JPS5932540B2 - High manganese nonmagnetic steel with excellent high temperature strength - Google Patents

Description

【発明の詳細な説明】 本発明は高温強度にすぐれた高マンガン非磁性鋼に係り
、特に７００℃附近の高温まで高強度、高耐力にして、
かつ高温耐酸化性にすぐれた高マンガン非磁性鋼に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high manganese nonmagnetic steel with excellent high temperature strength, and in particular to high strength and high yield strength up to high temperatures around 700°C.
The present invention also relates to a high-manganese nonmagnetic steel that has excellent high-temperature oxidation resistance.

近年、核融合施設、磁気浮上式鉄道を初め、その他のモ
ーター類や変圧器附属品等の分野で強磁場または弱磁場
環境下で磁場の影響を受けることの少ない安価な非磁性
鋼が強く要求されるようになつた。In recent years, there has been a strong demand for inexpensive non-magnetic steel that is less affected by magnetic fields in strong or weak magnetic field environments in the fields of nuclear fusion facilities, magnetic levitation trains, and other motors and transformer accessories. It started to be done.

更に最近ではかかる非磁性鋼が室温もしくはそれ以下の
温度で使用されるだけではなく、例えば製鉄所において
溶鋼の電磁撹拌装置の周辺材料の如く高温環境下で磁場
を印加する設備・器機等にも要求されるようになり、少
くとも７００℃附近の高温まで高強度、高耐力にして、
かつ高温耐酸化性のすぐれた非磁性鋼が要求されるよう
になつて来た。従来、非磁性鋼としては、主としてオー
ステナイト系ステンレス鋼が用いられているが、高価な
Ｎｉを多量含有することのほか、加工および熱処理に対
して磁性が不安定であり、更に強度材料として使用する
場合に耐力が低いという欠点があつた。Furthermore, recently, such non-magnetic steels are not only used at room temperature or lower temperatures, but also in equipment and devices that apply magnetic fields in high-temperature environments, such as surrounding materials for electromagnetic stirring devices for molten steel in steel plants. As demand has increased, high strength and high yield strength have been developed, at least up to high temperatures around 700°C.
There has also been a demand for non-magnetic steel with excellent high-temperature oxidation resistance. Traditionally, austenitic stainless steel has been mainly used as non-magnetic steel, but in addition to containing a large amount of expensive Ni, its magnetic properties are unstable when processed and heat treated, making it difficult to use as a strength material. In some cases, the drawback was that the yield strength was low.

そのため加工や熱処理に対して安定な非磁性を保持し、
かつ機械的特性にもすぐれ、価格も比較的低廉な高マン
ガン非磁性鋼が注目されるようになつた。しかし従来の
高マンガン鋼、例えば標準１３％Ｍｎ鋼は非磁性鋼とし
て一般に使用されているが、耐力および高温耐酸化性の
点で問題があり、７００℃附近までの高温環境下での使
用は困難である。かくの如く、従来の高マンガン非磁性
鋼は一般に高温強度が低く、また高温耐酸化性が悪いた
めに高温用途には適せず、またその目的のための新規の
非磁性鋼が開発されず今日に及んでいる現状である。本
発明の目的は、最近の需要家の要求に応えるため従来の
高マンガン非磁性鋼の欠点を克服し、高温強度、高温耐
力、高温耐酸化性にすぐれ、し、一かもコストの安い高
マンガン非磁性鋼を提供するにある。Therefore, it maintains stable non-magnetic properties against processing and heat treatment,
High-manganese nonmagnetic steel, which also has excellent mechanical properties and is relatively inexpensive, has attracted attention. However, conventional high manganese steels, such as standard 13% Mn steel, are commonly used as non-magnetic steels, but they have problems in terms of yield strength and high temperature oxidation resistance, and cannot be used in high temperature environments up to around 700℃. Have difficulty. As described above, conventional high-manganese non-magnetic steels generally have low high-temperature strength and poor high-temperature oxidation resistance, making them unsuitable for high-temperature applications, and no new non-magnetic steels have been developed for that purpose. This is the current situation that continues to this day. The purpose of the present invention is to overcome the drawbacks of conventional high-manganese non-magnetic steel in order to meet the demands of recent customers, and to develop a high-manganese steel that has excellent high-temperature strength, high-temperature yield strength, high-temperature oxidation resistance, and is also low in cost. To provide non-magnetic steel.

