JP4456058B2 - Spheroidizing agent for ductile cast iron and spheroidizing method for ductile cast iron - Google Patents
Spheroidizing agent for ductile cast iron and spheroidizing method for ductile cast iron Download PDFInfo
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本発明は、ダクタイル鋳鉄用球状化処理剤及びダクタイル鋳鉄の球状化処理方法に関する。 The present invention relates to a spheroidizing agent for ductile cast iron and a spheroidizing method for ductile cast iron.
パーライト系ダクタイル鋳鉄を製造する場合、Ｂ（ボロン）が混入すると、パーライトの析出量が減少して所定の機械的性質が得られない場合があることが知られている。ボロンは鋳造用耐火物に焼結促進剤として混合されるホウ砂から導入される場合もあるし、鋳鉄原料として用いられる高張力鋼板スクラップに含まれている場合もあるが一般の鋳造工場で用いられる分析装置では分析できないうえに、０．００１（重量％）=１０ＰＰＭ程度の微量でパーライト析出量の減少（フェライト析出量の増加）を招くので、一般的に行われる鋳鉄の成分管理方法では、予期せずに材質が不良になることがある。 When manufacturing pearlite type ductile cast iron, it is known that when B (boron) is mixed, the precipitation amount of pearlite is reduced, and predetermined mechanical properties may not be obtained. Boron may be introduced from borax mixed as a sintering accelerator in a refractory for casting, or may be contained in high-tensile steel scrap used as a raw material for cast iron, but is used in general foundries. In addition to being unable to analyze with the analysis apparatus provided, it causes a decrease in the amount of pearlite precipitation (increase in the amount of ferrite precipitation) in a small amount of about 0.001 (% by weight) = 10 PPM. Unexpectedly, the material may become defective.
また、特許文献１に記載の鋳鉄用添加剤のＣａ−Ｍｇ−ＲＥ−Ｆｅ−Ｓｉ合金は使用目的がパーライト系バーミキュラー鋳鉄製造用であり、本願目的とは異なる。また、特許文献２，３に記載の球状黒鉛鋳鉄は、本願目的と異なるため、成分範囲が異なる。
かかる従来の実情に鑑みて、本発明は、パーライト系ダクタイル鋳鉄の製造において、ボロンによる不測のパーライト析出量の減少を防止するためのダクタイル鋳鉄用球状化処理剤及びダクタイル鋳鉄の球状化処理方法を提供することを目的とする。 In view of such conventional circumstances, the present invention provides a spheroidizing treatment agent for ductile cast iron and a spheroidizing method for ductile cast iron for preventing an unexpected decrease in the amount of pearlite deposited due to boron in the manufacture of pearlite-based ductile cast iron. The purpose is to provide.
上記目的を達成するため、本発明に係るダクタイル鋳鉄用球状化処理剤の特徴は、Ｓｉを４０〜６０重量％、Ｍｇを２〜１０重量％、Ｃａを０．５〜６重量％、Ｚｒを０．２〜３重量％含有し、残部Ｆｅ及び不可避的不純物よりなることにある。 In order to achieve the above object, the spheroidizing agent for ductile cast iron according to the present invention is characterized in that Si is 40 to 60% by weight, Mg is 2 to 10% by weight, Ca is 0.5 to 6% by weight, and Zr is It is contained in an amount of 0.2 to 3% by weight, and consists of the balance Fe and inevitable impurities.
また、Ｓｉを４０〜６０重量％、Ｍｇを２〜１０重量％、Ｃａを０．５〜６重量％、Ｚｒを０．２〜３重量％、ＲＥを０．２〜６重量％含有し、残部Ｆｅ及び不可避的不純物よりなるように構成してもよい。 Moreover, Si contains 40 to 60% by weight, Mg 2 to 10% by weight, Ca 0.5 to 6% by weight, Zr 0.2 to 3% by weight, RE 0.2 to 6% by weight, You may comprise so that it may consist of remainder Fe and an unavoidable impurity.
上記目的を達成するため、本発明に係るダクタイル鋳鉄の球状化処理方法の特徴は、ダクタイル鋳鉄の球状化処理時に上記いずれかに記載のダクタイル鋳鉄用球状化処理剤を添加することによりＺｒを０．００２〜０．０４５重量％含むダクタイル鋳鉄を得ることにある。 In order to achieve the above object, the feature of the spheroidizing treatment method for ductile cast iron according to the present invention is that Zr is reduced to 0 by adding the spheroidizing agent for ductile cast iron as described above during spheroidizing treatment of ductile cast iron. It is to obtain a ductile cast iron containing 0.002 to 0.045% by weight.
