use.
耐食性を高めるために、耐熱性コーティング材を塗布することも試みられているが、窒化ホウ素質をはじめとして既存の耐熱性コーティング材はマグネシウムやマグネシウム合金の溶湯に対して耐食性を改善する効果が少なく、改善が望まれている。 In order to improve the corrosion resistance, it is also attempted to apply a heat resistant coating material, but existing heat resistant coating materials such as boron nitride are less effective in improving corrosion resistance against molten magnesium and magnesium alloys. Improvement is desired.
本発明は、このような従来の問題点に着目してなされたもので、マグネシウムやマグネシウムを含む合金のように浸食性の強い溶湯に対して優れた耐久性を示す低融点金属鋳造装置用部材、並びに前記部材を形成するのに使用される耐熱性コーティング材を提供することを目的とする。 The present invention has been made paying attention to such conventional problems, and is a member for a low-melting-point metal casting apparatus that exhibits excellent durability against a highly erodible molten metal such as magnesium or an alloy containing magnesium. Furthermore, it aims at providing the heat resistant coating material used in forming the said member.
上記の目的を達成するために、本発明は以下の耐熱性コーティング材及び低融点金属鋳造装置用部材を提供する。
（１）低融点金属を鋳造する鋳造装置において低融点金属の溶湯と接触する部材を被覆するコーティング材であって、フッ化物と無機バインダーとを含有することを特徴とする耐熱性コーティング材。
（２）更に他の耐火物を含有することを特徴とする上記（１）記載の耐熱性コ−ティング材。
（３）全固形分において、フッ化物がフッ素分として０．１〜５０質量％、無機バインダーが１〜３０質量％、他の耐火物が５〜９０質量％であることを特徴とする上記（２）記載の耐熱性コーティング材。
（４）フッ化物がフッ化カルシウム(ＣａＦ２)、フッ化マグネシム（ＭｇＦ２）及びクリオライト（Ｎａ３ＡｌＦ６）から選ばれる少なくとも１種であることを特徴とする上記（１）〜（３）の何れか１項に記載の耐熱性コーティング材。
（５）他の耐火物が窒化ホウ素(ＢＮ)であることを特徴とする上記（２）〜（４）の何れか１項に記載の耐熱性コーティング材。
（６）マグネシウムまたはマグネシウムを含む合金の溶湯と接触する部材に被覆されることを特徴とする上記（１）〜（５）の何れか１項に記載の耐熱性コーティング材。
（７）低融点金属を鋳造する鋳造装置において低融点金属の溶湯と接触する部材であって、上記（１）〜（６）の何れか１項に記載の耐熱性コーティング材からなる被膜で被覆されていることを特徴とする低融点金属鋳造装置用部材。
（８）気孔率５〜８０％の多孔質耐熱性成形体からなり、耐熱性コーティング材からなる被膜で被覆されていることを特徴とする上記（７）記載の低融点金属鋳造装置用部材。
（９）マグネシウムまたはマグネシウムを含む合金の溶湯と接触する部位に使用されることを特徴とする上記（７）または（８）記載の低融点金属鋳造装置用部材。
尚、本発明においてマグネシウムを含む合金とは、アルミニウムや亜鉛、スズ、鉛等のマグネシウム以外の低融点金属とマグネシウムとの合金全般を意味し、マグネシウムの含有率は問わないが、現実的には合金全量の０．１質量％〜９９．９質量％の範囲でマグネシウムを含むものである。
In order to achieve the above object, the present invention provides the following heat-resistant coating material and member for a low melting point metal casting apparatus.
(1) A heat-resistant coating material, which is a coating material for covering a member that contacts a molten metal of a low-melting point metal in a casting apparatus for casting a low-melting point metal, and contains a fluoride and an inorganic binder.
(2) The heat-resistant coating material as described in (1) above, further containing another refractory.
(3) In the above-mentioned, wherein the total solid content is 0.1 to 50% by mass of fluoride as fluorine content, 1 to 30% by mass of inorganic binder, and 5 to 90% by mass of other refractories ( 2) The heat-resistant coating material described.
