KR20000043687A - Spheroidal iron material for heat resisting and heat treatment method thereof - Google Patents

Spheroidal iron material for heat resisting and heat treatment method thereof Download PDF

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KR20000043687A
KR20000043687A KR1019980060092A KR19980060092A KR20000043687A KR 20000043687 A KR20000043687 A KR 20000043687A KR 1019980060092 A KR1019980060092 A KR 1019980060092A KR 19980060092 A KR19980060092 A KR 19980060092A KR 20000043687 A KR20000043687 A KR 20000043687A
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cast iron
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KR100325125B1 (en
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정재영
마봉열
안상호
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이구택
포항종합제철 주식회사
신현준
재단법인 포항산업과학연구원
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D5/00Heat treatments of cast-iron
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26Methods of annealing
    • C21D1/30Stress-relieving
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/84Controlled slow cooling
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/008Heat treatment of ferrous alloys containing Si
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C37/00Cast-iron alloys
    • C22C37/04Cast-iron alloys containing spheroidal graphite
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/005Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/12Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING 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
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/005Ferrite

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Child & Adolescent Psychology (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Abstract

PURPOSE: A spheroidal iron material for heat-resisting and a heat treatment method are provided to have excellent heat resistance, abrasion resistance and oxidization resistance. CONSTITUTION: A spheroidal iron material for heat resisting includes C:2.3 to 3.8wt %, Si:3.0 to 5.5 wt %, Mn: less than 1.0 wt %, Ni: less than 0.5wt %, Cr: less than 0.5wt %, W: o.01 to 6.0wt % and Mo: 0 to 3.0wt %. Herein, the rest is composed of Fe, and Mg, Zr, Bi added up in order to make impurities or black lead spheroidal. In addition, each or the sum of complex material of a rare earth element is 0.001 to 0.6wt%.

Description

내열용 구상흑연주철재 및 그 열처리방법Heat-resistant spheroidal graphite cast iron and its heat treatment method

본 발명은 선재 컨베이어 롤, 자동차 및 선박용 부품, 제철소의 이송설비, 윤활성을 요구하는 내마모 부품에 사용되는 소재에 관한 것으로서, 보다 상세하게는 우수한 내열성과 내마모성 그리고 내산화성을 가지는 내열용 구상흑연주철재 및 그 열처리방법에 관한 것이다.The present invention relates to a material used in wire rod conveyor rolls, automobile and marine parts, steelworks transfer equipment, wear-resistant parts requiring lubrication, and more particularly, spheroidal graphite for heat resistance having excellent heat resistance, abrasion resistance, and oxidation resistance. It relates to an iron material and a heat treatment method thereof.

일반적으로 구상흑연주철재는 인장강도뿐만 아니라 충격강도 및 연신률이 다른 주철재에 비하여 높기 때문에 고기능을 요구하는 데 주로 이용되고 있다. 특히 구상흑연주철재는 기계적 특성이 우수할 뿐만 아니라 다른 재질에 비하여 가격이 저렴하고 윤활성이 우수하기 때문에 제철소 설비용 부품이나 자동차 및 선박용 부품 그리고 내마모 부품의 기본 소재로 널리 사용되고 있다.In general, spherical graphite cast iron is mainly used to require high performance because the impact strength and elongation as well as the tensile strength is higher than other cast iron. In particular, spheroidal graphite cast iron is widely used as a basic material for steel mill equipment, automotive and marine parts, and wear-resistant parts because it has excellent mechanical properties, low cost, and excellent lubricity compared to other materials.

최근 선재 제조기술에서 생산효율을 증대시키기 위하여 생산속도가 증가되고 있을 뿐만 아니라 고합금강 선재 제조로 인하여, 선재 컨베이어 롤의 노출온도가 증가하는 추세에 있다. 따라서 선재 컨베이어 롤에 대한 부하가 점점 가혹하게 되고 있다.In recent years, the production speed is increased to increase the production efficiency in the wire rod manufacturing technology, and due to the manufacture of high-alloy steel wire rod, the exposure temperature of the wire rod conveyor roll is increasing. Therefore, the load on the wire rod conveyor roll is becoming increasingly severe.

