KR19980058369A - High manganese steel with excellent cryogenic impact properties and its manufacturing method - Google Patents

High manganese steel with excellent cryogenic impact properties and its manufacturing method Download PDF

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KR19980058369A
KR19980058369A KR1019960077693A KR19960077693A KR19980058369A KR 19980058369 A KR19980058369 A KR 19980058369A KR 1019960077693 A KR1019960077693 A KR 1019960077693A KR 19960077693 A KR19960077693 A KR 19960077693A KR 19980058369 A KR19980058369 A KR 19980058369A
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steel
molten steel
manganese steel
high manganese
molten
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KR100320959B1 (en
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박상덕
송치복
정경조
김창석
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서춘화
기아특수강 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/52—Manufacture of steel in electric furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/06—Deoxidising, e.g. killing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/064—Dephosphorising; Desulfurising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/001—Austenite

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  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

본 발명은 크롬(Cr), 니켈(Ni)이 다량 함유된 오스테나이트계 스테인레스강 및 9% 니켈(Ni)강 등 주로 저온에서 사용되는 구조용 소재에 있어서, 고가이고 전략적으로 중요한 원소인 Cr, Ni을 저가의 Mn, Al, Si로 대체하고, 첨가 C, Mo량을 조정함과 동시에 경희토류 원소(Ce, La, Nd, Pr, Y : 이하 RE라 칭함)를 소량 첨가하여 AL2O3, MnS 비금속개재물을 5μm이하의 구상인 RE계 복합개재물로 변화시켜 소량 잔존시키는 것을 큰 특징으로 하며, 이와 같은 새로운 합금설계로 낮은 제조원가와 간단한 열처리로 기존 저온용 소재보다 극저온에서 높은 충격인성을 보유함과 동시에 충격이방성을 극소화시킨 극저온용 망간강의 제조방법에 관한 것이다.The present invention is an expensive and strategically important element Cr, Ni in structural materials mainly used at low temperatures, such as austenitic stainless steel and 9% nickel (Ni) steel containing large amounts of chromium (Cr) and nickel (Ni). the cost of Mn, Al, replaced by Si, and addition of C, light rare earth element and at the same time adjusting the Mo amount (Ce, La, Nd, Pr , Y: hereinafter RE hereinafter) in small amount of AL 2 O 3, It is characterized by the small amount of MnS non-metallic inclusions changed into RE-based composite inclusions of 5μm or less.The new alloy design has higher impact toughness at cryogenic temperature than existing low-temperature materials due to low manufacturing cost and simple heat treatment. And a method for producing cryogenic manganese steel with minimal impact anisotropy.

본 발명에 따르면, 극저온용 망간강은 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지고, 그 제조방법은 상기 성분 범위들로 용제된 용강을 1,600±100℃에서 잉고트나 연속주조로서 응고시키는 단계; 응고된 상기 성분의 용강을 1,000∼1,300℃에서 일정시간 균질화 처리후 열간가공을 실시하는 단계; 및 1,100±100℃에서 일정시간 유지후 수냉하는 용체화처리를 실시하는 단계를 포함한다.According to the present invention, the cryogenic manganese steel is C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3%, Al 1 by weight. It contains ˜2.5%, Cu 0.1∼0.2%, the remainder is made up of trace impurities that can be contained during steel and Fe and electric, the production method is to melt molten steel in the above component range at 1,600 ± 100 ℃ Solidifying as an ingot or continuous casting; Performing hot working after homogenizing the molten steel of the solidified component at 1,000 to 1,300 ° C. for a predetermined time; And performing a solution treatment to hold water at a constant time at 1,100 ± 100 ° C. for water cooling.

Description

극저온 충격특성이 우수한 고망간강 및 그 제조방법High manganese steel with excellent cryogenic impact characteristics and its manufacturing method

본 발명은 크롬(Cr), 니켈(Ni)이 다량 함유된 오스테나이트계 스테인레스 강 및 9% 니켈강 등 주로 저온에서 사용되는 구조용 소재에 있어서 고가이고 전략적으로 중요한 원소인 Cr, Ni을 저가의 Mn, Al, Si으로 대체하고, 첨가 C, Mo량을 조정함과 동시에 경희토류원소(Co, LA, Nd, Pr, Y:이하 RE로 칭함)을 소량 첨가하여 Al2O3, MnS 비금속 개재물을 5μm이하의 구상인 RE계 복합개재물로 변화시켜 소량 잔존시키는 것을 큰 특징으로 하는 극저온용 소재에 관한 것으로서, 특히 극저온 충격특성이 우수한 고망간강 및 그 제조방법에 관한 것이다.In the present invention, Cr, Ni, which is an expensive and strategically important element in structural materials mainly used at low temperatures, such as austenitic stainless steel and 9% nickel steel, which contain a large amount of chromium (Cr) and nickel (Ni), are selected from Mn, Replace with Al, Si, adjust the amount of addition C, Mo, and add a small amount of light rare earth elements (Co, LA, Nd, Pr, Y: hereinafter referred to as RE) to add 5 μm of Al 2 O 3 and MnS nonmetallic inclusions. The present invention relates to a cryogenic material, which is characterized in that it is largely changed to the following spherical RE-based composite inclusions and remains in a small amount, and particularly relates to a high manganese steel having excellent cryogenic impact characteristics and a method of manufacturing the same.