(4) The above (1) to (3), wherein the fluoride is at least one selected from calcium fluoride (CaF 2 ), magnesium fluoride (MgF 2 ), and cryolite (Na 3 AlF 6 ). The heat resistant coating material according to any one of (1).
(5) The refractory coating material according to any one of (2) to (4) above, wherein the other refractory is boron nitride (BN).
(6) The heat-resistant coating material according to any one of (1) to (5) above, which is covered with a member that contacts a molten metal of magnesium or an alloy containing magnesium.
(7) A member that contacts a molten metal of a low melting point metal in a casting apparatus for casting the low melting point metal, and is coated with a film made of the heat resistant coating material according to any one of (1) to (6) above. A member for a low-melting-point metal casting apparatus, wherein
(8) The member for a low-melting-point metal casting apparatus according to (7), which is made of a porous heat-resistant molded body having a porosity of 5 to 80% and is coated with a film made of a heat-resistant coating material.
(9) The member for a low-melting-point metal casting apparatus according to (7) or (8), wherein the member is used for a portion that comes into contact with magnesium or a molten metal containing magnesium.
In the present invention, the magnesium-containing alloy means an alloy of magnesium and a low melting point metal other than magnesium, such as aluminum, zinc, tin, and lead. Magnesium is contained in the range of 0.1 mass% to 99.9 mass% of the total amount of the alloy.
本発明による耐熱性コーティング材は、適用箇所に、マグネシウムやマグネシウムを含む合金のように浸食性が高い金属の溶湯に対して非常に優れた耐食性を付与できる。そのため、部材の交換頻度は従来と比較して大幅に少なくて済み、所要時間と材料コストで、従来と比較してトータル的に非常に安価で低融点金属の鋳造が可能になる。 The heat-resistant coating material according to the present invention can impart excellent corrosion resistance to a molten metal having high erosion resistance such as magnesium or an alloy containing magnesium at an application site. Therefore, the replacement frequency of the members can be greatly reduced as compared with the conventional case, and the required time and material cost are totally lower compared with the conventional case, and low melting point metal can be cast.
以下、本発明に関して詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の耐熱性コーティング材は、フッ化物と無機バインダーとを分散液に配合したものである。 The heat resistant coating material of the present invention is obtained by blending a fluoride and an inorganic binder in a dispersion.
フッ化物は、特に制限はないが、フッ化カルシウム（ＣａＦ２）、フッ化マグネシウム（ＭｇＦ２）、クリオライト（Ｎａ３ＡｌＦ６）、フッ化リチウム（ＬｉＦ）、フッ化バリウム（ＢａＦ２）、フッ化アルミニウム（ＡｌＦ３）、フッ化ストロンチウム（ＳｒＦ２）、フッ化セリウム（ＣｅＦ３）、フッ化イットリウム（ＹＦ３）、フッ化ナトリウム（ＮａＦ）、フッ化カリウム（ＫＦ）、けいフッ化ナトリウム（Ｎａ２ＳｉＦ６）、けいフッ化アンモニウム（（ＮＨ４）２ＳｉＦ６）等の無機フッ化物が挙げられるが、特に安価であることから、フッ化カルシウム(ＣａＦ２)、フッ化マグネシム（ＭｇＦ２）及びクリオライト（Ｎａ３ＡｌＦ６）から選ばれる少なくとも１種を用いることが好ましい。また、フッ化物は、特に制限されるものではないが、平均粒径は小さい方が好ましく、３〜１５μｍが好ましく、５〜１０μｍがより好ましい。 Fluoride is not particularly limited, but calcium fluoride (CaF 2 ), magnesium fluoride (MgF 2 ), cryolite (Na 3 AlF 6 ), lithium fluoride (LiF), barium fluoride (BaF 2 ), Aluminum fluoride (AlF 3 ), strontium fluoride (SrF 2 ), cerium fluoride (CeF 3 ), yttrium fluoride (YF 3 ), sodium fluoride (NaF), potassium fluoride (KF), sodium fluorofluoride Inorganic fluorides such as (Na 2 SiF 6 ) and ammonium fluorofluoride ((NH 4 ) 2 SiF 6 ) can be mentioned, but since they are particularly inexpensive, calcium fluoride (CaF 2 ), magnesium fluoride (MgF) It is preferable to use at least one selected from 2 ) and cryolite (Na 3 AlF 6 ). The fluoride is not particularly limited, but the average particle diameter is preferably smaller, preferably 3 to 15 μm, and more preferably 5 to 10 μm.