発明者らによれば、ボロンが不測に混入される状況でダクタイル鋳鉄にＺｒ（ジルコニウム）を添加するとボロンによるパーライト析出量の減少効果を打ち消すことができることを見いだした。ジルコニウムはボロンと高融点かつ安定な化合物を形成することが知られており、安定な化合物としてボロンが固定されることによって効果が得られたものと推量される。 The inventors have found that when Zr (zirconium) is added to ductile cast iron in a situation where boron is unexpectedly mixed, the effect of reducing the amount of pearlite deposited by boron can be counteracted. Zirconium is known to form a high melting point and stable compound with boron, and it is assumed that the effect was obtained by fixing boron as a stable compound.
ジルコニウムは高融点（１８５５℃）かつ酸化されやすく、金属ジルコニウムを一般の鋳鉄溶解温度（１５００℃程度）の鋳鉄溶湯に安定に溶け込ませることは困難である。そのためにＦｅ−Ｓｉ−Ｚｒ 等の母合金として添加される場合もあるが、安定な歩留まりを得ることは難しい。そこで、ダクタイル鋳鉄の球状化処理剤として用いられるＦｅ−Ｓｉ−Ｍｇ−Ｃａ 合金（又はＦｅ−Ｓｉ−Ｍｇ−Ｃａ−ＲＥ 合金）にジルコニウムを含有させれば、ジルコニウムが低融点化するとともに、合金に含まれるＣａ、Ｍｇ、（ＲＥ） といったジルコニウムより酸素との親和力が強い元素が存在するので、鋳鉄溶湯に添加する際のジルコニウムの酸化減耗は軽微となる。そして、球状化処理時にＭｇ の気化による溶湯の撹拌も生じることから添加したジルコニウムを均一に撹拌、分散させることもできる。 Zirconium has a high melting point (1855 ° C.) and is easily oxidized, and it is difficult to stably dissolve metal zirconium in a cast iron melt having a general cast iron melting temperature (about 1500 ° C.). Therefore, it may be added as a master alloy such as Fe—Si—Zr 3, but it is difficult to obtain a stable yield. Therefore, if zirconium is contained in the Fe-Si-Mg-Ca alloy (or Fe-Si-Mg-Ca-RE alloy) used as a spheroidizing agent for ductile cast iron, the zirconium has a low melting point, and the alloy Since there are elements having a stronger affinity for oxygen than zirconium, such as Ca, Mg, (RE), contained in the alloy, the oxidation depletion of zirconium when added to the cast iron melt is minimal. Further, since stirring of the molten metal due to vaporization of Mg occurs during the spheroidizing treatment, the added zirconium can be uniformly stirred and dispersed.
上記本発明に係るダクタイル鋳鉄用球状化処理剤及びダクタイル鋳鉄の球状化処理方法の特徴によれば、パーライト系ダクタイル鋳鉄の製造において、ボロンによる不測のパーライト析出量の減少を防止するためのダクタイル鋳鉄用球状化処理剤及びダクタイル鋳鉄の球状化処理方法を提供するに至った。 According to the characteristics of the spheroidizing treatment agent for ductile cast iron and the spheroidizing treatment method for ductile cast iron according to the present invention, the ductile cast iron for preventing an unexpected decrease in the amount of pearlite deposited due to boron in the manufacture of pearlite-based ductile cast iron. Spheroidizing agent for use and a spheroidizing method for ductile cast iron.
本発明の他の目的、構成及び効果については、以下の発明の実施の形態の項から明らかになるであろう。 Other objects, configurations, and effects of the present invention will become apparent from the following embodiments of the present invention.
次に、添付図面を参照しながら、本発明をさらに詳しく説明する。
本発明に係る球状化処理剤は、ダクタイル鋳鉄の球状化処理時に添加されるものであり、この球状化処理剤は下記の成分が各重量％にて配合されたものが望ましい。
Next, the present invention will be described in more detail with reference to the accompanying drawings.
The spheroidizing treatment agent according to the present invention is added at the time of spheroidizing treatment of ductile cast iron, and the spheroidizing treatment agent preferably contains the following components in each weight%.
次に、成分範囲の理由を以下に表示する。なお、以下、パーセンテージは重量パーセンテージを意味するものとする。また、被覆材を使用する場合は被覆材も全体の重量に含まれるものとする。 Next, the reason for the component range is displayed below. Hereinafter, the percentage means a weight percentage. Moreover, when using a coating | covering material, a coating | covering material shall also be included in the whole weight.
