JP5072154B2 - High purity Fe-Cr alloy with excellent bending workability - Google Patents
High purity Fe-Cr alloy with excellent bending workability Download PDFInfo
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- JP5072154B2 JP5072154B2 JP2001279867A JP2001279867A JP5072154B2 JP 5072154 B2 JP5072154 B2 JP 5072154B2 JP 2001279867 A JP2001279867 A JP 2001279867A JP 2001279867 A JP2001279867 A JP 2001279867A JP 5072154 B2 JP5072154 B2 JP 5072154B2
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- 238000005452 bending Methods 0.000 title claims description 21
- 229910045601 alloy Inorganic materials 0.000 title claims description 18
- 239000000956 alloy Substances 0.000 title claims description 18
- 229910017060 Fe Cr Inorganic materials 0.000 title claims description 15
- 229910002544 Fe-Cr Inorganic materials 0.000 title claims description 15
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 title claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000011822 basic refractory Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
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- Treatment Of Steel In Its Molten State (AREA)
Description
【0001】
【産業上の利用分野】
本発明は、耐食性に優れたFe−Cr合金に、さらに曲げ加工性をも高めた高純度Fe−Cr合金に関する。
【0002】
【従来の技術】
一般にFe−Cr合金は耐食性を必要とする箇所に使用されている。Cr含有量の増加とともに耐食性は良くなっていくが、加工性は逆に低下してしまう。高Cr合金になるほど、C,Nは素材の靭性に悪影響を及ぼしている。加えてO,S,Pも悪影響を及ぼしている。特にCr含有量が30質量%以上となる高合金鋼においてその傾向は顕著である。
【0003】
【発明が解決しようとする課題】
そのため、Cr含有量が多いFe−Cr合金を耐食性が重視される建築用外装材等に曲げ加工を施して使用しようとする場合、加工時に割れが発生する問題がある。加工性改善のための各種の試みが提案されている。その一つとして、上記C,N等の不純物の影響を考え、それらの含有量を少なくすることが提案されている。真空誘導溶解炉を使用し、溶解前に原料や使用るつぼに付着・吸着されている水分等を極力気化除去するとともに、溶解中にあっても雰囲気からのN,Oのピックアップを極力抑え、適正な脱酸と高塩基度フラックスを使用しての脱硫を施してC,N,O,S,P含有量を極力低下させた材料を製造している。このような高純度合金でも、十分な曲げ加工性が得られない場合がある。
【0004】
曲げ加工性に及ぼす因子として、成分・組成の他に組織あるいは非金属介在物の形態等が挙げられているが、曲げ加工性に及ぼす不純物含有量と非金属介在物の形態の関係については明らかでない。
そこで、本発明は、このような問題を解消すべく案出されたものであり、高純度のFe−Cr合金において不純物含有量と非金属介在物の形態の関係を明らかにし、曲げ加工性に優れたFe−Cr合金を提供すること目的とする。
【0005】
【課題を解決するための手段】
本発明の曲げ加工性に優れた高純度Fe−Cr合金は、その目的を達成するため、Crを29.8〜90質量%含有し、C含有量,N含有量,O含有量,S含有量およびP含有量の合計量が0.020質量%以下で残部がFeおよび不可避的不純物からなる組成を有し、かつ酸化物系介在物中のAl2O3の割合が60質量%以上であることを特徴とする。
【0006】
【作用】
本発明者等は、Fe−Cr合金の曲げ加工性に及ぼす不純物成分C,N,S,P,Oならびに非金属介在物の影響について鋭意検討した。その結果、まず、C,N,S,P,O含有量の合計が0.020質量%を超えると、材料自体の延性、靭性が低下し、加工性を低下させることがわかった。