また、耐熱性コーティング材は、その他の耐火物を含有してもよい。本発明では、アルミニウム、マグネシウム、亜鉛、スズ、鉛、あるいはこれらの合金等のように概ね融点が８００℃以下の低融点金属の溶湯と接触する部材を対象としており、使用可能な耐火物は融点が８００℃以上のものである。具体的には、アルミナやシリカ、ムライト、ジルコニア、マグネシア、ケイ酸ジルコニウム等の酸化物系耐火物、窒化ホウ素や窒化珪素、窒化アルミニウム、サイアロン等の窒化物系耐火物、炭化珪素等の炭化物系耐火物、グラファイトや黒鉛等のカーボン系耐火物が挙げられる。中でも、濡れ性を向上させる効果が高いことから、窒化ホウ素が好ましい。 The heat resistant coating material may contain other refractories. In the present invention, a member that contacts a molten metal of a low melting point metal having a melting point of approximately 800 ° C. or lower, such as aluminum, magnesium, zinc, tin, lead, or an alloy thereof, is used. Is 800 ° C. or higher. Specifically, oxide refractories such as alumina, silica, mullite, zirconia, magnesia, and zirconium silicate, nitride refractories such as boron nitride, silicon nitride, aluminum nitride, and sialon, and carbides such as silicon carbide Examples of the refractory include carbon-based refractories such as graphite and graphite. Among these, boron nitride is preferable because of its high effect of improving wettability.
無機バインダーとしては、アルミナゾル、コロイダルシリカ、リン酸アルミニウム、けい酸ナトリウム等が挙げられ、これらを単独で、あるいは適宜混合して使用できる。特に、アルミナゾルはクラックの発生を抑制できるという点で好ましい。 Examples of the inorganic binder include alumina sol, colloidal silica, aluminum phosphate, sodium silicate, and the like, and these can be used alone or in an appropriate mixture. In particular, alumina sol is preferable in that it can suppress the occurrence of cracks.
また、分散液は、水の他に、エタノール、メタノール等のアルコールやトルエン等の有機溶媒が挙げられるが、扱いやすいといった観点からは水を用いることが好ましい。 In addition to water, examples of the dispersion include alcohols such as ethanol and methanol, and organic solvents such as toluene. From the viewpoint of easy handling, it is preferable to use water.
耐熱性コーティング材におけるフッ化物及び無機バインダーのそれぞれの含有量は、特に制限されるものではないが、十分な耐食性を確保するには、固形分全量において、フッ化物がフッ素分として０．１〜５０質量％、無機バインダーが１〜３０質量％、他の耐火物が５〜９０質量％であることが好ましく、フッ化物がフッ素分として５〜２０質量％であることがより好ましい。尚、フッ化物としては、０．１〜６５質量％を含有する。 Each content of the fluoride and the inorganic binder in the heat-resistant coating material is not particularly limited, but in order to ensure sufficient corrosion resistance, the fluoride is 0.1 to 0.1% as the fluorine content in the total solid content. 50% by mass, the inorganic binder is preferably 1 to 30% by mass, the other refractory is preferably 5 to 90% by mass, and the fluoride is more preferably 5 to 20% by mass as the fluorine content. In addition, as a fluoride, 0.1-65 mass% is contained.
尚、耐熱性コーティング材における固形分と分散液との配合比率には制限がなく、塗布性を考慮して適宜設定できる。例えば、フッ化物、無機バインダー及び他の耐火物の合計量と同様の分散液を混合攪拌することで、耐熱性コーティング材が得られる。 In addition, there is no restriction | limiting in the compounding ratio of solid content and dispersion liquid in a heat resistant coating material, and it can set suitably in consideration of applicability | paintability. For example, a heat-resistant coating material can be obtained by mixing and stirring a dispersion similar to the total amount of fluoride, inorganic binder and other refractory.