오스테나이트계 스테인레스 강 및 9% 니켈강은 현재 저온에서 주로 사용되는 구조용 소재로 대표되는데, 전자는 면심입방격자(Face Centered Cubic : FCC)구조로서 저온에서 인성은 높으나 고가의 크롬, 니켈을 다량 함유하고 있어 제조원가가 고가라는 문제점이 있으며, 후자는 체심입방격자(Body Centered Cubic : BCC)구조로서 저온에서 강도는 높으나 저온에서 취성파괴에 의한 연성-취성전이 온도영역이 존대하여 -196℃ 부근의 극저온에서 극격한 인성저하 및 니켈에 의한 높은 제조원가가 문제시 되었다.Austenitic stainless steels and 9% nickel steels are currently represented as structural materials mainly used at low temperatures. The former is a face centered cubic (FCC) structure, which has high toughness at low temperatures but contains a large amount of expensive chromium and nickel. The manufacturing cost is high, and the latter is Body Centered Cubic (BCC) structure, which has high strength at low temperature, but has a ductile-brittle transition temperature range due to brittle fracture at low temperature, so it is very low around -196 ℃. The problem of drastic toughness and high manufacturing cost due to nickel is problematic.

또한, 상기 소재들의 문제점을 해결하기 위하여 노력한 특허강(대한민국 특허공보 92-4941, 92-8686 및 일본특허공고공보 소 51-155541, 소 59-11661)이 이미 공지되었으나, 각각 열간 소성 가공방향(L)과 소성 가공직각방향(T)의 충격 이방성과 소입/소려의 열처리 과정 간략화를 함께 고려하지 않은 문제점이 존재한다.In addition, patent steels (Korean Patent Publications 92-4941, 92-8686 and Japanese Patent Publication Nos. 51-155541, 59-11661) have been already known for their efforts to solve the problems of the above materials. There is a problem that L) and the impact anisotropy in the plastic working perpendicular direction (T) are not considered together with the simplification of the heat treatment process.

저온에서 소재의 우수한 인성을 확보하기 위해서는 안정한 오스테나이트 단일상이 요구되며, 오스테나이트의 안정성이 작을 때는 강도는 크고 연성은 작게 되고 오스테나이트의 안정성이 클 때는 강도는 작고 연성은 크다.In order to secure excellent toughness of the material at low temperature, a stable austenitic single phase is required. When the austenite stability is small, the strength is high and the ductility is small. When the austenite stability is high, the strength is small and the ductility is large.

FCC 구조인 오스테나이트의 안정성은 크게 화학조성, 온도, 적층결함에너지, 변형량 등에 의해 영향을 받는데, 이중 화학조성 변화요인은 적층결함에너지에 영향을 미치고 이 적층결함에너지가 오스테나이트의 안정성에 영향을 미치는 중요한 요인이 되어, 결과적으로 화학조성 변화요인은 소재의 인성에 영향을 미친다.The stability of austenitic, FCC structure, is greatly influenced by chemical composition, temperature, stacking defect energy, deformation amount, etc. Of these, the chemical composition change factors affect stacking fault energy and this stacking fault energy affects austenite stability. This is an important factor, and consequently, changes in chemical composition affect the toughness of the material.

FCC 금속에서 적층결함에너지는 1/2[110]의 버거스 벡터를 가지는 완전전위가 1/6[112]의 부분전위 쌍으로 분해되어진 적층결함 영역의 넓이와 관련이 있다. 적층결함 에너지가 낮으면 넓은 적층결함 영역을 이루게 되고, 이 영역은 안정해져서 다른 슬립면으로의 교차슬립이 어려워진다. 이러한 적층결함 영역은 FCC의 (111)면상에 형성되고 이 영역이 FCC-HCP변태의 핵 생성 위치로 작용하게 되는데, 적층결함 에너지가 낮을 수록 적층 결함을 형성하는 영역은 넓어져서 γ-ε 변태가 용이하게 된다. 반면, 적층결함에너지가 높은 경우는 1/6[112]로 분해되어진 부분전위쌍으로 이루어지는 적층결함영역은 작아지고, 다른 슬립면으로의 교차슬립이 용이해져서 적층결함영역을 감소시키고, γ-ε 변태를 억제한다.The stack defect energy in FCC metals is related to the area of the stack defect region where the full potential with Burgers vector of 1/2 [110] is broken down into partial potential pairs of 1/6 [112]. Low lamination defect energy results in a wide lamination defect area, which becomes stable and makes it difficult to cross slip to other slip surfaces. The stacked defect region is formed on the (111) plane of the FCC, and this region serves as a nucleation site of the FCC-HCP transformation. The lower the deposition defect energy, the wider the region forming the stacking defect is, and thus the γ-ε transformation becomes larger. It becomes easy. On the other hand, when the lamination defect energy is high, the lamination defect region consisting of partial potential pairs decomposed into 1/6 [112] becomes small, and cross-slip to other slip surfaces becomes easy, thereby reducing the lamination defect region, γ-ε Suppress metamorphosis.