さらに、C,N,S,P,O含有量を少なくし高純度にして延性、靭性を改善しても、非金属介在物の形態によって加工性が大きく変化することがわかった。特に、Cr含有量が30質量%を超えるようになると材料自体の靭性が低くなるために、この傾向は顕著である。
従って、C,N,S,P,O含有量を少なくするとともに、異質物である非金属介在物の形態を無害化する必要があることがわかった。
【0007】
高純度Fe−Cr合金中の介在物としては、Al2O3やSiO2,MgOなどの酸化物系介在物が多く、それらが曲げ加工性に影響を及ぼしている。
具体的には、C,N,S,P,O含有量が少ない高純度Fe−Cr合金を、曲げ稜線が圧延方向に平行になるように曲げ試験を実施した際、Al2O3含有量が60質量%よりも少ない酸化物系介在物の場合、曲げ加工時に介在物を起点として亀裂が発生することがわかった。Al2O3含有量が60質量%よりも少ない酸化物系介在物は、熱延時に長く展伸するJISG0555で規定されるA系介在物形態であり、曲げ稜線上にこのような形態の介在物が存在すれば、そこを起点として亀裂が入ることがわかった。
【0008】
一方、介在物を、Al2O3を60質量%以上含有するアルミナ系やMgOを含むスピネル系のようなJISG0555で規定されるC系介在物形態にすれば、曲げ加工時に亀裂の起点にならず、加工割れが発生し難いことを突き止めた。
なお、酸化物系介在物中のAl2O3含有量は、酸性溶液やヨウ素アルコールあるいは非水溶媒系溶液を用いてメタルを溶解し酸化物系介在物を抽出した後、湿式分析法を用いて求めればよい。
【0009】
本発明をもう一度整理する。
Cr含有量:8〜90質量%
Cr含有量が8質量%に満たないと耐食性の点で劣り、90質量%を超えると耐食性の向上効果は飽和し、逆に延性、靭性が低下して加工性が悪くなる。
【0010】
[C]+[N]+[O]+[S]+[P]≦0.020質量%
C、N、O、S、P含有量の合計が0.020質量%を超えると、素材そのものの延性,靭性が低下して加工性が悪くなる。特にCr含有量が30質量%以上のものにあってはその傾向が強くなる。具体的には上記不純物含有量が多くなると、冷間圧延の際、板切れや端部われが発生し易くなり、製造性が著しく低下し、製品の歩留まりを著しく低下させるので、上記不純物含有量は合計で0.020質量%以下にする。なお、[X]はX成分の
含有量を示す。
【0011】
酸化物系介在物中のAl 2 O 3 の割合:60質量%以上
酸化物系介在物中のAl2O3の割合が60質量%よりも少ないと、A系介在物になり易く、曲げ稜線に沿って介在物が存在すると曲げ加工の際、介在物が割れの起点になり易い。
【0012】
上記のような不純物含有量の少ないFe−Cr合金は、真空誘導溶解炉を用いて塩基性耐火材製のるつぼに原料を装入し、10-3〜10-4Torr程度の真空下で原料が溶解しない温度まで加熱・保持して原料やるつぼに付着・吸着されている水分等を気化除去した後、大気からのO,Nのピックアップを防止するために溶解炉内を速やかに高純度乾燥Arガス雰囲気に変え、このArガス雰囲気下で溶解,脱酸することで製造できる。
脱酸精錬の際、Alを主成分とする脱酸剤を用いれば、Al2O3を60質量%以上含有するアルミナ系やスピネル系の介在物とすることができる。
【0013】
【実施例】
100kgVIMを用いて、80kgのFe−Cr合金を溶解、鋳造した。るつぼには、CaOクリンカーを予め焼成した95質量%の純度のCaOるつぼを使用した。溶解原料には99%の電解Fe、電解Crを用いた。1×10-4Torrの真空度で原料およびるつぼを十分にベーキングし、原料、るつぼの付着水等を十分に気化除去した後、溶解タンク内にArガスを導入した。Ar気圧は1気圧とし、Arガスは流し続けた。ArガスからのO,Nのピックアップを極力抑えるために、用いるArガスは、N2含有量:0.0005体積%以下で、露点:−50℃の高純度乾燥Arガスとした。
【0014】
Arガス雰囲気中で原料を溶解し目標温度に達した後、脱酸剤としてAlを添加し、CaOとSiO2の質量比(CaO/SiO2)を2.5とした高塩基度フラックスを添加して脱酸精錬を行った。その後、Arガス雰囲気下で鋳型に注入し、鋳塊を得た。
比較例として、10-3Torrの真空下で原料を溶解鋳造した(試験No.6,9)。その他の精錬条件は本発明例と同条件とした。試験No.7,8,10の比較例では、CaOるつぼを用いてAr雰囲気で溶解し、脱酸剤はSiとMnを用いた。その他の溶解、精錬、鋳造の条件は本発明例と同条件とした。
本発明条件および比較例条件で得られた合金鋳塊の化学成分および酸化物介在物組成を表1に示す。なお、酸化物系介在物中のAl2O3含有量はメチルアルコールに10質量%のアセチルアセトンと1質量%のテトラメチルアンモニウムクロライドを加えた非水溶媒系溶液を用いてメタルを電解溶解し酸化物系介在物を抽出した後、湿式分析法を用いて求めた。
【0015】
これら鋳塊に対して熱間圧延、冷間圧延を実施し、板厚0.5mmの冷延板製品を作製した。この製品に対して、曲げ稜線が圧延方向に平行な密着曲げ試験を実施した。
その結果を表1に併せて示す。
本発明成分範囲および酸化物系介在物の範囲の試験No.1〜5では、酸化物系介在物に起因する割れは発生しなかった。