종래의 선재 컨베이어 롤 재료는 통상의 3%Si-3%C계 구상흑연주철재를 많이 사용하고 있다. 또한 다른 내열용 구상흑연주철재로는 독일특허 제 3,628,157 호에서 Fe-Si-C-Mo-Ni계 주철재에 Cu를 중량비로 1.0∼1.5%까지 다량 함유시켜 열전도도를 향상시킨 펄라이트 조직의 연소엔진용 소재를 제안하였다. 또한 최근에는 미국특허 제 4,889,687 호와 같이 Bi를 중량비로 0.0015∼0.015%를 첨가시켜 저온 충격특성을 향상시킨 기술과 Si 및 C 외에 Cr, V, Nb, Ti, Ta, Mo, W, Ni, Co 그리고 Cu 등과 같이 매우 다양한 합금 원소를 첨가시켜 주로 마르텐사이트 조직을 가지게 하여 내마모성을 향상시킨 미국특허 제 4,435,226 호가 있다.Conventional wire rod conveyor rolls use a lot of conventional 3% Si-3% C-based nodular cast iron. In addition, as another heat-resistant nodular cast iron material, in German Patent No. 3,628,157, the Fe-Si-C-Mo-Ni-based cast iron contained a large amount of Cu in a weight ratio of 1.0 to 1.5% to improve the thermal conductivity. Proposed engine material. In addition, as in US Pat. No. 4,889,687, Bi has added 0.0015 to 0.015% by weight to improve the low temperature impact characteristics, and in addition to Si and C, Cr, V, Nb, Ti, Ta, Mo, W, Ni, Co In addition, there is US Patent No. 4,435,226 which adds a variety of alloying elements such as Cu and has a martensite structure to improve wear resistance.

일반적으로 선재 컨베이어 롤은 이송되는 선재의 재질, 치수, 온도, 인발속도, 냉각조건 및 사용조건에 적절한 재질을 선택해야 한다. 특히, 선재 컨베이어 롤은 롤의 측면에 냉각핀 역할을 하는 흠을 만들어 냉각효율을 향상시키고 있지만, 선재의 품질제어를 위하여 냉각장치 설치가 어려워 고온의 선재 이송에 의하여 600∼900℃의 고온에 쉽게 노출된다. 그러므로 선재 컨베이어 롤의 표면은 고온의 선재로부터 많은 열을 공급받아 산화가 촉진된다. 또한 산화된 롤 표면은 이송되는 선재에 의하여 손상되고 손상된 롤 표면에는 박리된 산화 스케일이 고착된다. 이러한 산화 스케일의 고착은 롤 표면 균열의 모양에 따라 촉진된다. 이 결과, 롤 표면을 거칠게 할뿐만 아니라 선재 표면 품질을 저해하는 원인이 된다.In general, wire conveyor rolls should be selected from materials suitable for the material, dimensions, temperature, drawing speed, cooling and operating conditions of the wire being transferred. In particular, the wire conveyor roll improves the cooling efficiency by creating a flaw that acts as a cooling fin on the side of the roll, but it is difficult to install a cooling device for quality control of the wire rod. Exposed. Therefore, the surface of the wire conveyor roll receives a lot of heat from the high temperature wire rod to promote oxidation. In addition, the oxidized roll surface is damaged by the wire rod to be transported, and the peeled oxidation scale is fixed to the damaged roll surface. Fixation of this oxidation scale is promoted depending on the shape of the roll surface cracks. As a result, not only the roll surface is roughened but it also becomes a cause of impairing wire rod surface quality.

그러므로 선재 컨베이어 롤용 소재는 무엇보다 내산화성이 우수해야 한다. 또한 롤은 선재와 접촉할 때, 주편의 자체 하중에 의한 부하를 받기 때문에 롤 소재는 이러한 하중에 견디기 위한 고온 강도를 필요로 한다.Therefore, the wire conveyor roll material should be excellent in oxidation resistance above all. The roll material also requires high temperature strength to withstand these loads because the rolls are subjected to the load of the cast steel when it comes in contact with the wire rod.