また、耐熱性コーティング材はスラリーであることから、例えば、次のような添加剤を含有することで塗布性や安定性が高まり、好ましい。何れもスラリー全量に対する量で、メチルセルロースやカルボキシメチルセルロース、ポリエチレングリコール等の増粘剤を０．１〜８質量％、ポリビニルアルコール等の有機バインダーを０．１〜８質量％、窒素硫黄系の防腐剤を０．１〜２質量％、乳酸や酢酸等の安定化剤を０．１〜２質量％、イソプロピルアルコールやリン酸系の分散剤を０．１〜２質量％添加してもよい。 Further, since the heat-resistant coating material is a slurry, for example, it is preferable to contain the following additives to improve applicability and stability. All are based on the total amount of the slurry, 0.1-8% by weight of a thickener such as methylcellulose, carboxymethylcellulose, polyethylene glycol, etc., 0.1-8% by weight of an organic binder such as polyvinyl alcohol, and a nitrogen-sulfur preservative. 0.1 to 2% by mass, a stabilizer such as lactic acid or acetic acid may be added to 0.1 to 2% by mass, and isopropyl alcohol or a phosphoric acid-based dispersant may be added to 0.1 to 2% by mass.
本発明はまた、上記耐熱性コーティング材からなる被膜で被覆した低融点金属鋳造装置用部材を提供する。耐熱性コーティング材は、既存の低融点金属鋳造装置用部材に広く適用でき、金属製の部材にも適用できる。中でも、耐熱性コーティング材からなる被膜の密着強度に優れ、更に耐熱性等にも優れることから、気孔率が５〜８０％、好ましくは５０〜８０％の多孔質の耐熱性成形体からなる部材を被覆することが好ましい。とりわけ、断熱性能や比強度、加工性等に優れることからけい酸カルシウムを含むものが好ましい。けい酸カルシウムは、特に制限はないが、ワラストナイト（ＣａＳｉＯ３）、トバモライト（５ＣａＯ・６ＳｉＯ２・５Ｈ２Ｏ）及びゾノトライト(６ＣａＯ・６ＳｉＯ２・Ｈ２Ｏ)から選ばれる少なくとも１種であることが好ましく、これらを１０〜１００質量％の割合で含有することが好ましい。 The present invention also provides a member for a low-melting-point metal casting apparatus coated with a film made of the above heat-resistant coating material. The heat-resistant coating material can be widely applied to existing low melting point metal casting apparatus members, and can also be applied to metal members. Among them, a member made of a porous heat-resistant molded article having a porosity of 5 to 80%, preferably 50 to 80%, because it is excellent in adhesion strength of a film made of a heat-resistant coating material and is also excellent in heat resistance and the like. It is preferable to coat. In particular, those containing calcium silicate are preferred because of excellent heat insulation performance, specific strength, workability, and the like. Calcium silicate is not particularly limited, but is at least one selected from wollastonite (CaSiO 3 ), tobermorite (5CaO · 6SiO 2 · 5H 2 O) and zonotlite (6CaO · 6SiO 2 · H 2 O). It is preferable to contain these at a ratio of 10 to 100% by mass.
また、けい酸カルシウム単体であってもよいが、必要に応じて、従来から耐熱材料に配合されている公知の材料を添加してもよい。中でも、補強繊維の添加は好ましく、ガラス繊維や炭素繊維、セラミックス繊維等を０．１〜３質量％の割合で添加させることができる。尚、これら補強繊維の繊維径や繊維長は、繊維径３〜１５μｍ、繊維長３〜１０ｍｍのものが補強効果に優れ、好ましい。 Moreover, although calcium silicate single-piece | unit may be sufficient, you may add the well-known material conventionally mix | blended with the heat-resistant material as needed. Among these, addition of reinforcing fibers is preferable, and glass fibers, carbon fibers, ceramic fibers, and the like can be added at a ratio of 0.1 to 3% by mass. In addition, as for the fiber diameter and fiber length of these reinforcing fibers, those having a fiber diameter of 3 to 15 μm and a fiber length of 3 to 10 mm are excellent in the reinforcing effect and are preferable.