本発明のこの目的は次の要旨の２発明によつて達成され
る。This object of the present invention is achieved by the following two inventions.

第１発明の要旨とするところは次の如くである。The gist of the first invention is as follows.

すなわち重量比にてＣ：０．４〜１．５％，Ｓｉ：３％
以下、Ｍｎ：１４〜３５％，Ｃｒ：３〜１８％，Ｎｉ：
０．１５〜ｌ％，Ｖ：０．１〜ｌ％，Ｎ：０．０２〜０
．１７０，Ｂ：０．００１〜０．１％を含み残部はＦｅ
および不可避的不純物より成ることを特徴とする高温強
度にすぐれた高マンガン非磁性鋼、である。次に第２発
明の要旨とするところは、上記第１発明の主要成分のほ
かに更に、７７０以下のＡｌ，２％以下のＴｉ，２％以
下のＮｂ，２％以下のＺｒ，Ｏ，ｌ％以下のＣａのうち
より選ばれた１種または２種以上を含有し残部はＦｅお
よび不可避的不純物より成ることを特徴とする高温強度
にすぐれた高マンガン非磁性鋼である。That is, C: 0.4 to 1.5%, Si: 3% in weight ratio
Below, Mn: 14-35%, Cr: 3-18%, Ni:
0.15-1%, V: 0.1-1%, N: 0.02-0
．． 170,B: Contains 0.001 to 0.1%, the balance being Fe
This is a high-manganese nonmagnetic steel with excellent high-temperature strength and characterized by consisting of unavoidable impurities. Next, the gist of the second invention is that in addition to the main components of the first invention, Al of 770 or less, Ti of 2% or less, Nb of 2% or less, Zr, O, L of 2% or less This is a high-manganese non-magnetic steel with excellent high-temperature strength, which is characterized by containing one or more selected types of Ca in an amount of % or less, with the remainder consisting of Fe and unavoidable impurities.

すなわち、本発明者らは本発明の目的を達成する高マン
ガン非磁性鋼の研究実験を繰返した結果、Ｎｉならびに
Ｖの添加量を低減させることによりコストを低減し、Ｃ
を高強度が得られる適応量含有せしめ、更に微量のＢお
よび適量のＶの複合添加ならびに適量のＮ添加により、
その固溶ならびに析出効果によつて室温は勿論、高温に
おける耐力が著しく改善され、かつＣｒ，Ｎｉ，Ｖの複
合添加を行うことによつて高温耐酸化性も良好となるこ
とを見出し、更にこれらの主要成分のほかに適量のＡｌ
，Ｔｉ，Ｎｂ，Ｚｒ，Ｃａのうちより選ばれた１種また
は２種以上を添加させることにより本発明鋼の効果が一
段と発揮されることを見出し本発明を得たものである。
本発明鋼の成分各元素の限定理由について説明する。That is, as a result of repeated research experiments on high manganese nonmagnetic steel that achieves the object of the present invention, the present inventors have found that by reducing the amounts of Ni and V added, the cost can be reduced, and C
By containing an appropriate amount of B to obtain high strength, and further adding a small amount of B and an appropriate amount of V, and adding an appropriate amount of N,
We found that the solid solution and precipitation effects significantly improve the yield strength not only at room temperature but also at high temperatures, and that by adding Cr, Ni, and V in combination, high-temperature oxidation resistance also improves. In addition to the main components of
The present invention was achieved by discovering that the effects of the steel of the present invention can be further enhanced by adding one or more selected from among , Ti, Nb, Zr, and Ca.
The reason for limiting each element of the steel of the present invention will be explained.

Ｃ： Ｃの存在はオーステナイト相を安定にして非磁性とする
に有効であり、また強度上昇に対する効果も大きく、そ
のために少くとも０．４％を必要とする。C: The presence of C is effective in stabilizing the austenite phase and making it non-magnetic, and also has a large effect on increasing strength, so at least 0.4% is required.