그러나 일반 3%Si-3%C계 선재 컨베이어 롤은 롤에 대한 부하가 가혹한 경우에 롤의 표면온도가 상승하게 되면서 내산화성이 열악해지고, 고온강도도 낮아지는 결점이 있다. 독일특허 제 3,628,157 호는 열전도도를 개선하기 위하여 첨가되는 다량의 Cu가 주조시, Cu 편석을 발생시키기 때문에 균일하고 안정된 산화피막의 형성이 어려울 뿐만 아니라 주철재의 인성 및 연성이 열악하다. 미국특허 제 4,889,687 호는 Si가 1.5∼2.3%로 낮아서 내산화성이 상대적으로 열악하다는 단점이 있다. 그리고 미국특허 제 4,435,226 호는 고가의 V, Nb, Ta, 그리고 Ni(또는 Co)를 다량 함유하기 때문에 비경제적이라는 단점이 있다. 또한 독일특허 제 3,628,157 호와 미국특허 제 4,435,226 호는 각각 펄라이트와 마르텐사이트 조직을 갖기 때문에 연성이 매우 낮을 뿐만 아니라 미세 조직의 고온 안정성이 낮아 변태유기 변형을 발생시킬 수 있다는 문제점이 있다.However, the general 3% Si-3% C wire rod roll has a drawback that the surface temperature of the roll is increased when the load on the roll is severe, so that the oxidation resistance is poor and the high temperature strength is also lowered. German Patent No. 3,628,157 is not only difficult to form a uniform and stable oxide film but also poor in toughness and ductility of cast iron because a large amount of Cu added to improve thermal conductivity causes Cu segregation during casting. U.S. Patent No. 4,889,687 has a disadvantage in that the oxidation resistance is relatively poor because Si is 1.5 to 2.3%. In addition, US Patent No. 4,435,226 has a disadvantage of being uneconomical because it contains a large amount of expensive V, Nb, Ta, and Ni (or Co). In addition, German Patent No. 3,628,157 and U.S. Patent No. 4,435,226 have pearlite and martensite structures, respectively, and thus have low ductility and low temperature stability of microstructures, thereby causing metamorphic organic deformation.

따라서 본 발명은 내열성, 내마모성, 그리고 내산화성을 가지며, 특히 내산화성이 우수한 내열용 구상흑연주철재 및 그 열처리방법을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a heat-resistant spheroidal graphite cast iron having heat resistance, abrasion resistance, and oxidation resistance, and particularly excellent in oxidation resistance, and a heat treatment method thereof.

도 1은 종래 비교재와 발명재를 700℃ 대기중에 200시간 노출시켰을 때, Si 함량과 무게 증가량의 관계로 내산화성의 차이를 도시한 그래프이다.1 is a graph showing the difference in oxidation resistance in relation to Si content and weight increase amount when the conventional comparative material and the inventive material are exposed to the air at 700 ° C. for 200 hours.

이를 실현하기 위한 본 발명의 내열용 구상흑연주철재는 중량비로, C:2.2∼3.8%, Si:3.0∼5.5%, Mn:1.0% 이하, Ni:0.5% 이하, Cr:0.5% 이하, W:0.01∼6.0%, Mo:0∼3.0%를 포함하고, 나머지는 Fe, 불가피한 불순물 또는 흑연의 구상화를 위하여 첨가되는 Mg, Zr, Bi, 그리고 희토류 원소의 복합물이 각각 또는 합이 0.001∼0.6%의 조성으로 이루어짐을 특징으로 한다.The heat-resistant spheroidal graphite cast iron material of the present invention for achieving this is C: 2.2 to 3.8%, Si: 3.0 to 5.5%, Mn: 1.0% or less, Ni: 0.5% or less, Cr: 0.5% or less, W : 0.01% to 6.0%, Mo: 0% to 3.0%, the remainder being 0.001% to 0.6%, respectively, or a combination of Mg, Zr, Bi, and rare earth elements added for spheroidization of Fe, unavoidable impurities or graphite Characterized in that the composition is made of.

