JP6968369B2 - Inoculant for cast iron containing oxides - Google Patents
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本発明は、ダクタイル鋳鉄などの黒鉛粒数を増加させるための鋳鉄用接種剤に関するものである。 The present invention relates to an inoculant for cast iron for increasing the number of graphite grains such as ductile cast iron.
従来から黒鉛粒数を増加させるための鋳鉄用接種剤としては、母合金のなかに硫黄と黒鉛球状化元素との化合物を含有することを特徴とし、さらに詳細には、硫黄と化合したマグネシウムとの化合物、硫黄と化合した希土類元素との化合物、硫黄とマグネシウムと希土類元素との化合物のいずれかの化合物を含有する母合金としたことを特徴とするものが存在する（特許文献１）。 Conventionally, the injecting agent for cast iron for increasing the number of graphite grains has been characterized by containing a compound of sulfur and a graphite spheroidizing element in the mother alloy, and more specifically, magnesium combined with sulfur. (Patent Document 1), there is a compound characterized by containing a compound of any of the above compounds, a compound of a rare earth element compounded with sulfur, and a compound of sulfur, magnesium, and a rare earth element (Patent Document 1).
さらに、この種の鋳鉄用接種剤としては、球状黒鉛鋳鉄の溶湯処理の際に溶湯に接触させられる球状黒鉛鋳鉄用接種剤であって、ＳｉＣ粉末と少なくともＦｅ−Ｓｉ系合金とを複合化してなるものが存在する（特許文献２）。 Further, this kind of injecting agent for cast iron is an injecting agent for spheroidal graphite cast iron that is brought into contact with the molten metal during the molten metal treatment of spheroidal graphite cast iron, and is a composite of SiC powder and at least an Fe—Si alloy. (Patent Document 2).
また、この種の鋳鉄用接種剤としては、球状黒鉛鋳鉄の鋳鉄溶湯に接種を行うためのＢｉ系接種剤であって、Ｂｉと、Ｎｉ、Ｃｕのいずれか１種または２種とを含む混合物または合金であることを特徴とするものが存在する（特許文献３）。 Further, this kind of inoculator for cast iron is a Bi-based inoculator for inoculating molten cast iron of spheroidal graphite cast iron, and is a mixture containing Bi and any one or two of Ni and Cu. Alternatively, there is one characterized by being an alloy (Patent Document 3).
ダクタイル鋳鉄などの鋳造において、接種剤による黒鉛粒数の増加によって得られる効果としては、鋳鉄の材質強度の向上、引け性（鋳造不良）の低減、鋳造歩留まりの向上（コスト低減）などが考えられる。 In casting of ductile cast iron, etc., the effects obtained by increasing the number of graphite grains by the injectant are considered to be improvement of the material strength of cast iron, reduction of shrinkage (casting defect), improvement of casting yield (cost reduction), etc. ..
そこで、本発明は、従来の接種剤と同等以上に黒鉛粒数を増加させる接種剤を提供することを目的としてなされたものである。 Therefore, the present invention has been made for the purpose of providing an inoculant that increases the number of graphite grains to be equal to or higher than that of a conventional inoculant.
そのため、本発明の鋳鉄用接種剤は、ＦｅーＳｉ系合金粉末と、酸化ビスマス粉末と、酸化ランタン粉末と、酸化セリウム粉末と、酸化アンチモン粉末とを含有してなるものとしている。 Therefore, the inoculant for cast iron of the present invention comprises Fe-Si alloy powder, bismuth oxide powder, lanthanum oxide powder, cerium oxide powder, and antimony oxide powder.
そして、本発明の鋳鉄用接種剤は、接種剤全量において、ＦｅーＳｉ系合金粉末の元素組成は、Ｆｅが２１〜２５重量％、Ｓｉが６０〜７５重量％、Ｃａが０．５〜３．０重量％、Ａｌが０．５〜２．０重量％、Ｚｒが０〜４．０重量％であるものとしている。 In the cast iron inoculant of the present invention, the elemental composition of the Fe-Si alloy powder is 21 to 25% by weight for Fe, 60 to 75% by weight for Si, and 0.5 to 3 for Ca in the total amount of the inoculant. It is assumed that 0.0% by weight, Al is 0.5 to 2.0% by weight, and Zr is 0 to 4.0% by weight.
さらに、本発明の鋳鉄用接種剤は、接種剤全量において、酸化ビスマス粉末の含有量は０．０１〜１０．０重量％、酸化ランタン粉末の含有量は０．０１〜１０．０重量％、酸化セリウム粉末の含有量は０．０１〜１０．０重量％、酸化アンチモン粉末の含有量は０．０１〜１０．０重量％であるものとしている。 Further, the inoculant for cast iron of the present invention has a content of bismuth oxide powder of 0.01 to 10.0% by weight and a content of lanthanum oxide powder of 0.01 to 10.0% by weight in the total amount of the inoculant. The content of the cerium oxide powder is 0.01 to 10.0% by weight, and the content of the antimony oxide powder is 0.01 to 10.0% by weight.