けい酸カルシウムを含む多孔質の成形体を得るには、公知の製造方法を用いることができ、例えば、抄造法や脱水プレス法が用いられればよい。具体的には、けい酸カルシウム原料や補強用繊維を含む水性スラリーを脱水成形して例えば板状の脱水成形物とし、脱水成形物を水熱処理すればよい。尚、けい酸カルシウム原料は、石灰原料とけい酸原料との混合物であり、石灰、ゾノトライト、ワラストナイト、けい石等で構成される。また、水性スラリーには消泡剤や凝集剤を添加することが好ましく、それぞれスラリー中に固形物換算で０．０１〜０．３質量％の割合で添加することができる。消泡剤は、得られる低融点金属鋳造装置用耐熱材料に残留しない方が好ましく、そのため水溶性のものを用いて脱水成形時に水とともに排出することが好ましい。 In order to obtain a porous molded body containing calcium silicate, a known production method can be used. For example, a papermaking method or a dehydration press method may be used. Specifically, an aqueous slurry containing a calcium silicate raw material and reinforcing fibers may be dehydrated to form, for example, a plate-shaped dehydrated molded product, and the dehydrated molded product may be hydrothermally treated. The calcium silicate raw material is a mixture of a lime raw material and a silicate raw material, and is composed of lime, zonotlite, wollastonite, silica, and the like. Moreover, it is preferable to add an antifoamer and a coagulant | flocculant to an aqueous slurry, and it can add in the ratio of 0.01-0.3 mass% in conversion of a solid in a slurry, respectively. It is preferable that the antifoaming agent does not remain in the heat-resistant material for the low-melting-point metal casting apparatus to be obtained. For this reason, it is preferable to use a water-soluble material and discharge it with water during dehydration molding.
水熱処理は、脱水成形物をオートクレーブに入れ、水蒸気雰囲気下で加熱すればよい。この水熱処理はけい酸カルシウムの合成が完了するまで行う必要があり、けい酸カルシウム原料の組成、脱水成形物の大きさ、生成させるけい酸カルシウムの種類に応じて適宜設定されるが、水蒸気圧０．９〜１．８ＭＰａ、処理時間２〜２０時間が適当である。 In the hydrothermal treatment, the dehydrated molded product may be placed in an autoclave and heated in a steam atmosphere. This hydrothermal treatment needs to be carried out until the synthesis of calcium silicate is completed, and is set as appropriate depending on the composition of the calcium silicate raw material, the size of the dehydrated molded product, and the type of calcium silicate to be produced. 0.9 to 1.8 MPa and a processing time of 2 to 20 hours are appropriate.
水熱処理後に乾燥して、そのまま使用に供することができるが、この状態でのけい酸カルシウムの結晶形態はワラストナイトとゾノトライトの混合であり、より耐食性を高めるためにゾノトライトの結晶水を脱水させる目的で焼成することが好ましい。焼成は、結晶水を脱水できれば制限がなく、例えば窒素雰囲気中で６００〜８００℃、２〜５時間行うのが適当である。焼成後のけい酸カルシウムの結晶形態はゾノトライトが脱水しているため、ワラストナイトが主成分となっている。 It can be dried after hydrothermal treatment and used as it is, but the crystalline form of calcium silicate in this state is a mixture of wollastonite and zonotolite, and the crystallization of zonotlite crystallization water is dehydrated in order to enhance the corrosion resistance. It is preferable to fire for the purpose. The firing is not limited as long as water of crystallization can be dehydrated. For example, the firing is suitably performed in a nitrogen atmosphere at 600 to 800 ° C. for 2 to 5 hours. The crystal form of calcium silicate after firing is mainly wollastonite because zonotlite is dehydrated.