본 발명의 내열용 구상흑연주철재의 열처리방법은 중량비로, C:2.2∼3.8%, Si:3.0∼5.5%, Mn:1.0% 이하, Ni:0.5% 이하, Cr:0.5% 이하, W:0.01∼6.0%, Mo:0∼3.0%를 포함하고, 나머지는 Fe, 불가피한 불순물 또는 흑연의 구상화를 위하여 첨가되는 Mg, Zr, Bi, 그리고 희토류 원소의 복합물이 각각 또는 합이 0.001∼0.6%로 조성되는 구상흑연주철재를, 700∼1200℃에서 오스테나이트화한 후에 서냉하여 페라이트 조직을 갖게 하거나, 200∼700℃에서 유지하여 잔류응력을 완화시키거나, 700∼1200℃에서 오스테나이트화한 후에 공냉 또는 급냉한 후에 300∼700℃에서 탬퍼링하여 강도를 향상시킴을 특징으로 한다.The heat treatment method of the heat-resistant spheroidal graphite cast iron of the present invention is C: 2.2 to 3.8%, Si: 3.0 to 5.5%, Mn: 1.0% or less, Ni: 0.5% or less, Cr: 0.5% or less, W: 0.01 to 6.0%, Mo: 0 to 3.0%, the remainder being 0.001 to 0.6%, respectively, or a combination of Fe, Mg, Zr, Bi, and rare earth elements added for spheroidization of unavoidable impurities or graphite. After forming the spheroidal graphite cast iron, which is austenitic at 700 to 1200 ° C, it is slowly cooled to give a ferrite structure, or it is maintained at 200 to 700 ° C to relieve residual stress or austenite at 700 to 1200 ° C. After air cooling or quenching, it is characterized in that the strength is improved by tampering at 300 to 700 ° C.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

C는 구상흑연주철에서 Mg, Zr, Bi 그리고 희토류 원소의 화합물과 함께 첨가되어 주로 구형의 흑연입자로 존재하며, 회주철에서 존재하는 긴 리본 모양의 플레이크흑연에 비하여 강도, 연신률, 그리고 충격특성과 같은 기계적 특성을 향상시킨다. C 함량이 2.2% 미만인 경우에는, 흑연의 구상화가 어려워 플레이크흑연의 형성이 조장되므로 주철재의 기계적 특성이 현저히 감소한다. 또한 3.8%를 초과하면, 흑연화가 조장되어 구상화가 어렵게 된다. 따라서 C의 함량을 2.2∼3.8%로 한정한다.C is added with Mg, Zr, Bi, and rare earth elements in Spheroidal Graphite Iron, and is mainly present as Spherical Graphite Particles, and compared with Long Ribbon Flake Graphite in Gray Cast Iron, such as strength, elongation, and impact characteristics. Improve mechanical properties. If the C content is less than 2.2%, the spheroidization of graphite is difficult to promote the formation of flake graphite, so that the mechanical properties of the cast iron material are significantly reduced. If it exceeds 3.8%, graphitization is encouraged and spheroidization becomes difficult. Therefore, the content of C is limited to 2.2 to 3.8%.

Si는 구상흑연주철에서 기지조직을 형성하는 기본 합금원소로서, 기본적인 내산화성을 확보하기 위하여 3.0∼5.5%로 그 범위를 한정한다. Si의 함량이 3.0% 미만이 되면 기지조직의 내산화성이 열악해지고, 5.5% 초과 시에는 파괴인성 및 충격특성이 저하되는 단점이 있다.Si is a basic alloy element that forms a matrix structure in spherical graphite iron, and its range is limited to 3.0 to 5.5% in order to secure basic oxidation resistance. When the content of Si is less than 3.0%, the oxidation resistance of the matrix structure is poor, and when the content of Si is more than 5.5%, fracture toughness and impact characteristics are deteriorated.

Mn은 강도향상을 위한 펄라이트 조장 원소로 첨가되기도 하지만, 1.0%를 초과하게 되면, 셀간 탄화물 형성을 조장하여 인성의 열화를 초래하게 되므로 그 함량을 1.0% 이하로 한정한다.Mn may be added as a pearlite-promoting element for improving strength, but if it exceeds 1.0%, it promotes the formation of carbide between cells, leading to deterioration of toughness, so the content is limited to 1.0% or less.