本発明の鋳鉄用接種剤は、以上に述べたように構成されており、従来の接種剤と同等以上に黒鉛粒数を増加させることができるものとなった。 The inoculant for cast iron of the present invention is configured as described above, and the number of graphite grains can be increased to the same level as or higher than that of the conventional inoculant.
以下、本発明の鋳鉄用接種剤を実施するための形態を詳細に説明する。 Hereinafter, embodiments for carrying out the inoculant for cast iron of the present invention will be described in detail.
本発明の鋳鉄用接種剤は、ＦｅーＳｉ系合金粉末と、酸化ビスマス粉末と、酸化ランタン粉末と、酸化セリウム粉末と、酸化アンチモン粉末とを含有してなるものとしている。 The inoculant for cast iron of the present invention comprises Fe-Si alloy powder, bismuth oxide powder, lanthanum oxide powder, cerium oxide powder, and antimony oxide powder.
そして、本発明の鋳鉄用接種剤において、ＦｅーＳｉ系合金粉末は、ＣａおよびＡｌを含有しており、これらに加え必要に応じてＺｒを含有したものとしており、接種剤全量において、ＦｅーＳｉ系合金の元素組成は、Ｆｅが２１〜２５重量％、Ｓｉが６０〜７５重量％、Ｃａが０．５〜３．０重量％、Ａｌが０．５〜２．０重量％、Ｚｒが０〜４．０重量％であるものとしており、Ｆｅが２１〜２５重量％、Ｓｉが６２〜７０重量％、Ｃａが０．７〜２．３重量％、Ａｌが１．０〜１．２重量％、Ｚｒが０〜１．６重量％であるものとするのが好ましい。 In the inoculant for cast iron of the present invention, the Fe-Si alloy powder contains Ca and Al, and if necessary, Zr is contained in addition to these. The elemental composition of the Si alloy is 21 to 25% by weight of Fe, 60 to 75% by weight of Si, 0.5 to 3.0% by weight of Ca, 0.5 to 2.0% by weight of Al, and Zr. It is assumed to be 0 to 4.0% by weight, Fe is 21 to 25% by weight, Si is 62 to 70% by weight, Ca is 0.7 to 2.3% by weight, and Al is 1.0 to 1.2%. It is preferable that% by weight and Zr are 0 to 1.6% by weight.
さらに、本発明の鋳鉄用接種剤は、接種剤全量において、酸化ビスマス粉末の含有量は０．０１〜１０．０重量％、好ましくは０．４〜４．６重量％、酸化ランタン粉末の含有量は０．０１〜１０．０重量％、好ましくは０．３〜３．９重量％、酸化セリウム粉末の含有量は０．０１〜１０．０重量％、好ましくは０．１〜１．１重量％、酸化アンチモン粉末の含有量は０．０１〜１０．０重量％、好ましくは０．０５〜０．５重量％であるものとしている。 Further, the inoculant for cast iron of the present invention contains 0.01 to 10.0% by weight, preferably 0.4 to 4.6% by weight of bismuth oxide powder, and contains lanthanum oxide powder in the total amount of the inoculant. The amount is 0.01 to 10.0% by weight, preferably 0.3 to 3.9% by weight, and the content of the cerium oxide powder is 0.01 to 10.0% by weight, preferably 0.1 to 1.1. The content of the antimony oxide powder is 0.01 to 10.0% by weight, preferably 0.05 to 0.5% by weight.
本発明の鋳鉄用接種剤において、酸化ビスマス粉末、酸化ランタン粉末、酸化セリウム粉末および酸化アンチモン粉末の各含有量を前記範囲としたのは、これらの各含有量が前記範囲より少ない場合には黒鉛粒数の増加があまり見られず、これらの各含有量が前記範囲より多い場合にもそれ以上の黒鉛粒数の増加があまり見られないと共に、過剰添加するとこれら酸化物の凝集浮上を起こしたり、球状化阻害の恐れがあるからである。 In the inoculant for cast iron of the present invention, the content of each of bismuth oxide powder, lanthanum oxide powder, cerium oxide powder and antimony oxide powder is set in the above range when each of these contents is less than the above range, graphite. The increase in the number of grains is not so much seen, and even when the content of each of these is higher than the above range, the increase in the number of graphite grains is not so much seen, and when it is excessively added, these oxides are aggregated and levitated. This is because there is a risk of inhibition of spheroidization.