しかし、１．５％を越すと熱間加工性が悪くなり製造性
に問題を生じるので０，４〜１．５７０の範囲に限定し
た。Ｓｉ： Ｓｉが３％より多くなると高マンガン鋼では冷間加時に
割れを発生するので３％以下とした。However, if it exceeds 1.5%, hot workability deteriorates and problems arise in manufacturability, so it is limited to a range of 0.4 to 1.570. Si: If Si exceeds 3%, cracks will occur in high manganese steel during cold working, so it was set to 3% or less.

Ｍｎ：Ｍｎはオーステナイト相を安定にして非磁性鋼と
するのに欠かせない元素であり、高温強度を保持するた
めに少くとも１４％を必要とする。Mn: Mn is an essential element for stabilizing the austenite phase to make non-magnetic steel, and requires at least 14% to maintain high temperature strength.

しかし３５％を越えると加工性が悪化するので１４〜３
５？の範囲に限定した。Ｃｒ： Ｃｒの添加はＮｉおよびＶとの複合添加により高温耐酸
化性を著しく向上させることを見出したことによる。However, if it exceeds 35%, workability deteriorates, so 14-3
5? limited to the range of Cr: It has been found that the addition of Cr in combination with Ni and V significantly improves high temperature oxidation resistance.

この効果を発揮させるために少くとも３％を必要とする
も、１８％を越すとδ相の混入を来たし、透磁率の増大
を招くので３〜１８７０の範囲に限定した。Ｎｉ： ３〜１８７００）Ｃｒの添加によりＶ，Ｎｉを複合添加
することによつて高温耐酸化性を著しく向上させる作用
を見出したことによるも、Ｎｌ：０．１５％未満ではそ
の効果が現れず、少くとも０，１５％を必要とする。Although at least 3% is required to exhibit this effect, if it exceeds 18%, the δ phase will be mixed in, leading to an increase in magnetic permeability, so it is limited to a range of 3 to 1870. Ni: 3 to 18,700) Although it was discovered that the addition of Cr and the combined addition of V and Ni significantly improved high-temperature oxidation resistance, the effect did not appear when Nl was less than 0.15%. , requires at least 0.15%.

しかしＮ１は高価であり、しかもｌ％を越えた添加では
その効果は飽和の傾向を示し多量の使用はコストの上昇
を来たすのでｌ％以下に限定し、０．１５〜１７０の範
囲内とした。Ｖ：上記の如くＶはＣｒ，Ｎｉとの複合添
加により高温１１酸化性を著しく改善する効果があり、
更にＶはＢとの複合添加によつて、その固溶ならびに析
出効果により室温及び高温での耐力を著しく改善せしめ
ることを見出した。However, N1 is expensive, and if it is added in excess of 1%, its effect tends to be saturated, and its use in large quantities increases the cost, so it is limited to 1% or less, and within the range of 0.15 to 170. . V: As mentioned above, V has the effect of significantly improving high-temperature 11 oxidation property when combined with Cr and Ni.
Furthermore, it has been found that when V is added in combination with B, the yield strength at room temperature and high temperature is significantly improved due to its solid solution and precipitation effects.

そのためにＶ：０．１％以上の添加を必要とするも、ｌ
％を越えての添加は、その効果が飽和傾向を示し、Ｖは
高価な元素であり、コスト上昇に見合う程の効果が得ら
れないので０．１−１７０の範囲に限定した。Ｎ： Ｎはオーステナイト相を安定化し非磁性とする効果が大
きく、更に固溶ならびに窒化物を生成して高温強度を高
める作用があるが、０．０２？未満ではその効果が現わ
れず、一方０．１％を越えての添加は強度上昇のメリツ
１・よりも窒化物の増加による鋼の脆化の方のデメリツ
トの方が強くなるので、０．０２〜０．１７０の範囲に
限定した。Therefore, it is necessary to add V: 0.1% or more, but l
If added in excess of 5%, the effect tends to be saturated, and since V is an expensive element, the effect is not commensurate with the increase in cost. N: N has a great effect of stabilizing the austenite phase and making it non-magnetic, and also has the effect of increasing high-temperature strength by forming solid solutions and nitrides, but 0.02? If it is less than 0.1%, the effect will not be apparent, while if it is added more than 0.1%, the disadvantage of embrittlement of the steel due to the increase in nitrides will outweigh the advantage of increasing strength. -0.170.