Ni은 Mn과 마찬가지로 펄라이트 조장 원소로 첨가되기도 하지만, 그 가격이 고가이어서 특별한 이유 없이는 사용하지 않으며, 0.5%를 초과하면 재료의 가격을 상승시키므로 그 함량을 0.5% 이하로 한정한다.Ni is added as a pearlite-producing element like Mn, but its price is expensive and is not used for no particular reason. If it exceeds 0.5%, Ni increases the price of the material and limits its content to 0.5% or less.

Cr은 탄화물 형성을 조장하는 원소로서 Cr 함유량이 0.5%를 초과하게 되면, 탄화물이 과잉 형성되어 소재의 인성을 저하시키므로 그 함량을 0,5% 이하로 한정한다.Cr is an element that promotes the formation of carbides. When the Cr content exceeds 0.5%, carbides are excessively formed and the toughness of the material is lowered, so the content is limited to 0,5% or less.

그리고 W은 본 발명재에서 가장 중요한 원소로서 고온강도 뿐만 아니라 내산화성을 향상시킨다. W은 무거운 원소의 하나로서 고온 산화 시, W원자의 확산 속도가 느리기 때문에 산화막 형성을 억제하는 역활을 담당한다. 0.01% 이하에서는 그 효과가 미미하고 6.0%를 초과하면 셀간 탄화물이 다량 형성되어 인성이 저하되는 단점이 있다. 따라서 W의 함량을 0.01∼6.0%로 한정한다. 또한 Mo을 W과 함께 첨가시켜 W의 내산화성 향상의 효과를 극대화할 수 있으며, 이 때 셀간 탄화물이 과잉으로 형성되는 3.0%를 초과하지 않아야 한다.And W is the most important element in the present invention improves oxidation resistance as well as high temperature strength. W is one of the heavy elements and plays a role of suppressing the formation of an oxide film because the diffusion rate of W atoms is slow during high temperature oxidation. If the amount is less than 0.01%, the effect is insignificant, and if it exceeds 6.0%, a large amount of carbides are formed between cells, thereby reducing the toughness. Therefore, the content of W is limited to 0.01 to 6.0%. In addition, Mo may be added together with W to maximize the effect of improving the oxidation resistance of W, at which time the intercell carbides should not exceed 3.0%, which is excessively formed.

이하 본 발명을 실시예를 통하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

본 발명에서는 표 1에 개시된 바와 같이 조성되는 구상흑연주철재를 제조하여 경도, 인장 특성 및 내산화 특성을 평가하였다.In the present invention, the spherical graphite cast iron material prepared as shown in Table 1 was prepared to evaluate the hardness, tensile properties and oxidation resistance.

[표 1] 구상흑연주철재의 화학조성 (단위 : 중량%)[Table 1] Chemical Composition of Spheroidal Graphite Cast Iron (Unit: wt%)

CC SiSi MnMn NiNi CrCr MoMo WW 비교재 1Comparative material 1 3.473.47 2.752.75 0.310.31 0.210.21 0.0240.024 -- -- 비교재 2Comparative material 2 3.313.31 3.603.60 0.310.31 0.020.02 0.0230.023 -- -- 비교재 3Comparative material 3 3.363.36 3.403.40 0.490.49 0.010.01 0.1200.120 0.170.17 -- 발명재 1Invention 1 3.463.46 3.723.72 0.230.23 0.020.02 0.0250.025 -- 0.470.47 발명재 2Invention Material 2 3.363.36 3.653.65 0.250.25 0.020.02 0.0310.031 0.250.25 0.650.65