강중의 니켈은 높은 적층 결함에너지를 형성하여 전위의 교차슬립을 용이하게 하여 벽개파괴보다 소성변형을 먼저 일어나게 하므로써 강의 저온인성을 향상시키며, 순수하게니켈을 망간으로만 대체하면 보다 낮은 적층결함에너지에 의해 니켈강에서는 나타나지 않는 ε-마르텐사이트가 나타난다. 이러한 ε-마르텐사이트의 발생은 합금의 강도는 증가시키지만 연성을 저하시킨다. 따라서 니켈을 함유하고 있는 재료를 망간으로 대체하고자 할 때는 인성향성과 더불어 ε-마르텐사이트의 발생으 최대한 억제하는 것이 중요하다.Nickel in steel forms high lamination defect energy and facilitates cross slip of dislocations, causing plastic deformation to occur earlier than cleavage, thereby improving low-temperature toughness of steel, and purely replacing nickel with manganese gives lower lamination defect energy. As a result, [epsilon] -martensite which does not appear in nickel steel appears. The generation of ε-martensite increases the strength of the alloy but decreases the ductility. Therefore, when replacing nickel-containing materials with manganese, it is important to suppress the generation of ε-martensite as well as the toughness.

본 발명은 기존 저온용 소재에 다량 함유된 니켈, 크롬을 망간으로 대체하고, 이에 따라 저온에서 나타날 수 있는 ε-마르텐사이트의 발생을 억제하기 위하여 적정량 알루미늄, 실리콘을 첨가함과 동시에 탄소, 몰리브덴 성분 조정을 통하여 극저온에서도 오스테나이트 단일상을 유지하므로써 저가이고 극저온 충격특성이 우수한 고망간강의 제조를 가능하게 하는 극저온 충격특성을 우수한 고망간강 및 그 제조 방법을 제공하는데 그 목적이 있다.The present invention replaces nickel and chromium contained in a large amount of existing low-temperature materials with manganese, and in order to suppress the generation of ε-martensite that may appear at low temperatures, an appropriate amount of aluminum and silicon is added, and carbon and molybdenum components are added. It is an object of the present invention to provide a high-manganese steel having excellent cryogenic impact characteristics and a method of manufacturing the same, which enables the production of high-manganese steel having low cost and excellent cryogenic impact characteristics by maintaining austenite single phase even at cryogenic temperatures.

또한, 본 발명은 상기 제조방법에 의하여 성분조정을 완료후 소량의 RE를 진공정련직후, 연주시 하주주입관내 및 몰드내인 특정 첨가시기에 2성분 이상 첨가하여 Al2O3, MnS의 단독생성을 완전하게 제어함과 동시에 5μm이하의 구상인 RE계 복합개재물(RE-oxysulfide, RE-sulfide)로 변화시켜 소량 잔존시킴에 따라 청정도 향상, 응고조직개선, 석출탄화물 미세화 및 오스테나이트 입도 미세화를 달성하므로써, 우수한 저온충격인성 및 충격 이방성이 극소화된 고망간강의 제조를 가능하게 할 수 있는 극저온 충격특성이 우수한 고망간장 및 그 제조방법을 제공하는데 다른 목적이 있다.In addition, the present invention is a single production of Al 2 O 3 , MnS by adding two or more components at the specific addition time in the injection molding pipe and the mold after performing a small amount of RE immediately after vacuum refining, after completing the component adjustment by the manufacturing method Control and at the same time change to RE-oxysulfide (RE-oxysulfide, RE-sulfide), which is less than 5μm, to improve cleanliness, improve coagulation structure, refine precipitated carbide and refine austenite grain size Another object of the present invention is to provide a high manganese soy sauce having excellent cryogenic impact characteristics, which can enable the production of high manganese steel having excellent low temperature impact toughness and low impact anisotropy.

도1A는 본 발명의 실시예에 따른 고망간강의 상온에서의 미세조직사진이고, 도1B는 고망간강의 -196℃ 충격시험 후 미세조직사진.Figure 1A is a microstructure photograph at room temperature of high manganese steel according to an embodiment of the present invention, Figure 1B is a microstructure photograph after the -196 ℃ impact test of high manganese steel.