Ｂ：Ｂは微量添加によつて結晶粒界に析出し、Ｖと複合
添加によつて共に固浴ならびに析出効果を生じて、室温
ならびに高温強度を著しく改善する作用があることを見
出した。B: It has been found that when B is added in a small amount, it precipitates at the grain boundaries, and when added in combination with V, both produce a solid bath and precipitation effect, and have the effect of significantly improving room temperature and high temperature strength.

その効果は０．００１％未満では発揮されず、０．００
１７０以上添加量の増加と共に効果も増すが、０．１％
を越すと浴接性の悪化を来たすので０．００１〜０．１
％の範囲に限定した。上記各限定量成分をもつて基本組
成し、その他はＦｅおよび不可避的不純物より成る高マ
ンガン非磁性鋼によつて本発明の目的が達成されるが、
更に７％以下のＡｌ，２７Ｏ以下のＴｉ，２７Ｏ以下の
Ｎｂ，２％以下のＺｒ，Ｏ．ｌ％以下のＣａのうちより
選ばれた１種または２種以上を添加し、残部はＦｅおよ
び不可避的不純物より成る高マンガン非磁性鋼はより効
果的に本発明の目的を達成し得ることが判明した。The effect is not exhibited at less than 0.001%, and 0.00%
The effect increases as the amount added increases over 170, but 0.1%
If it exceeds 0.001 to 0.1, the bath adhesion will deteriorate.
% range. Although the object of the present invention is achieved by a high manganese nonmagnetic steel whose basic composition has each of the above-mentioned limited amounts of components and the rest consists of Fe and unavoidable impurities,
Further, 7% or less Al, 27O or less Ti, 27O or less Nb, 2% or less Zr, O. It is believed that a high manganese non-magnetic steel to which one or more selected types of Ca is added in an amount of 1% or less, and the remainder is Fe and unavoidable impurities, can more effectively achieve the object of the present invention. found.

これらの成分元素の限定理由は次の如くである。Ａｌ： Ａｌは高マンガン非磁性鋼の高温における強度ならびに
耐酸化性の向上に効果があるが、多量の添加はコストの
上昇を来たすので７７０以下に限定した。The reasons for limiting these component elements are as follows. Al: Al is effective in improving the strength and oxidation resistance of high-manganese nonmagnetic steel at high temperatures, but since adding a large amount increases cost, it is limited to 770 or less.

Ｔｉ，Ｎｂ，Ｚｒ： Ｔｌ，Ｎｂ，Ｚｒはいずれも母相の結晶粒の成長を抑制
する効果があり、更に固溶ならびに析出効果により高温
強度を増大する。Ti, Nb, Zr: Tl, Nb, and Zr all have the effect of suppressing the growth of crystal grains in the matrix, and further increase high-temperature strength due to solid solution and precipitation effects.

しかしそれぞれ２％を越えると酸化物の生成が顕著とな
り、高温耐酸化性を低下させるので２％以下に限定した
。Ｃａ：Ｃａは少量の添加によつて鋼の清浄度を改善し
、高温耐酸化性を改善する効果があるが、多量の添加は
鋼の製造性を害するので０．１％以下に限定した。However, if each exceeds 2%, the formation of oxides becomes noticeable and the high-temperature oxidation resistance deteriorates, so the content is limited to 2% or less. Ca: Adding a small amount of Ca has the effect of improving the cleanliness of steel and improving high-temperature oxidation resistance, but adding a large amount impairs the manufacturability of the steel, so it was limited to 0.1% or less.

実施例第１発明および第２発明の高マンガン非磁性鋼２
１種類を溶製し、従来の高マンガン鋼およびステンレス
鋼ＳＵＳ３Ｏ４および本発明鋼に類似するも本発明の限
定成分に合致しない比較鋼に対して室温ならびに７００
℃における耐力、引張強さ、伸びおよび高温耐酸化性を
比較した。Example High manganese nonmagnetic steel 2 of the first and second inventions
One type was melt-produced and heated at room temperature and at
The yield strength, tensile strength, elongation and high temperature oxidation resistance at °C were compared.