즉, 전기로를 이용하여 여러 가지 주철재를 용해 및 접종처리한 후, 금형주조 또는 연속주조를 통하여, 표 1에 개시된 바와 같은 직경 110mm의 구상흑연주철을 제조하였다. 발명재 1, 2는 비교재 1, 2, 3과 달리 W을 함유하고 있다. 물론 비교재 1은 Si를 2.75% 함유하므로 본 발명의 범위를 벗어나고 있다. 구상흑연주철재의 경도시험은 Rockwell B등급에서 100kg 하중에서 10번 이상 측정한 후에 평균하여 평가하였다. 내산화성은, 600∼1000℃에서 200시간 동안 대기중에 노출된 상태를 유지하였으며, 노출 전, 후의 무게 차이를 측정하여 평가하였다.That is, after dissolving and inoculating various cast iron materials by using an electric furnace, spherical graphite cast iron having a diameter of 110 mm as shown in Table 1 was manufactured through mold casting or continuous casting. Inventive material 1, 2 contains W unlike the comparative materials 1, 2, and 3. Of course, Comparative Material 1 contains 2.75% of Si, which is beyond the scope of the present invention. Hardness test of spheroidal graphite cast iron was evaluated by average of 10 times or more at 100kg load in Rockwell B grade. Oxidation resistance was maintained at 600-1000 ° C. for 200 hours in the air, and evaluated by measuring the difference in weight before and after exposure.

[표 2] 구상흑연주철재의 경도 및 내산화 특성[Table 2] Hardness and Oxidation Resistance of Spheroidal Graphite Cast Irons

경도(HRB)Hardness (HR B ) 산화 후 무게 증가량(g)Weight increase after oxidation (g) 외부Out 중심부center 660℃660 ℃ 700℃700 ℃ 비교재 1Comparative material 1 89.989.9 89.789.7 0.05380.0538 0.23030.2303 비교재 2Comparative material 2 84.884.8 88.288.2 0.05750.0575 0.15910.1591 비교재 3Comparative material 3 91.091.0 92.092.0 0.05020.0502 0.19360.1936 발명재 1Invention 1 92.692.6 92.892.8 0.02920.0292 0.09030.0903 발명재 2Invention Material 2 93.593.5 94.094.0 0.02120.0212 0.07860.0786

고온 노출로 인한 산화량은 표 2에 개시된 바와 같이, 600℃에 노출되는 경우, 기존의 비교재 1, 2, 3은 산화로 인하여 0.0502∼0.575g의 무게 증가량을 보인 반면에 W을 함유한 발명재 1, 2는 0.0212∼0.0292g으로, 발명재 1, 2는 비교재 1, 2, 3보다 거의 2배 이상의 우수한 내산화성을 보인다. 또한 700℃에 노출되는 경우에도, 비교재 1, 2, 3은 0.1591∼0.2303g으로 발명재 1, 2의 0.0786∼0.0903g에 비하여 매우 열악한 내산화성을 보인다는 것을 알 수 있다. 이를 그래프로 도시한 것이 도 1이다.Oxidation amount due to high temperature exposure, as shown in Table 2, when exposed to 600 ℃, comparative materials 1, 2, 3 shows a weight increase of 0.0502 ~ 0.575g due to oxidation, while the invention containing W Ashes 1 and 2 are 0.0212 to 0.0292g, and invention materials 1 and 2 show almost twice as good oxidation resistance as comparative materials 1, 2 and 3. In addition, even when it is exposed to 700 degreeC, comparative materials 1, 2, and 3 are 0.1591-0.2303g, and it turns out that they show very poor oxidation resistance compared with 0.0786-0.903g of invention materials 1 and 2. This is illustrated in a graph of FIG. 1.

또 비교재 1, 2, 3의 경도는 최소 84.8에서 최대 92.0으로 발명재 1, 2의 경도 범위인 92.6∼94.0에 비해 상대적으로 낮다. 일반적으로 경도가 높을수록 긁힘 마모에 대한 저항성이 증가하므로 발명재 1, 2의 내마모성이 비교재 1, 2, 3보다 우수하다는 것을 알 수 있다.In addition, the hardness of Comparative Materials 1, 2, and 3 is at least 84.8 to 92.0, which is relatively lower than 92.6 to 94.0, which is the hardness range of Inventive Materials 1 and 2. In general, the higher the hardness, the higher the resistance to scratching wear, and thus, the wear resistance of the inventive materials 1 and 2 can be seen to be superior to the comparative materials 1, 2 and 3.