（実施例１〜５）
ＦｅーＳｉ系合金粉末と、酸化ビスマス粉末と、酸化ランタン粉末と、酸化セリウム粉末と、酸化アンチモン粉末とを混合して、表１に示すような元素および化合物組成の接種剤を調製し、ダクタイル鋳鉄系溶湯中に０．１重量％添加した。そして接種処理された溶湯から、鋳造により円柱形状のテストピ−スを作製し、実施例１〜５の接種調製鋳鉄を得た。
(Examples 1 to 5)
Fe-Si alloy powder, bismuth oxide powder, lanthanum oxide powder, cerium oxide powder, and antimony oxide powder are mixed to prepare an inoculant having an element and compound composition as shown in Table 1 and ductile. 0.1% by weight was added to the cast iron-based molten metal. Then, a cylindrical test piece was produced from the inoculated molten metal by casting to obtain inoculated prepared cast iron of Examples 1 to 5.
（比較例１〜４）
ＦｅーＳｉ系合金粉末と、酸化ビスマス粉末、酸化ランタン粉末、酸化セリウム粉末のうちの一種とを混合して、表１に示すような元素および化合物組成の接種剤を調製し、ダクタイル鋳鉄系溶湯中に０．１重量％添加した。そして接種処理された溶湯から、鋳造により円柱形状のテストピ−スを作製し、比較例１〜４の接種調製鋳鉄を得た。
(Comparative Examples 1 to 4)
The Fe-Si alloy powder is mixed with one of bismuth oxide powder, lanthanum oxide powder, and cerium oxide powder to prepare an inoculant having the element and compound composition as shown in Table 1, and a ductile cast iron-based molten metal is prepared. 0.1% by weight was added therein. Then, a cylindrical test piece was produced from the inoculated molten metal by casting to obtain inoculated prepared cast iron of Comparative Examples 1 to 4.
（比較例５、６）
ＣａとＡｌを含有するＦｅーＳｉ系合金粉末、Ｃａ、ＡｌおよびＺｒを含有するＦｅーＳｉ系合金粉末の表１に示すような元素組成の接種剤を調製し、ダクタイル鋳鉄系溶湯中に０．１重量％添加した。そして接種処理された溶湯から、鋳造により円柱形状のテストピ−スを作製し、比較例５、６の接種調製鋳鉄を得た。
(Comparative Examples 5 and 6)
An inoculant having an elemental composition as shown in Table 1 of the Fe-Si alloy powder containing Ca and Al and the Fe-Si alloy powder containing Ca, Al and Zr was prepared, and 0 was added to the ductile cast iron-based molten metal. .1% by weight was added. Then, a cylindrical test piece was produced from the inoculated molten metal by casting to obtain inoculated prepared cast iron of Comparative Examples 5 and 6.
そして、このようにして得られた実施例１〜５、比較例１〜６の接種調製鋳鉄の肉厚部組織を顕微鏡により観察した黒鉛粒数は、表１に示すように、実施例１が４５８個／ｍｍ2 、実施例２が４３４個／ｍｍ2 、実施例３が４８５個／ｍｍ2 、実施例４が５０８個／ｍｍ2 、実施例５が４６３個／ｍｍ2 であり、比較例１が４２６個／ｍｍ2 、比較例２が４０２個／ｍｍ2 、比較例３が３８６個／ｍｍ2 、比較例４が３５６個／ｍｍ2 、比較例５が３７５個／ｍｍ2 、比較例６が３５９個／ｍｍ2 であった。 Then, as shown in Table 1, the number of graphite grains in which the thick part structure of the inoculated prepared cast iron of Examples 1 to 5 and Comparative Examples 1 to 6 thus obtained was observed with a microscope is as shown in Example 1. 458 pieces / mm 2 , Example 2 is 434 pieces / mm 2 , Example 3 is 485 pieces / mm 2 , Example 4 is 508 pieces / mm 2 , Example 5 is 463 pieces / mm 2 , and comparative examples. 1 is 426 pieces / mm 2 , Comparative Example 2 is 402 pieces / mm 2 , Comparative Example 3 is 386 pieces / mm 2 , Comparative Example 4 is 356 pieces / mm 2 , Comparative Example 5 is 375 pieces / mm 2 , Comparative Example. 6 was 359 pieces / mm 2 .
以上の結果、実施例１〜５の黒鉛粒数は、実施例２を除いていずれも４５０個／ｍｍ2 以上であり、比較例１〜６の黒鉛粒数は、比較例１、２を除いて４００個／ｍｍ2 以下であり、これらの平均値においても、実施例では４７０個／ｍｍ2 、比較例では３８４個／ｍｍ2 となり、本発明の実施例における黒鉛粒数は、比較例における黒鉛粒数との比較において明らかな有意差が見られた。 As a result of the above, the number of graphite grains in Examples 1 to 5 was 450 / mm 2 or more in all cases except Example 2, and the number of graphite grains in Comparative Examples 1 to 6 was excluding Comparative Examples 1 and 2. The average value thereof is 400 pieces / mm 2 or less, 470 pieces / mm 2 in the example and 384 pieces / mm 2 in the comparative example, and the number of graphite grains in the examples of the present invention is in the comparative example. A clear significant difference was found in comparison with the number of graphite grains.