Ｓｉ(シリコン ４０−６０％)
Ｓｉ 量４０％以下では本成分系の合金は安定に製造することが困難であり、Ｓｉ：６０％以上ではコストが高くなる一方で球状化処理剤としての機能は改善されません。
Si (silicon 40-60%)
If the Si content is 40% or less, it is difficult to produce the alloy of this component system stably. If Si is 60% or more, the cost increases, but the function as a spheroidizing agent is not improved.
Ｍｇ（マンガン ２−１０％）
球状化処理は一般に鋳鉄溶湯にＭｇ を０．０２−０．０４％歩留まらせる操作であるが、球状化処理剤中のＭｇ 含有量が２％以下では球状化剤の添加量が多くなり、球状化処理に伴う溶湯の温度ドロップが大きくなるとともに処理コストが高くなり実用的ではない。また、Ｍｇ 含有量が１０％を超えるとサンドイッチ法球状化処理時のMgの気化に伴う反応が強くなりすぎ溶湯が飛散して作業上危険となる。
Mg (Manganese 2-10%)
The spheroidizing treatment is generally an operation in which the cast iron melt has a Mg content of 0.02 to 0.04%. However, when the Mg content in the spheroidizing agent is 2% or less, the amount of spheroidizing agent added increases. The temperature drop of the molten metal accompanying the spheroidizing treatment increases and the processing cost increases, which is not practical. On the other hand, if the Mg content exceeds 10%, the reaction accompanying the vaporization of Mg during the spheroidizing process of the sandwich method becomes too strong, and the molten metal is scattered, which is dangerous for work.
Ｃａ(カルシウム ０．５−６％)
Ｃａ は球状化補助と、球状化反応強度の抑制、球状化処理後に発生する反応生成物の性状操作の目的で添加される。しかし、０．５％以下ではその効果がなく、６％以上ではＭｇ の気化反応が抑制されすぎて球状化処理反応が不安定になるとともに、球状化処理後の反応生成物の量が多くなりすぎて実用性を失う。Ｃａは望ましくは４％であることがさらに適切である。
Ca (calcium 0.5-6%)
Ca is added for the purpose of spheroidizing assistance, suppression of the spheroidizing reaction strength, and property manipulation of the reaction product generated after the spheroidizing treatment. However, at 0.5% or less, there is no effect, and at 6% or more, the Mg vaporization reaction is suppressed too much and the spheroidizing reaction becomes unstable, and the amount of reaction products after the spheronizing process increases. Too much loses practicality. More preferably, Ca is desirably 4%.
Ｚｒ(ジルコニウム ０．２−３％)
この範囲であれば安定した合金を製造することができ、Ｚｒ：２％の合金であれば上述の効果が得られる。Ｚｒ 量の下限は本件にあげる効果が得られないこと、Ｚｒ はダクタイル鋳鉄に過剰に添加されると黒鉛球状化率を低下させるとともに、炭化物を生成するので上限値はこの値までが適切である。
Zr (Zirconium 0.2-3%)
If it is this range, a stable alloy can be manufactured, and the above-mentioned effect will be acquired if it is a Zr: 2% alloy. The lower limit of the amount of Zr is ineffective in the present case, and if Zr is excessively added to ductile cast iron, the graphite spheroidization rate is lowered and carbide is generated, so the upper limit is appropriate up to this value. .
ＲＥ（レアアース ０．２−６％）
ＲＥ は球状化補助と、有害微量元素の球状化阻害作用を取り除く目的で添加され、この場合は通常０．２％以上添加されます。しかし、ＲＥは含有量が６％以上と多い場合、球状化処理後のダクタイル鋳鉄の黒鉛化能力を低下させて、引け性を増大させたり、炭化物を生成する。また、ＲＥ は鋳造品の特性によって、異常黒鉛の原因として作用する場合があり、このような用途ではＲＥ を全く含有しないものが必要となる。
RE (Rare Earth 0.2-6%)
RE is added for the purpose of spheroidizing and removing the spheroidizing inhibitory action of harmful trace elements. In this case, RE is usually added in an amount of 0.2% or more. However, when the RE content is as high as 6% or more, the graphitization ability of the ductile cast iron after the spheroidizing treatment is reduced, and the shrinkage is increased or the carbide is generated. In addition, RE may act as a cause of abnormal graphite depending on the characteristics of the cast product. In such applications, RE containing no RE is required.
−残部Ｆｅ （鉄）と不可避的混入物
不可避的に混入する成分としては、例えば、Ｍｎ、Ｐ、Ｃｒ、Ｔｉ、Ａｌ、Ｓｎ 等が挙げられる。
-Remainder Fe (iron) and unavoidable contaminants Examples of components inevitably mixed include Mn, P, Cr, Ti, Al, and Sn.
次に、上記球状化処理剤の実施例について説明する。
Ｚｒ 入り黒鉛球状化剤の実施例１
Next, examples of the spheroidizing agent will be described.