도2A는 본 발명의 실시예에 따른 고망간강의 비금속 개재물 형상을 도시한 사진이고, 도2B는 종래의 실시예에 따른 망간강의 비금속개재물 형상을 비교한 사진.Figure 2A is a photograph showing the shape of the non-metallic inclusions of high manganese steel according to an embodiment of the present invention, Figure 2B is a photograph comparing the shape of the non-metallic inclusions of manganese steel according to a conventional embodiment.

상기 목적을 달성하기 위한, 본 발명의 극저온 충격특성이 우수한 고망간강은, 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지는 것을 특징으로 하며, 용강내 산소량을 10ppm이하, 황량을 50ppm이하로 하는 예비 탈산 및 예비 탈황과정을 기본으로 한다.The high manganese steel excellent in the cryogenic impact characteristics of the present invention for achieving the above object is C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5 as weight%. %, Mo 0.1-0.3%, Al 1-2.5%, Cu 0.1-0.2%, and the remaining amount is characterized by consisting of trace impurities that can be contained during steelmaking with Fe, 10ppm oxygen in molten steel Hereinafter, based on preliminary deoxidation and preliminary desulfurization with a sulfur content of 50 ppm or less.

상기 목적을 달성하기 위한 본 발명의 극 저온 충격특성이 우수한 고망간강은 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%, RE 0.0001∼1.5%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지는 것을 특징으로 하며, 용강내 산소량을 10ppm이하, 황량을 50ppm이하로 하는 예비 탈산 및 예비 탈황과정을 기본으로 한다.High manganese steel excellent in the ultra-low temperature impact characteristics of the present invention for achieving the above object is C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5% , Mo 0.1-0.3%, Al 1-2.5%, Cu 0.1-0.2%, RE 0.0001-1.5%, and the remaining amount is characterized by consisting of trace impurities that can be contained during steelmaking with Fe, It is based on the preliminary deoxidation and preliminary desulfurization process with the amount of oxygen in molten steel less than 10ppm and sulfur less than 50ppm.

또한 상기 목적을 달성하기 위한 본 발명의 극 저온 충격특성이 우수한 고망간강의 제조방법은, 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%, RE 0.0001∼1.5%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지는 성분 범위들로 용제된 용강을 1,600±100℃에서 일정시간 유지후 수냉하는 용체화처리를 실시하는 단계를 포함한다.In addition, the manufacturing method of high manganese steel excellent in the ultra-low temperature impact characteristics of the present invention for achieving the above object is C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3%, Al 1 to 2.5%, Cu 0.1 to 0.2%, RE 0.0001 to 1.5%, and the remaining amount is composed of trace impurities that can be contained during steelmaking with Fe And performing a solution treatment to hold the molten steel dissolved in the component ranges at a water temperature of 1,600 ± 100 ° C. for a predetermined time and then to water-cool it.

이하, 본 발명강의 화학성분 첨가 이유와 성분범위를 중량%로 나타내고 한정이유를 설명한다.Hereinafter, the reason for adding the chemical component of the inventive steel and the component range are shown in weight%, and the reason for limitation is described.

C : C는 오스테나이트의 안정성을 높이는 원소이고 높은 적층결함에너지 영역에서도 ε-마르텐사이트의 발생을 억제한다. 0.45% 이하에서는 오스테나이트 안정화 효과가 둔화되며, 0.6% 이상에서는 용접성 감소 및 탄화물 과다 석출에 의해 저온 충격인성이 감소하므로 0.45∼0.55%로 한정한다.C: C is an element that enhances the stability of austenite and suppresses the generation of ε-martensite even in a high stacking defect energy region. At 0.45% or less, the austenite stabilization effect is slowed, and at 0.6% or more, the low temperature impact toughness decreases due to reduced weldability and excessive precipitation of carbide, so it is limited to 0.45 to 0.55%.

Si : Si는 고망간강에서 저온에서의 ε-마르텐사이트의 발생을 억제하고 강력한 탈산제로 작용함과 동시에 고용강화효과가 있는 원소로서 적극적으로 첨가하지만, 과량첨가시 용접성 불량, 특히 공정탄화물 과다 생성에 의해 충격인성이 오히려 저하되고, 미량첨가될 경우 탈산력 감소, 고용강화 효과 및 ε-마르텐사이트 발생 억제효과가 둔화되므로 0.4∼0.8%로 한정한다.Si: Si is an element that has the effect of inhibiting the generation of ε-martensite at low temperature in high manganese steel and acts as a strong deoxidizer and has a solid solution strengthening effect. The impact toughness is rather lowered, and when it is added in a small amount, the deoxidation force decreases, the solid solution strengthening effect, and the ε-martensite generation inhibition effect are slowed, so it is limited to 0.4 to 0.8%.