また、実施例１の黒鉛粒数は、４５８個／ｍｍ2 であったが、これは酸化ビスマス、酸化ランタン、酸化セリウムおよび酸化アンチモンの各粉末の合計含有量が１．０１重量％である場合の数値である。 The number of graphite grains in Example 1 was 458 / mm 2 , which is the case where the total content of each powder of bismuth oxide, lanthanum oxide, cerium oxide and antimony oxide is 1.01% by weight. It is a numerical value of.
実施例２の黒鉛粒数は、４３４個／ｍｍ2 であったが、これは酸化ビスマス、酸化ランタン、酸化セリウムおよび酸化アンチモンの各粉末の合計含有量が３重量％である場合の数値である。 The number of graphite grains in Example 2 was 434 / mm 2 , which is a value when the total content of each powder of bismuth oxide, lanthanum oxide, cerium oxide and antimony oxide is 3% by weight. ..
実施例３の黒鉛粒数は、４８５個／ｍｍ2 であったが、これは酸化ビスマス、酸化ランタン、酸化セリウムおよび酸化アンチモンの各粉末の合計含有量が５．０１重量％である場合の数値である。 The number of graphite grains in Example 3 was 485 / mm 2 , which is a value when the total content of each powder of bismuth oxide, lanthanum oxide, cerium oxide and antimony oxide is 5.01% by weight. Is.
実施例４の黒鉛粒数は、５０８個／ｍｍ2 であったが、これは酸化ビスマス、酸化ランタン、酸化セリウムおよび酸化アンチモンの各粉末の合計含有量が１０重量％である場合の数値である。 The number of graphite grains in Example 4 was 508 grains / mm 2 , which is a value when the total content of each powder of bismuth oxide, lanthanum oxide, cerium oxide and antimony oxide is 10% by weight. ..
実施例５の黒鉛粒数は、４６３個／ｍｍ2 であったが、これは酸化ビスマス、酸化ランタン、酸化セリウムおよび酸化アンチモンの各粉末の合計含有量が１０重量％である場合の数値である。 The number of graphite grains in Example 5 was 463 / mm 2 , which is a value when the total content of each powder of bismuth oxide, lanthanum oxide, cerium oxide and antimony oxide is 10% by weight. ..
したがって、本発明の鋳鉄用接種剤は、酸化ビスマス粉末の含有量が０．４６〜４．５６重量％、酸化ランタン粉末の含有量が０．３９〜３．８７重量％、酸化セリウム粉末の含有量が０．１１〜１．０７重量％、酸化アンチモン粉末の含有量が０．０５〜０．５重量％であれば、これらの合計含有量の多い少ないに左右されず、より顕著な黒鉛粒数の増加が確認された。 Therefore, the inoculant for cast iron of the present invention contains 0.46 to 4.56% by weight of bismuth oxide powder, 0.39 to 3.87% by weight of lanthanum oxide powder, and cerium oxide powder. When the amount is 0.11 to 1.07% by weight and the content of the antimony oxide powder is 0.05 to 0.5% by weight, the total content of these is not affected by a large amount or a small amount, and more remarkable graphite grains are obtained. An increase in the number was confirmed.
なお、比較例１は、黒鉛粒数が４２６個／ｍｍ2 と比較例の中で一番多かったが、本発明の最も少ない実施例３の黒鉛粒数４３４個／ｍｍ2 よりさらに少なく、しかも実施例３の酸化ビスマス、酸化ランタン、酸化セリウムおよび酸化アンチモンの各粉末の合計含有量は３重量％であるのに対し、比較例１の酸化ビスマス粉末の含有量は１０．１８重量％と本発明の前記各粉末の合計含有量の範囲を超えており、本発明に比べ黒鉛粒数の増加率は低いといえる。 In Comparative Example 1, the number of graphite grains was 426 / mm 2, which was the largest among the comparative examples, but it was even smaller than the smallest number of graphite grains in Example 3 of the present invention, which was 434 / mm 2. The total content of each powder of bismuth oxide, lanthanum oxide, cerium oxide and antimony oxide in Example 3 was 3% by weight, whereas the content of bismuth oxide powder in Comparative Example 1 was 10.18% by weight. It is beyond the range of the total content of each of the powders of the present invention, and it can be said that the rate of increase in the number of graphite grains is lower than that of the present invention.
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