본 발명은 W을 첨가하여 기지조직을 페라이트로 안정화시키고 산화막 형성 속도를 감소시킴으로써 내산화성을 향상시키고, W이 M23C6과 같은 조대한 탄화물의 천이를 지연시키고 M2C를 안정화하므로 내열성, 내마모성은 물론 내산화성을 더욱 향상시킬 수 있다.The present invention improves oxidation resistance by stabilizing the matrix structure with ferrite by adding W and reducing the rate of oxide film formation, and because W delays the transition of coarse carbides such as M 23 C 6 and stabilizes M 2 C, Wear resistance as well as oxidation resistance can be further improved.

또한 본 발명은 상기 구상흑연주철재를 700∼1200℃에서 오스테나이트화한 후에 서냉하여 페라이트 조직을 가지게 하므로 열팽창계수를 작게 하고, 연신률과 같은 기계적 특성을 향상시킬 수 있다. 200∼700℃에서 유지하여 잔류응력을 완화시키므로 기계적 특성을, 700∼1200℃에서 오스테나이트화한 후에 공냉 또는 급냉한 후에 300∼700℃에서 탬퍼링하므로 강도를 각각 향상시킬 수 있다.In addition, the present invention is austenitic the spherical graphite cast iron material at 700 ~ 1200 ℃ and then cooled slowly to have a ferrite structure, so that the coefficient of thermal expansion can be reduced, and mechanical properties such as elongation can be improved. Since the residual stress is alleviated by maintaining at 200 to 700 ° C., the mechanical properties are austenited at 700 to 1200 ° C., followed by air cooling or quenching, and then tempered at 300 to 700 ° C., thereby improving the strength.

Claims (4)