一方、[C]+[N]+[O]+[S]+[P]>0.020質量%となった比較例No.6および9では素材の延性、靭性が不足したため冷間加工時に割れが発生して製品化できなかった。
また、[C]+[N]+[O]+[S]+[P]は0.020質量%以下であるものの、酸化物系介在物中のAl2O3含有量が60質量%に満たない比較例No.7,8,10では、酸化物系介在物を起点とした割れが発生していた。
【0016】
【0017】
【発明の効果】
以上に説明したように、高純度のFe−Cr合金において不純物であるC,N,O,S,Pの含有量を極力低減し、しかも介在する酸化物系介在物の組成をAl2O3含有量が60質量%以上のものとすることにより、製品中の酸化物系介在物を圧延方向に平行に伸延させた形態とし、曲げ加工時の割れ発生がなくなり、曲げ加工性を著しく向上させることができた。[0001]
[Industrial application fields]
The present invention relates to a high-purity Fe-Cr alloy that further improves bending workability to an Fe-Cr alloy having excellent corrosion resistance.
[0002]
[Prior art]
In general, Fe—Cr alloys are used in places that require corrosion resistance. Corrosion resistance improves as the Cr content increases, but the workability decreases. The higher the Cr alloy, the more C and N have an adverse effect on the toughness of the material. In addition, O, S, and P have an adverse effect. This tendency is particularly noticeable in high alloy steels with a Cr content of 30% by mass or more.
[0003]
[Problems to be solved by the invention]
For this reason, when an Fe-Cr alloy having a high Cr content is to be used after being bent on a building exterior material or the like where corrosion resistance is important, there is a problem that cracking occurs during processing. Various attempts to improve workability have been proposed. As one of them, it has been proposed to reduce the content of these impurities in consideration of the influence of impurities such as C and N. Use a vacuum induction melting furnace to vaporize and remove water adhering to and adsorbed to raw materials and crucibles before melting as much as possible, and suppress pickup of N and O from the atmosphere as much as possible even during melting. Desulfurization using high dehydration and high basicity flux is used to produce a material in which the C, N, O, S, and P contents are reduced as much as possible. Even with such a high-purity alloy, sufficient bending workability may not be obtained.
[0004]
Factors affecting bending workability include the structure and form of non-metallic inclusions in addition to the component and composition, but the relationship between the impurity content affecting bending workability and the form of non-metallic inclusions is clear. Not.