Mn : Mn은 오스테나이트 안정화 원소이고 모재를 강화하는 원소로서 저온 충격인성 확보에 필수적인 원소로 적극적으로 첨가하지만, Al 및 Si 첨가량과 관계하여 22% 이상 첨가할 경우 첨가량에 상응하는 인성향상 효과를 기대할 수 없고, 16% 이하로 첨가될 경우 α(알파프라임)-마르텐사이트 및 ε-마르텐사이트가 발생되어 저온 취성의 위엄이 있으므로 16∼22%로 한정한다.Mn: Mn is an austenite stabilizing element and an element that strengthens the base material, and is actively added as an element essential for securing low-temperature impact toughness.However, if it is added more than 22% in relation to the amount of Al and Si added, the toughness improvement effect corresponding to the added amount is expected. If it is added below 16%, α (alphaprime) -martensite and ε-martensite are generated, so that the low temperature brittleness is dignified, it is limited to 16 to 22%.

Cr : Cr은 오스테나이트 안정화 원소이고 모재를 강화하는 원소로서 내식성부여 및 저온 충격인성 확보를 위하여 첨가한다. 소량 첨가시 상기 효과를 기대할 수 없고, 과량 첨가시 첨가량에 비하여 경제적이지 못할 뿐만 아니라 거대 Cr 탄화물 과다 생성에 의해 충격인성이 오히려 저하된다. 본 발명에선 Mn으로 대체한 관계로 상기 효과들과경제성을 함께 고려하여 2∼5.5%로 한정한다.Cr: Cr is an austenite stabilizing element and is an element that strengthens the base metal and is added to impart corrosion resistance and to secure low temperature impact toughness. When the addition of a small amount, the above effect cannot be expected, it is not economical compared to the addition amount when the addition is excessive, and the impact toughness is rather lowered due to the excessive formation of large Cr carbide. In the present invention, the relationship with Mn is limited to 2 to 5.5% in consideration of the effects and economics.

Mo : Mo는 오스테나이트를 안정화하고 모재를 강화시킬 목적으로 첨가한다. 소량 첨가시 상기 효과를 기대할 수 없고, 과량 첨가시 경제적이지 못할 뿐만 아니라 오히려 안정화 탄화물의 중가로 인하여 피삭성 및 충격인성을 해치므로 0.1∼0.3%로 한정한다.Mo: Mo is added for the purpose of stabilizing austenite and strengthening the base metal. When the addition of a small amount can not be expected, the effect is not economical when the addition is excessive, rather limit the machinability and impact toughness due to the weight of the stabilized carbide is limited to 0.1 to 0.3%.

Al : Al은 강력한 탄산제로서 결정립 미세화 효과가 있다. 또한 고 망간강에 있어서 광범위한 온도범위에서 오스테나이트를 안정화하며, 적층결함에너지를 높여 ε-마르텐사이트의 발생을 억제함에 따라 극저온 충격인성 확보에 필수적인 원소이다. 그러나, Mn함유량과 관계하여 1%이하에서는 ε-마르텐사이트가 발생되며, 2.5% 이상에서는 δ-페라이트의 형성에 의한 2상 조직이 나타나 오히려 저온 충격인성을 저하시키므로 1∼2.5%로 한정한다.Al: Al is a strong carbonate and has a grain refinement effect. In addition, stabilizing austenite over a wide range of temperatures in high manganese steel, and it is an essential element to secure cryogenic impact toughness by increasing the stacking defect energy to suppress the generation of ε-martensite. However, ε-martensite is generated at 1% or less with respect to Mn content, and at 2.5% or more, biphasic structure due to the formation of δ-ferrite appears and thus lowers the low temperature impact toughness, so it is limited to 1 to 2.5%.

Cu : Cu는 오스테나이트 안정화, 내식성 부여 및 석출강화를 위하여 첨가한다. 소량첨가시 상기 효과를 개대할 수 없고, 과량 첨가시 적열취성에 의해 열간가공성을 해치므로 0.1∼0.2%로 한정한다.Cu: Cu is added for austenite stabilization, corrosion resistance and precipitation strengthening. When the small amount is added, the above effects cannot be improved, and when added in an excessive amount, the hot workability is impaired due to the red brittleness, so it is limited to 0.1 to 0.2%.

경희토류 원소(RE) : Ce, La, Nd, Pr, Y의 경희토류 원소는 Al2O3, MnS 비금속개재물의 형상을 구상화시키며, 이에 따라 청정도 향상, 응고조직 개선, 석출탄화물 미세화, 오스테나이트 입도 미세화를 달성하여 충격특성 향상 및 피삭성을 향상시킬 목적으로 첨가한다. 소량 첨가시 상기 효과를 기대할 수 없고, 과량 첨가시 오히려 상기 특성을 해칠 뿐만 아니라 첨가량에 비하여 경제적이지 못하므로 0.0001∼0.15%로 한정한다.Light rare earth elements (RE): Light rare earth elements of Ce, La, Nd, Pr, and Y shape the shape of Al 2 O 3 and MnS nonmetallic inclusions, thus improving cleanliness, improving solidification structure, minimizing precipitated carbides, and austenite. Nitride is added for the purpose of achieving finer particle size and improving impact characteristics and machinability. When the small amount is added, the above effect cannot be expected, and when the excessive amount is added, it is not only harmful to the above characteristics, but also economical compared to the added amount, so it is limited to 0.0001 to 0.15%.