중량비로, C:2.2∼3.8%, Si:3.0∼5.5%, Mn:1.0% 이하, Ni:0.5% 이하, Cr:0.5% 이하, W:0.01∼6.0%, Mo:0∼3.0%를 포함하고, 나머지는 Fe, 불가피한 불순물 또는 흑연의 구상화를 위하여 첨가되는 Mg, Zr, Bi, 그리고 희토류 원소의 복합물이 각각 또는 합이 0.001∼0.6%의 조성으로 이루어짐을 특징으로 하는 내열용 구상흑연주철재.By weight ratio, C: 2.2-3.8%, Si: 3.0-5.5%, Mn: 1.0% or less, Ni: 0.5% or less, Cr: 0.5% or less, W: 0.01-6.0%, Mo: 0-3.0% are included And the remainder of which is a composite of Mg, Zr, Bi, and rare earth elements added for spheroidization of Fe, unavoidable impurities or graphite, respectively, or a sum of 0.001 to 0.6% of the heat-resistant spheroidal graphite cast iron material . 중량비로, C:2.2∼3.8%, Si:3.0∼5.5%, Mn:1.0% 이하, Ni:0.5% 이하, Cr:0.5% 이하, W:0.01∼6.0%, Mo:0∼3.0%를 포함하고, 나머지는 Fe, 불가피한 불순물 또는 흑연의 구상화를 위하여 첨가되는 Mg, Zr, Bi, 그리고 희토류 원소의 복합물이 각각 또는 합이 0.001∼0.6%로 조성되는 구상흑연주철재를,By weight ratio, C: 2.2-3.8%, Si: 3.0-5.5%, Mn: 1.0% or less, Ni: 0.5% or less, Cr: 0.5% or less, W: 0.01-6.0%, Mo: 0-3.0% are included The remainder is a spherical graphite cast iron material in which a composite of Mg, Zr, Bi, and rare earth elements added for spheroidization of Fe, unavoidable impurities, or graphite, respectively or in a sum of 0.001 to 0.6%, 700∼1200℃에서 오스테나이트화한 후에 서냉하여 페라이트 조직을 가지게 하는 내열용 구상흑연주철재 열처리방법.A heat-treatment method for heat-resistant spheroidal graphite cast iron which has austenitized at 700 to 1200 ° C., followed by slow cooling to give a ferrite structure. 중량비로, C:2.2∼3.8%, Si:3.0∼5.5%, Mn:1.0% 이하, Ni:0.5% 이하, Cr:0.5% 이하, W:0.01∼6.0%, Mo:0∼3.0%를 포함하고, 나머지는 Fe, 불가피한 불순물 또는 흑연의 구상화를 위하여 첨가되는 Mg, Zr, Bi, 그리고 희토류 원소의 복합물이 각각 또는 합이 0.001∼0.6%로 조성되는 구상흑연주철재를,By weight ratio, C: 2.2-3.8%, Si: 3.0-5.5%, Mn: 1.0% or less, Ni: 0.5% or less, Cr: 0.5% or less, W: 0.01-6.0%, Mo: 0-3.0% are included The remainder is a spherical graphite cast iron material in which a composite of Mg, Zr, Bi, and rare earth elements added for spheroidization of Fe, unavoidable impurities, or graphite, respectively or in a sum of 0.001 to 0.6%, 200∼700℃에서 유지하여 잔류응력을 완화시키는 내열용 구상흑연주철재 열처리방법.Heat treatment method for heat-resistant spheroidal graphite cast iron which is maintained at 200-700 ° C to relieve residual stress. 중량비로, C:2.2∼3.8%, Si:3.0∼5.5%, Mn:1.0% 이하, Ni:0.5% 이하, Cr:0.5% 이하, W:0.01∼6.0%, Mo:0∼3.0%를 포함하고, 나머지는 Fe, 불가피한 불순물 또는 흑연의 구상화를 위하여 첨가되는 Mg, Zr, Bi, 그리고 희토류 원소의 복합물이 각각 또는 합이 0.001∼0.6%로 조성되는 구상흑연주철재를,By weight ratio, C: 2.2-3.8%, Si: 3.0-5.5%, Mn: 1.0% or less, Ni: 0.5% or less, Cr: 0.5% or less, W: 0.01-6.0%, Mo: 0-3.0% are included The remainder is a spherical graphite cast iron material in which a composite of Mg, Zr, Bi, and rare earth elements added for spheroidization of Fe, unavoidable impurities, or graphite, respectively or in a sum of 0.001 to 0.6%, 700∼1200℃에서 오스테나이트화한 후에 공냉 또는 급냉한 후에 300∼700℃에서 탬퍼링하는 내열용 구상흑연주철재 열처리방법.A heat-resistant spheroidal graphite cast iron heat-treatment method which is tempered at 300 to 700 ° C after austenitizing at 700 to 1200 ° C, followed by air cooling or quenching.
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KR101013843B1 (en) * 2007-11-09 2011-02-14 현대자동차주식회사 High Strength and High Oxidation Resist Hi Silicon Ferritic CGI Cast Iron
KR101040658B1 (en) * 2010-11-30 2011-06-10 (주)희원금속 Spheroidal graphite cast iron for ultra low temperature

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EP0430241B1 (en) * 1989-11-30 1996-01-10 Hitachi Metals, Ltd. Wear-resistant compound roll
JPH0741849A (en) * 1993-07-26 1995-02-10 Aisin Takaoka Ltd Production of high proof stress austempered spheroidal graphite cast
KR970065735A (en) * 1996-03-29 1997-10-13 김무 Highly Ductile Ductile Iron and its Manufacturing Method
JPH10273711A (en) * 1997-03-28 1998-10-13 Ube Ind Ltd Production of thick spheroidal graphite cast iron article for high temperature use
KR100212817B1 (en) * 1997-04-07 1999-08-02 이광래 Method of manufacturing ductile cast iron with high toughness made of cast iron
KR19980085543A (en) * 1997-05-29 1998-12-05 김영귀 High Strength High Toughness Spheroidal Graphite Cast Iron

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KR101013843B1 (en) * 2007-11-09 2011-02-14 현대자동차주식회사 High Strength and High Oxidation Resist Hi Silicon Ferritic CGI Cast Iron
KR101040658B1 (en) * 2010-11-30 2011-06-10 (주)희원금속 Spheroidal graphite cast iron for ultra low temperature

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