Therefore, the present invention has been devised to solve such problems, and in high-purity Fe-Cr alloys, the relationship between the impurity content and the form of non-metallic inclusions is clarified and bending workability is improved. An object is to provide an excellent Fe—Cr alloy.
[0005]
[Means for Solving the Problems]
The high-purity Fe-Cr alloy having excellent bending workability according to the present invention contains 29.8 to 90% by mass of Cr, C content, N content, O content, S content in order to achieve the object. The total amount of P and the P content is 0.020% by mass or less, the balance is Fe and inevitable impurities , and the proportion of Al 2 O 3 in the oxide inclusions is 60% by mass or more. It is characterized by being.
[0006]
[Action]
The present inventors diligently studied the influence of impurity components C, N, S, P, O and non-metallic inclusions on the bending workability of the Fe—Cr alloy. As a result, first, it was found that when the total content of C, N, S, P, and O exceeds 0.020% by mass, the ductility and toughness of the material itself are lowered and workability is lowered.
Furthermore, it was found that even if the content of C, N, S, P, and O is reduced and the purity is increased to improve ductility and toughness, the workability varies greatly depending on the form of nonmetallic inclusions. In particular, when the Cr content exceeds 30% by mass, the toughness of the material itself decreases, and this tendency is remarkable.
Therefore, it has been found that it is necessary to reduce the C, N, S, P, and O contents and to make the form of the non-metallic inclusions that are foreign substances harmless.
[0007]
As inclusions in the high purity Fe—Cr alloy, there are many oxide type inclusions such as Al 2 O 3 , SiO 2 , and MgO, which affect bending workability.
Specifically, when a bending test was performed on a high-purity Fe—Cr alloy having a low C, N, S, P, and O content such that the bending ridge line was parallel to the rolling direction, the Al 2 O 3 content was determined. In the case of oxide inclusions having a content of less than 60% by mass, it was found that cracks occurred starting from the inclusions during bending. The oxide-based inclusion having an Al 2 O 3 content of less than 60% by mass is an A-based inclusion form defined by JISG0555 that extends long during hot rolling, and such an inclusion is present on the bending ridge line. It was found that if there was an object, it would crack from that point.
[0008]
On the other hand, if the inclusion is made into a C-based inclusion form defined by JISG0555, such as an alumina system containing 60% by mass or more of Al 2 O 3 or a spinel system containing MgO, it becomes a starting point of cracking during bending. As a result, it was found that it was difficult for processing cracks to occur.
In addition, the content of Al 2 O 3 in the oxide inclusions is determined using a wet analysis method after dissolving the metal and extracting the oxide inclusions using an acidic solution, iodine alcohol, or a non-aqueous solvent solution. Find it.
[0009]
The present invention is organized again.
Cr content: 8 to 90% by mass
If the Cr content is less than 8% by mass, the corrosion resistance is inferior, and if it exceeds 90% by mass, the effect of improving the corrosion resistance is saturated, and conversely, the ductility and toughness are lowered and the workability is deteriorated.
[0010]
[C] + [N] + [O] + [S] + [P] ≦ 0.020 mass%
When the total content of C, N, O, S, and P exceeds 0.020% by mass, the ductility and toughness of the material itself are lowered and workability is deteriorated. In particular, when the Cr content is 30% by mass or more, the tendency becomes strong. Specifically, when the impurity content is increased, during cold rolling, sheet breakage and edge cracking are likely to occur, the productivity is significantly reduced, and the yield of the product is significantly reduced. Is 0.020 mass% or less in total. In addition, [X] shows content of X component.
[0011]
The ratio of Al 2 O 3 oxide-based inclusions: the ratio of Al 2 O 3 of 60 wt% or more <br/> oxide inclusions in less than 60 mass% results in A-type inclusions When inclusions exist along the bending ridgeline, the inclusions are likely to become the starting point of cracking during bending.