第１表はこれらの供試材の組成を示し、従来鋼Ａは標準
１３％Ｍｎ鋼、従来鋼ＢはＣｒ５％を添加した２４％Ｍ
ｎ鋼、従来鋼Ｃは３０％Ｍｎ鋼であり、従来鋼ＤはＳＵ
Ｓ３０４である。本発明鋼７１６１〜１７は１８％Ｍｎ
鋼をベースとしたものであり、うち本発明鋼痛１１は特
に８２０℃にて６時間時効処理を行つたものであり、本
発明鋼Ａ６ｌ８〜２１は３０％Ｍｎ鋼をベースにしたも
のである。比較鋼は成分が本発明の成分を逸脱したもの
である。これらの供試材はすべて１１００℃で溶体化処
理後水靭処理を行い、本発明鋼腐１１は前記時効処理を
行つた後、丸棒試験片によつて透磁率の測定をし、更に
ＪｌＳｌ４Ａ号による丸棒試験片による引張試，験を行
つた。Table 1 shows the composition of these test materials. Conventional steel A is a standard 13% Mn steel, and conventional steel B is a 24% Mn steel with 5% Cr added.
n steel, conventional steel C is 30% Mn steel, and conventional steel D is SU
This is S304. Inventive steels 7161-17 are 18% Mn
Steel-based steels, among which Invention Steel No. 11 was aged at 820°C for 6 hours, and Invention Steels A6l8 to 21 were based on 30% Mn steel. . The comparative steel has a composition different from that of the present invention. All of these test materials were subjected to water toughness treatment after solution treatment at 1100°C, and after the steel rot 11 of the present invention was subjected to the above-mentioned aging treatment, the magnetic permeability was measured using a round bar test piece, and further JlSl4A A tensile test was conducted using a round bar test piece according to No.

次に高温耐酸化性の良否の判定は１．５ｍｍＸ１５ｍ１
Ｌ×５０龍の板を用いて７００℃の大気中での３５時間
連続加熱試験によつて行つた。上記すべての試験結果は
第２表に示すとおりである。第２表より明らかな如く、
透磁率はいずれの鋼種とも１．０１以下であつて良好な
非磁性鋼である。Next, the judgment of high temperature oxidation resistance is 1.5mm x 15m1
A continuous heating test was conducted at 700° C. for 35 hours in the atmosphere using a L×50 dragon plate. The results of all the above tests are shown in Table 2. As is clear from Table 2,
All steel types have magnetic permeability of 1.01 or less and are good non-magnetic steels.

本発明鋼の機械的性質は室温では従来鋼より耐力が上昇
しており、７００℃では耐力、引張強さとも従来鋼より
も大幅に改善されている。特に本発明鋼慮１１は時効処
理を施すことにより室温ならびに高温での耐力が従来鋼
より大幅に改善されている。Regarding the mechanical properties of the steel of the present invention, at room temperature, the yield strength is higher than that of the conventional steel, and at 700° C., both the yield strength and tensile strength are significantly improved compared to the conventional steel. In particular, by aging the steel material 11 of the present invention, the yield strength at room temperature and high temperature is significantly improved compared to conventional steel.

更に本発明鋼の高温耐酸化性も従来鋼よりもすぐれてい
る。次に比較鋼ａはＶ，Ｂを含まず、比較鋼ｂはＣｒ，
Ｎｌ，Ｂを含まず、比較鋼ＣはＣｒ，Ｂを含まない高マ
ンガン鋼であるが、いずれも室温および７００℃の高温
で耐力および引張強さとも本発明鋼に比してはるかに劣
つており、更に高温耐酸化性も本発明鋼に比して劣つて
いることを示している。Furthermore, the high temperature oxidation resistance of the steel of the present invention is also superior to that of conventional steel. Next, comparative steel a does not contain V and B, and comparative steel b contains Cr,
Although Comparative Steel C is a high manganese steel that does not contain Nl and B, and does not contain Cr and B, both yield strength and tensile strength at room temperature and high temperature of 700°C are far inferior to the steel of the present invention. Furthermore, this shows that the high temperature oxidation resistance is also inferior to that of the steel of the present invention.