尚、けい酸カルシウムを含む多孔質の成形体は、上記に限らず、市販品を使用することもできる。 In addition, the porous molded object containing a calcium silicate is not restricted to the above, A commercial item can also be used.
耐熱性コーティング材からなる被膜の膜厚は、特に制限されるものではないが、十分な耐食性を得るためには、３０μｍ以上であることが好ましく、５０μｍ以上がより好ましい。尚、必要以上に厚い被膜を形成しても耐食性の更なる向上は見込めず、膜厚の上限は１００μｍとするのが適当である。 The film thickness of the film made of the heat resistant coating material is not particularly limited, but is preferably 30 μm or more, and more preferably 50 μm or more in order to obtain sufficient corrosion resistance. It should be noted that even if a film that is thicker than necessary is formed, further improvement in corrosion resistance cannot be expected, and the upper limit of the film thickness is suitably 100 μm.
被膜形成方法にも制限がなく、刷毛等による塗布、スプレーによる噴霧、浸漬等、適宜選択できる。 There is no restriction | limiting also in the film formation method, Application | coating with a brush etc., spraying by spraying, immersion, etc. can be selected suitably.
そして、耐熱性コーティング材を塗布した後、乾燥して水分を蒸発させて被膜を形成することで、本発明の低融点金属鋳造装置用耐熱材料が得られる。本発明の低融点金属鋳造装置用耐熱材料は、被膜中のフッ化物により優れた耐食性が付与されており、特にマグネシウムやマグネシウムを含む合金の溶湯と接触する部位に最適である。また、多孔質耐熱性成形体としてけい酸カルシウムを用いた場合には、加工性に優れ、切削加工等により容易に所望形状に加工することができるようになる。そのため、マグネシウムやマグネシウム合金を鋳造する装置の注湯ボックスや樋、保持炉等の内張り材、あるいはフロートやスパウト、ホット・トップリング、トランジションプレート等の付属部材として好適である。 And after apply | coating a heat resistant coating material, the heat resistant material for low melting metal casting apparatuses of this invention is obtained by drying and evaporating a water | moisture content and forming a film. The heat-resistant material for a low-melting-point metal casting apparatus of the present invention is imparted with excellent corrosion resistance due to the fluoride in the film, and is particularly suitable for a portion that comes into contact with magnesium or a molten alloy containing magnesium. Further, when calcium silicate is used as the porous heat-resistant molded article, it is excellent in workability and can be easily processed into a desired shape by cutting or the like. Therefore, it is suitable as a lining material such as a pouring box, a slag, and a holding furnace of an apparatus for casting magnesium or a magnesium alloy, or an accessory member such as a float, a spout, a hot top ring, or a transition plate.
以下に実施例及び比較例を挙げて本発明について更に説明するが、本発明はこれにより制限されるものではない。 EXAMPLES The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereby.
（実施例１〜１２、比較例１〜２）
表１〜３に示す配合物を２０分間混合攪拌し、コーティング材を調製した。尚、配合物の詳細は以下のとおりである。
(Examples 1-12, Comparative Examples 1-2)
The formulations shown in Tables 1 to 3 were mixed and stirred for 20 minutes to prepare a coating material. The details of the blend are as follows.
このコーティング材をニチアス株式会社製「ルミボード ＬＨ−２００Ｓ」（気孔率７１％）に坪量２００ｇ／ｍ３となるように塗布した後、１０５℃で２４時間乾燥して試験体を作製した。尚、前記気孔率はＪＩＳ Ｒ ２６１４に準じて測定した。そして、試験体について下記に示す浸食試験を行った。 The coating material was applied to “Lumiboard LH-200S” (porosity 71%) manufactured by NICHIAS Corporation so as to have a basis weight of 200 g / m 3, and then dried at 105 ° C. for 24 hours to prepare a test specimen. The porosity was measured according to JIS R 2614. And the erosion test shown below was done about the test body.