[실시예]EXAMPLE

하기의 표1에 발명강과 종래강의 화학성분 및 RE%/S%와 [RE%][S%]는 나타내었다.Table 1 below shows the chemical composition, RE% / S% and [RE%] [S%] of the inventive and conventional steels.

발멸강(A∼F)은 진공유도로에서 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%, RE 0.0001∼1.5%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지는 성분 범위들로 용제된 용강을 용제후 10Kg급 잉고트로 제작하였고, 종래강(G∼I) 역시 진공유도로를 이용하여 용강을 용제후 10Kg급 잉고트로 제작하였다. 제작된 잉고트는 1,200±50℃로 가열하여 5시간 균질화 처리를 행하고, 1170℃에서 32mmψ로 열간가공을 행한 후, 용체화처리(1,100±20℃, 1시간, 수냉)를 실시하였다. 단 종래강 J는 소입/소려 처리를 하였다. 이후, 온도 변화에 따른 충격특성을 평가하기 위하여 액체질소를 이용하여 상온, -100℃, -196℃에서 KSB0810의 규정에 따라 충격 시험을 실시하였다.The ignition steel (A to F) is C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3% by weight in vacuum induction. , 1 to 2.5% of Al, 0.1 to 0.2% of Cu, and 0.0001 to 1.5% of RE, and the remaining amount is 10Kg after dissolving molten steel in the component range consisting of Fe and trace impurities that may be contained in steelmaking. It was made of grade ingot, and the conventional steel (G ~ I) was also made of 10Kg grade ingot after the molten steel using the vacuum induction. The produced ingot was heated to 1,200 ± 50 ° C., homogenized for 5 hours, hot worked at 1170 ° C. for 32 mm, and then subjected to solution treatment (1,100 ± 20 ° C., 1 hour, water cooling). However, the conventional steel J was quenched / polished. Then, in order to evaluate the impact characteristics according to the temperature change, the impact test was carried out in accordance with the provisions of KSB0810 at room temperature, -100 ℃, -196 ℃ using liquid nitrogen.

[표 1] TABLE 1

발명강(A∼F)과 종래강(G∼J)의 충격특성을 온도변화에 따라 평가한 결과를 충격치 및 열간 소성 가공방향과 소성 가공 직각방향의 충격 이방성비(T/L)로 구분하여 표2에 나타내었다.The results of evaluating the impact characteristics of the inventive steels (A to F) and the conventional steels (G to J) according to the temperature change are divided into the impact value and the impact anisotropy ratio (T / L) in the hot plastic working direction and the perpendicular direction of plastic working. Table 2 shows.

[표 2] TABLE 2

표2를 참조하면, 전체적으로 볼 때, 상온, -100℃, -196℃ 모두에서 발명강이 종래강에 비하여 충격인성이 우수하다. 또한, 발명강은 종래강에 비하여 충격 이방성비가 1에 가깝게 분석됨에 따라 열간 소성 가공방향과 소성 가공 직각방향의 충격이방성이 극소화되었다. 특히 -196℃의 극저온 충격특성은 종래강에 비하여 현저하게 나타난다.Referring to Table 2, when viewed as a whole, the invention steel has excellent impact toughness as compared with the conventional steel at room temperature, -100 ° C, and -196 ° C. In addition, compared to the conventional steel, the invention steel has an impact anisotropy ratio close to 1, thereby minimizing the impact anisotropy in the hot plastic working direction and the plastic working perpendicular direction. In particular, the cryogenic impact characteristic of -196 ℃ is remarkable compared to the conventional steel.

도1A와 도1B는 발명강 A의 용체화 처리후 상온 및 -196℃ 충격시험후의 미세조직을 각각 나타낸 것이다.1A and 1B show the microstructure after the solution temperature treatment of the inventive steel A and the impact test at room temperature and −196 ° C., respectively.

도1A를 참조하면, 본 발명강은 상온에서 안정한 오스테나이트 조직을 보이고, -196℃ 충격시험후 미세조직 역시 안정한 오스테나이트 조직에 변형 유기 오스테나이트 조직이 보인다. 또한 도면에 도시하지는 않았지만, 발명강 모두에서 같은 미세조직을 나타낸다.Referring to Figure 1A, the present invention steel exhibits a stable austenite structure at room temperature, and after the -196 ℃ impact test microstructure also shows a modified organic austenite structure in a stable austenite structure. In addition, although not shown in the drawings, the same microstructure is shown in all the inventive steels.