Example 1 of Zr-containing graphite spheroidizing agent
４０００Ｋｇ 高周波炉にて、表１に示す成分の球状黒鉛鋳鉄元湯を溶製した。処理量４００Ｋｇ のサンドイッチ球状化処理取鍋で、表３に示す添加剤の条件で連続して黒鉛球状化処理を行った。カバー剤はいずれもセラミクス系カバー剤を０．８％用い、ボロンはＦｅ−Ｂ 合金として添加した。球状化処理温度は１５００℃±２０℃とし、接種は行わなかった。球状化処理後に溶湯を、ノックオフＫｂ型試験片鋳型に鋳造して顕微鏡組織を調査した。なお、セラミクス系カバー剤としては、例えば酸化マグネシウムを主成分とするカバー剤が挙げられる。 In a 4000 Kg high-frequency furnace, spheroidal graphite cast iron base water having the components shown in Table 1 was melted. A graphite spheroidizing treatment was continuously performed under the additive conditions shown in Table 3 in a sandwich spheroidizing treatment ladle with a throughput of 400 kg. As the cover agent, 0.8% ceramic cover agent was used, and boron was added as an Fe-B alloy. The spheroidizing temperature was 1500 ° C. ± 20 ° C., and no inoculation was performed. After the spheroidizing treatment, the molten metal was cast into a knock-off Kb type test piece mold, and the microstructure was examined. In addition, as a ceramics-type cover agent, the cover agent which has magnesium oxide as a main component is mentioned, for example.
得られた試料の顕微鏡組織を図１に示す。処理番号１では従来の球状化処理剤を用いて、ボロンの影響を受けない場合に相当し、フェライトの析出量は少ない。処理番号２は従来の球状化処理剤を用いて、ボロン０．００２％の影響を受けた場合であり、フェライトの析出量は明らかに増加している。処理番号３はボロン０．００２％の影響を受けながら、本発明品によって球状化処理を行った場合であるが、フェライトの析出量は少ない。
Ｚｒ 入り黒鉛球状化剤の実施例２
１５００Ｋｇ 高周波炉にて、表４に示す成分の球状黒鉛鋳鉄元湯を溶製した。処理量３００Ｋｇ のサンドイッチ球状化処理取鍋で、表６ に示す添加剤の条件で連続して黒鉛球状化処理を行った。カバー剤はいずれもセラミクス系カバー剤を１．０％用い、ボロンはＦｅ−Ｂ 合金として添加した。球状化処理温度は１５４０℃±２０℃とし、接種は行わなかった。球状化処理後に溶湯を、ノックオフＫｂ 型試験片鋳型に鋳造して顕微鏡組織を調査した。
Example 2 of Zr-containing graphite spheroidizing agent
Spheroidal graphite cast iron hot water having the components shown in Table 4 was melted in a 1500 Kg high frequency furnace. A graphite spheroidizing treatment was continuously performed in a sandwich spheroidizing ladle having a throughput of 300 kg under the additive conditions shown in Table 6. As the cover agent, a ceramics-based cover agent was used at 1.0%, and boron was added as an Fe-B alloy. The spheroidizing temperature was 1540 ° C. ± 20 ° C., and no inoculation was performed. After the spheroidizing treatment, the molten metal was cast into a knock-off Kb type test piece mold, and the microstructure was examined.
得られた試料の顕微鏡組織を図２に示す。処理番号４では従来の球状化処理剤を用いて、ボロンの影響を受けない場合に相当し、フェライトはほとんど析出していない。処理番号５は従来の球状化処理剤を用いて、ボロン０．００１５％の影響を受けた場合であり、球状黒鉛の周囲にフェライトの析出量が認められる。処理番号６はボロン０．００１５％の影響を受けながら、少量のＺｒ（Ｚｒ：０．１％）を含有する球状化剤によって処理を行った場合であり、球状黒鉛の周辺にフェライトの析出が認められる。処理番号７はボロン０．００１５％の影響を受けながら、本発明品（Ｚｒ：２．０％含有）で球状化処理を行った場合である。前２者と比較してフェライトの析出量は明らかに少ない。処理番号８はボロン０．００１５％の影響を受けながら、本発明品（Ｚｒ：０．２％含有）で球状化処理を行った場合である。若干のフェライトが析出しているが、明らかなフェライトの減少効果が認められる。
本発明は、ダクタイル鋳鉄用球状化処理剤及びダクタイル鋳鉄の球状化処理方法として利用することができる。 The present invention can be used as a spheroidizing agent for ductile cast iron and a spheroidizing method for ductile cast iron.
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