＜浸食試験＞
試験体から一辺が約７０ｍｍの正方形で、厚さが２５ｍｍの試験片を切り出し、図２に模式的に示すように、セッターの上に配置した試験片のほぼ中心部にマグネシウム合金（ＡＺ３１）からなる直径８ｍｍで高さ１０ｍｍの円柱を置き、円柱の上面に０．２ＭＰａの荷重を加えた状態で、アルゴン雰囲気中で室温から２時間かけて８００℃まで昇温してマグネシウム合金を溶融させ、その後、マグネシウム合金融液の液面上に同荷重を負荷した状態で、アルゴン雰囲気中、８００℃にて１時間保持し、マグネシウム合金融液と試験片との接触状態を保った。１時間後、開圧してマグネシウム合金融液を試験片の表面から回収し、室温まで冷却した後、試験片の断面を観察してマグネシウム合金融液との接触により浸食された部分の面積を測定した。結果を同表に示すが、実用上特に問題なしに「○」、実用上問題ありに「×」を記した。
<Erosion test>
A test piece having a square of about 70 mm on one side and a thickness of 25 mm was cut out from the test specimen, and as shown schematically in FIG. 2, a magnesium alloy (AZ31) was formed at the substantially central portion of the test piece placed on the setter. A cylinder having a diameter of 8 mm and a height of 10 mm is placed, and with a 0.2 MPa load applied to the upper surface of the cylinder, the magnesium alloy is melted by raising the temperature from room temperature to 800 ° C. over 2 hours in an argon atmosphere. Then, in the state which loaded the same load on the liquid surface of the magnesium compound financial liquid, it hold | maintained at 800 degreeC in argon atmosphere for 1 hour, and the contact state of a magnesium compound financial liquid and a test piece was maintained. One hour later, the pressure is released and the magnesium combined liquid is collected from the surface of the test piece, cooled to room temperature, and then the cross section of the test piece is observed to measure the area of the portion eroded by contact with the magnesium combined financial liquid. did. The results are shown in the same table, and “◯” is marked with no practical problem, and “X” is marked with practical problem.
実施例１〜１２のようにフッ化物と無機バインダーとを含むコーティング材からなる被膜を形成することで、耐食性が格段に向上することがわかる。また、無機バインダーとしてコロイダルシリカを用いた実施例７及び実施例８では被膜に微小クラックが見られたが、被膜の表面性状も良好である。 It turns out that corrosion resistance improves markedly by forming the film which consists of a coating material containing a fluoride and an inorganic binder like Examples 1-12. In Example 7 and Example 8 using colloidal silica as the inorganic binder, fine cracks were observed in the film, but the surface properties of the film were also good.
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| JPS6110077A (en) * | 1984-06-26 | 1986-01-17 | 品川白煉瓦株式会社 | Lining structure for molten iron vessel |
| JPH03106558A (en) * | 1989-09-20 | 1991-05-07 | Honda Motor Co Ltd | Nozzle member for casting and production thereof |
| JPH05104239A (en) * | 1991-10-09 | 1993-04-27 | Kurosaki Refract Co Ltd | Tool for casting low melting point metal having two or more layer coating |
| JPH1147906A (en) * | 1997-07-29 | 1999-02-23 | Toshiba Mach Co Ltd | Erosion resistant hybrid ladle |
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|---|---|---|---|---|
| JPS6110077A (en) * | 1984-06-26 | 1986-01-17 | 品川白煉瓦株式会社 | Lining structure for molten iron vessel |
| JPH03106558A (en) * | 1989-09-20 | 1991-05-07 | Honda Motor Co Ltd | Nozzle member for casting and production thereof |
| JPH05104239A (en) * | 1991-10-09 | 1993-04-27 | Kurosaki Refract Co Ltd | Tool for casting low melting point metal having two or more layer coating |
| JPH1147906A (en) * | 1997-07-29 | 1999-02-23 | Toshiba Mach Co Ltd | Erosion resistant hybrid ladle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9003784B2 (en) | 2008-11-24 | 2015-04-14 | Emitec Gesellschaft Fuer Emissionstechnologie Mbh | Electrical conductor, thermoelectric generator and motor vehicle |
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