도2A와 도2B는 열간 소성가공후 발명강 C 및 종래강 I의 비금속개재물 혀상을 각각 도시한 것이다.2A and 2B show the nonmetallic inclusion tongues of inventive steel C and conventional steel I, respectively, after hot plastic working.

도2B를 참조하면, 종래강 I의 경우, MnS는 가공방향으로 연신되고, Al2O3는 가공방향으로 깨어진 것이 보인다. 반면, 도2A에 도시된 발명강 C의 경우, 5μm이하의 구상인 RE계 복합 개재물이 열간가공후에도 연신되거나 깨어짐 없이 잉고트 상태 그대로를 유지하고 있다.Referring to Fig. 2B, in the case of the conventional steel I, MnS is drawn in the machining direction, and Al 2 O 3 is broken in the machining direction. On the other hand, in the case of the inventive steel C shown in Fig. 2A, the RE-based composite inclusion having a spherical shape of 5 μm or less is maintained in the ingot state without being stretched or broken even after hot working.

따라서, 발명강 A, B, C는 기존 저온용 소재인 오스테나이트계 스테인레스강(종래강 G)과 9% 니켈강(종래강 J)에 다량 함유된 고가의 Cr, Ni 함량을 낮춤과 동시에 고가의 Cr, Ni을 저가의 Mn, Al, Si으로 대체하고 함유 C, Mo량을 조정한 결과 실온 및 저온에서 안정한 오스테나이트를 형성하고 순수 망간강(종래강 H, I)에서 나타날 수 있는 ε-마르텐사이트의 형성을 최대한 억제하므로써 우수한 충격인성을 보유할 뿐만 아니라 제조원가가 낮다는 잇점이 있다.Therefore, the invention steels A, B, and C reduce the content of expensive Cr and Ni contained in a large amount of austenitic stainless steel (conventional steel G) and 9% nickel steel (conventional steel J), which are existing materials for low temperature. By replacing Cr and Ni with inexpensive Mn, Al and Si, and adjusting the amount of C and Mo contained, they form stable austenite at room temperature and low temperature, and ε-martensite which can be seen in pure manganese steel (traditional steels H and I). By suppressing the formation of maximally, not only has excellent impact toughness but also low manufacturing cost.

또한, 발명강 D, E, F는 위 발명강의 성분조성에 소량의 RE를 첨가하여 종래 저온용 소재의 충격인성 저하 및 충격이방성비를 크게 하는 Al2O3, MnS 비금속 개재물의 단독생성을 완전하게 제어함과 동시에 5μm 이하의 구상 형태의 RE계 복합개재물을 소량 잔존시키므로써, 청정도 향상, 응고조직 개선, 오스테나이트 입도미세화 및 석출탄화물 미세화를 이루어 보다 우수한 충격 특성을 보유한다.In addition, the invention steels D, E, and F completely add the small amount of RE to the composition of the above invention steel to completely produce the Al 2 O 3 and MnS non-metallic inclusions which increase the impact toughness and impact anisotropy ratio of the conventional low temperature material. In addition, by controlling and maintaining a small amount of spherical RE-based composite inclusions of 5μm or less, it has better impact characteristics by improving cleanliness, improving coagulation structure, micronizing austenite, and minimizing precipitated carbide.

이상의 실시예로부터 본 발명강은 우수한 저온 충격특성을 얻기 위한 새로운 합금설계로 고가의 합금원소를 갖는 종래강보다 낮은 제조원가라는 잇점 뿐만 아니라 실온 및 극저온에서도 우수한 충격특성을 함께 보장한다.From the above embodiment, the present invention is a new alloy design for obtaining excellent low-temperature impact characteristics, as well as the advantages of lower manufacturing cost than conventional steel having expensive alloying elements, as well as excellent impact characteristics at room temperature and cryogenic temperature.

여기에서는 본 발명의 특정 실시예에 대하여 설명하고 도시하였지만, 당업자에 의하여 이에 대한 수정과 변형을 할 수 있다. 따라서, 이하 특허청구범위는 본 발명의 진정한 사상과 범위에 속하는 한 모든 수정과 변형을 포함하는 것으로 이해할 수 있다.Although specific embodiments of the present invention have been described and illustrated herein, modifications and variations can be made by those skilled in the art. Accordingly, the following claims are to be understood as including all modifications and variations as long as they fall within the true spirit and scope of the present invention.