[0012]
The Fe—Cr alloy having a low impurity content as described above is charged with a raw material in a basic refractory crucible using a vacuum induction melting furnace, and the raw material under a vacuum of about 10 −3 to 10 −4 Torr. After heating and holding to a temperature that does not dissolve, vaporize and remove the water adhering to and adsorbed to the raw material and crucible, and then rapidly dry the inside of the melting furnace to prevent O and N pick-up from the atmosphere It can manufacture by changing to Ar gas atmosphere and melt | dissolving and deoxidizing in this Ar gas atmosphere.
If a deoxidizer containing Al as a main component is used during deoxidation refining, an alumina or spinel inclusion containing 60% by mass or more of Al 2 O 3 can be obtained.
[0013]
【Example】
80 kg of Fe—Cr alloy was melted and cast using 100 kg VIM. As a crucible, a CaO crucible having a purity of 95% by mass obtained by firing a CaO clinker in advance was used. 99% electrolytic Fe and electrolytic Cr were used as melting raw materials. The raw material and the crucible were sufficiently baked at a vacuum of 1 × 10 −4 Torr, and the raw material, water adhering to the crucible and the like were sufficiently vaporized and removed, and then Ar gas was introduced into the dissolution tank. Ar pressure was 1 atm, and Ar gas was kept flowing. In order to suppress pickup of O and N from the Ar gas as much as possible, the Ar gas used was a high-purity dry Ar gas having an N 2 content of 0.0005% by volume or less and a dew point of −50 ° C.
[0014]
After melting the raw materials in the Ar gas atmosphere and reaching the target temperature, Al is added as a deoxidizer, and a high basicity flux with a mass ratio of CaO to SiO 2 (CaO / SiO 2 ) of 2.5 is added. Then deoxidation refining was performed. Thereafter, it was poured into a mold in an Ar gas atmosphere to obtain an ingot.
As a comparative example, the raw material was melted and cast under a vacuum of 10 −3 Torr (Test Nos. 6 and 9). Other refining conditions were the same as those in the present invention. Test No. In Comparative Examples 7, 8, and 10, dissolution was performed in an Ar atmosphere using a CaO crucible, and Si and Mn were used as deoxidizers. Other melting, refining, and casting conditions were the same as those in the examples of the present invention.
Table 1 shows the chemical composition and oxide inclusion composition of the alloy ingot obtained under the conditions of the present invention and the comparative example. The content of Al 2 O 3 in the oxide inclusions is oxidized by dissolving the metal by electrolysis using a non-aqueous solvent system solution in which 10% by mass of acetylacetone and 1% by mass of tetramethylammonium chloride are added to methyl alcohol. After extracting physical inclusions, it was determined using a wet analysis method.
[0015]
These ingots were hot-rolled and cold-rolled to produce cold-rolled sheet products having a sheet thickness of 0.5 mm. The product was subjected to an adhesion bending test in which the bending ridge line was parallel to the rolling direction.
The results are also shown in Table 1.
Test No. in the range of the component of the present invention and the range of oxide inclusions In 1-5, the crack resulting from an oxide type inclusion did not generate | occur | produce.
On the other hand, the comparative example No. which became [C] + [N] + [O] + [S] + [P]> 0.020 mass%. In 6 and 9, since the ductility and toughness of the material were insufficient, cracks occurred during cold working, and the product could not be produced.
[C] + [N] + [O] + [S] + [P] is 0.020% by mass or less, but the content of Al 2 O 3 in the oxide inclusions is 60% by mass. Comparative Example No. In 7, 8, and 10, cracks were generated starting from oxide inclusions.
[0016]
[0017]
【Effect of the invention】
As described above, the content of C, N, O, S, and P as impurities in the high purity Fe—Cr alloy is reduced as much as possible, and the composition of the intervening oxide inclusions is changed to Al 2 O 3. By making the content 60% by mass or more, the oxide inclusions in the product are extended in parallel with the rolling direction, cracking is eliminated during bending, and bending workability is remarkably improved. I was able to.
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