上記実施例より明らかな如く、本発明鋼はＭｎ：１４〜
３５％の高マンガン鋼であるが、Ｃ，Ｓｉ，Ｃｒ，Ｎｉ
，Ｖ，Ｎ，Ｂのその他の基本組成を適正に限定し、更に
必要により適正量のＡｌ，Ｔｉ，Ｎｂ，Ｚｒ，Ｃａのう
ちより選ばれた１種または２種以上を添加することによ
り、従来の高マンガン非磁性鋼の欠点を克服し、次の如
き効果を収めることができた。As is clear from the above examples, the steel of the present invention has Mn: 14 to
Although it is a 35% high manganese steel, it contains C, Si, Cr, Ni
, V, N, and B, and if necessary, by adding an appropriate amount of one or more selected from among Al, Ti, Nb, Zr, and Ca, We were able to overcome the drawbacks of conventional high manganese nonmagnetic steel and achieve the following effects.

イ）従来の高温強度、高温耐力もしくは高温耐酸化性の
改善を意図した非磁性鋼に比較してＮｉ，Ｖ等の高価合
金の含有量が少ないのでコストが女いｏ（ロ）室温なら
びに７００℃の高温に爪、て耐力、引張強さとも、従来
鋼より格段にすぐれ、かつ高温耐酸化性もすぐれている
。B) Compared to conventional non-magnetic steel intended to improve high-temperature strength, high-temperature yield strength, or high-temperature oxidation resistance, the content of expensive alloys such as Ni and V is lower, so the cost is lower. It has much better yield strength and tensile strength than conventional steel, and also has excellent high-temperature oxidation resistance.

←→ 伸びは従来鋼に比較して遜色がない。←→ Elongation is comparable to conventional steel.

目 透磁率は１．０１以下を示しすぐれた非磁性鋼であ
る。It is an excellent non-magnetic steel with a magnetic permeability of 1.01 or less.

上記本発明鋼独自の効果を有するので電磁力による浴鋼
攪拌装置材料その他非磁性にして高温強度、高温耐力も
しくは高温耐酸化性を要求する広い分野における用途に
適応できる。Since the steel of the present invention has the above-mentioned unique effects, it can be used as a material for bath steel stirring equipment using electromagnetic force, and in a wide range of other fields requiring non-magnetic properties such as high-temperature strength, high-temperature yield strength, or high-temperature oxidation resistance.

Claims (1)

【特許請求の範囲】 １ 重量比にてＣ：０．４〜１．５％、Ｓｉ：３％以下
、Ｍｎ：１４〜３５％、Ｃｒ：３〜１８％、Ｎｉ：０．
１５〜１％、Ｖ：０．１〜１％、Ｎ：０．０２〜０．１
％、Ｂ：０．００１〜０．１％を含み残部はＦｅおよび
不可避的不純物より成ることを特徴とする高温強度にす
ぐれた高マンガン非磁性鋼。 ２ 重量比にてＣ：０．４〜１．５％、Ｓｉ：３％以下
、Ｍｎ：１４〜３５％、Ｃｒ：３〜１８％、Ｎｉ：０．
１５〜１％、Ｖ：０．１〜１％、Ｎ：０．０２〜０．１
％、Ｂ：０．００１〜０．１％を含み、更に７％以下の
Ａｌ、２％以下のＴｉ、２％以下のＮｂ、２％以下のＺ
ｒ、０．１％以下のＣａのうちより選ばれた１種または
２種以上を含有し残部はＦｅおよび不可避的不純物より
成ることを特徴とする高温強度にすぐれた高マンガン非
磁性鋼。[Claims] 1. C: 0.4 to 1.5%, Si: 3% or less, Mn: 14 to 35%, Cr: 3 to 18%, Ni: 0.
15-1%, V: 0.1-1%, N: 0.02-0.1
%, B: 0.001 to 0.1%, with the remainder consisting of Fe and inevitable impurities. 2 In terms of weight ratio, C: 0.4 to 1.5%, Si: 3% or less, Mn: 14 to 35%, Cr: 3 to 18%, Ni: 0.
15-1%, V: 0.1-1%, N: 0.02-0.1
%, B: 0.001 to 0.1%, and further contains 7% or less Al, 2% or less Ti, 2% or less Nb, 2% or less Z
A high-manganese non-magnetic steel having excellent high-temperature strength, characterized in that it contains one or more selected from the group consisting of 0.1% or less of Ca, and the remainder consisting of Fe and unavoidable impurities.