Claims (9)

중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지는 것을 특징으로 하는 극저온특성이 우수한 고망간강.As weight% C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3%, Al 1 to 2.5%, Cu 0.1 to 0.2% And, the remaining amount is high manganese steel having excellent cryogenic characteristics, characterized in that consisting of trace impurities that can be contained during steelmaking with Fe and electricity. 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%, RE 0.0001∼1.5%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지는 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강.As weight% C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3%, Al 1 to 2.5%, Cu 0.1 to 0.2% , Manganese steel with excellent cryogenic impact characteristics, characterized in that it contains 0.001% to 1.5% of RE, and the remaining amount is made of Fe and trace impurities that may be contained during steelmaking. 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%, RE 0.0001∼1.5%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지고, 용강내 산소량을 10ppm이하, 황량을 50ppm이하로 하는 예비 탈산 및 예비 탈황과정을 기본으로하는 용제된 용각을 준비하는 단계; 준비된 용강을 잉고트나 연속주조로서 응고시키는 단계; 응고된 상기 성분의 용강을 일정시간 균질화 처리후 열간가공을 실시하는 단계; 및 열간가공된 용강을 소정온도에서 일정시간 유지후 수냉하는 용체화처리단계를 포함하는 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강의 제조방법.As weight% C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3%, Al 1 to 2.5%, Cu 0.1 to 0.2% , 0.001% to 1.5% of RE, and the remaining amount is composed of trace impurities that can be contained in steelmaking with Fe, and basic deoxidation and preliminary desulfurization process with oxygen content of less than 10ppm and sulfur content less than 50ppm Preparing a molten molten metal to be prepared; Solidifying the prepared molten steel as an ingot or continuous casting; Performing hot working on the molten steel of the solidified component after homogenizing for a predetermined time; And a solution treatment step of cooling the hot-processed molten steel at a predetermined temperature for a predetermined time and then water-cooling the molten steel. 제3항에 있어서, 상기 응고단계의 온도는 1,600±100℃ 범위인 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강의 제조방법.The method of claim 3, wherein the temperature of the solidification step is 1,600 ± 100 ℃ range excellent cryogenic impact characteristics. 제3항에 있어서, 상기 균질화 처리는 1,000~1,300℃범위에서 실시하는 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강의 제조방법.The method of manufacturing high manganese steel having excellent cryogenic impact characteristics according to claim 3, wherein the homogenization treatment is performed in a range of 1,000 to 1,300 ° C. 제3항에 있어서, 상기 용체화 처리단계에서의 유지온도는 1,100±100℃ 범위에서 실시하는 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강의 제조방법.The method for producing high manganese steel having excellent cryogenic impact characteristics according to claim 3, wherein the holding temperature in the solution treatment step is performed in a range of 1,100 ± 100 ° C. 중량%로서 C 0.45∼0.55%, Si 0.4∼0.8%, Mn 16∼22%, Ni 1.5∼4%, Cr 2∼5.5%, Mo 0.1∼0.3%, Al 1∼2.5%, Cu 0.1∼0.2%를 함유하고, 잔량은 Fe와 전기로 제강시 함유될 수 있는 미량 불순물들로 이루어지고, 용강내 산소량을 10ppm이하, 황량을 50ppm이하로 하는 예비 탈산 및 예비 탈황과정을 기본으로하는 용제된 용각을 준비하는 단계; 준비된 용강을 잉고트나 연속주조로서 응고시키는 단계; 응고된 상기 성분의 용강을 일정시간 균질화 처리후 열간가공을 실시하는 단계; 및 열간가공된 용강을 소정온도에서 일정시간 유지후 수냉하는 용체화처리단계를 포함하는 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강의 제조방법.As weight% C 0.45 to 0.55%, Si 0.4 to 0.8%, Mn 16 to 22%, Ni 1.5 to 4%, Cr 2 to 5.5%, Mo 0.1 to 0.3%, Al 1 to 2.5%, Cu 0.1 to 0.2% The remaining amount is composed of trace impurities that can be contained during steelmaking with Fe, and the molten molten metal based on the preliminary deoxidation and preliminary desulfurization process having the amount of oxygen in the molten steel below 10 ppm and the sulfur amount below 50 ppm. Preparing; Solidifying the prepared molten steel as an ingot or continuous casting; Performing hot working on the molten steel of the solidified component after homogenizing for a predetermined time; And a solution treatment step of cooling the hot-processed molten steel at a predetermined temperature for a predetermined time and then water-cooling the molten steel. 제7항에 있어서, 상기 균질화 처리는 1,000∼1,300℃범위에서 실시하는 것을 특징으로 하는 극저온 충격특성이 우수한 고망간강의 제조방법.8. The method for producing high manganese steel having excellent cryogenic impact characteristics according to claim 7, wherein the homogenization treatment is performed in the range of 1,000 to 1,300 deg. 제7항에 있어서, 상기 용체화 처리단계에서의 유지온도는 1,100±100℃범위에서 실시하는 것을 특징으로 하는 극 저온 충격특성이 우수한 고망간강의 제조방법.8. The method for producing high manganese steel having excellent low temperature impact characteristics according to claim 7, wherein the holding temperature in the solution treatment step is performed at a range of 1,100 ± 100 ° C.
KR1019960077693A 1996-12-30 1996-12-30 METHOD FOR MANUFACTURING HIGH Mn-STEEL EXCELLENT IN IMPACT TOUGHNESS AT ULTRA LOW TEMPERATURE KR100320959B1 (en)

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