WO2019107699A1 - Acier austénitique ayant une résistance à la température ambiante et à haute température par une réduction du chrome (cr) - Google Patents

Acier austénitique ayant une résistance à la température ambiante et à haute température par une réduction du chrome (cr) Download PDF

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WO2019107699A1
WO2019107699A1 PCT/KR2018/008541 KR2018008541W WO2019107699A1 WO 2019107699 A1 WO2019107699 A1 WO 2019107699A1 KR 2018008541 W KR2018008541 W KR 2018008541W WO 2019107699 A1 WO2019107699 A1 WO 2019107699A1
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strength
high temperature
chromium
carbide
content
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English (en)
Korean (ko)
Inventor
유지성
이성학
김기용
김형준
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KEYYANG PRECISION CO Ltd
POSTECH Academy Industry Foundation
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KEYYANG PRECISION CO Ltd
POSTECH Academy Industry Foundation
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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
    • 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
    • C22C38/44—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

Definitions

  • the present invention relates to an austenitic steel excellent in high temperature strength, more specifically, a heat resistant stainless steel used for a high temperature such as a turbo charger or an automobile exhaust system, and is a high-priced alloy element nickel
  • the present invention relates to austenitic steel capable of replacing Ni with a low-cost alloy element and reducing the content of chromium (Cr), realizing improved high-temperature properties as compared with conventional heat-resistant stainless steels, and improving cost competitiveness.
  • High temperature austenitic steels have been used for turbochargers and exhaust systems in automobiles, as they not only have excellent hardness, strength, thermal-mechanical fatigue life and fracture toughness but also have thermally stable microstructure.
  • the turbocharger improves the output of the engine by compressing and supplying a large amount of air into the cylinder of the engine.
  • the turbocharger rotates the turbine wheel in the turbine housing using the exhaust gas discharged from the engine, And a structure in which a compressor wheel in a compressor housing that compresses air in the air by transmitting a rotational force generated when the wheel rotates is rotated and supplied to the engine.
  • the turbine housing accommodating such a turbine wheel is continuously brought into contact with the exhaust gas at 800 to 900 ° C discharged from the engine, the turbine housing receives a very high thermal shock according to the output of the engine. Therefore, the turbine housing has excellent strength at high temperature, As shown in Fig.
  • high temperature austenitic steels such as SCH 22 heat resistant stainless steels are currently used.
  • high heat resistant stainless steels include Ni %, which is a major cause of increasing the manufacturing cost of the turbine housing.
  • Korean Patent Laid-Open Publication No. 2016-0091041 discloses a carbon steel sheet comprising 0.4 to 0.5 wt% of carbon (C), 1.0 to 2.0 wt% of silicon (Si), 1.0 to 2.0 wt% of manganese (Mn) Nickel (Ni): 9.0 to 12.0 wt%, chromium (Cr): 21 to 24 wt%, niobium: 1.0 to 2.5 wt%, tungsten (W): 0.5 to 3.5 wt% (Nb) and tungsten (W) are added through an alloy containing a rare earth element, a rare earth element, and other unavoidable impurities while significantly reducing the content of nickel (Ni), thereby improving castability and high temperature strength.
  • C carbon
  • Si silicon
  • Mn manganese
  • Ni nickel
  • Cr chromium
  • niobium 1.0 to 2.5 wt%
  • tungsten (W) 0.5 to 3.5 wt% (
  • niobium (Nb) and tungsten (W), which are added to replace nickel (Ni), are expensive alloying elements.
  • niobium (Nb) There is a problem that the brittleness of the alloy is increased.
  • the present invention aims at providing a high temperature austenitic steel having improved room temperature and high temperature tensile properties as compared with conventional alloys while lowering the production cost by reducing the content of nickel (Ni) and chromium (Cr) We will do it.
  • the present invention provides a method of manufacturing a semiconductor device, comprising: 0.35 to 0.5 wt% of carbon; 1.0 to 2.0 wt% of silicon; 5.0 to 8.0 wt% of manganese; (C) content of the alloying elements, and the content of iron (Fe) and inevitable impurities is less than 16.5 wt%, chromium (Cr) 20-24 wt%, molybdenum Austenitic steel excellent in high-temperature strength, in which the ratio of Cr (Cr) content, C Cr / C C is 50 to 60, is provided.
  • the present invention relates to a method of manufacturing a nickel-metal hydride alloy, which is a method of replacing manganese (Mn), which is a relatively inexpensive alloying element, with nickel (Ni) at a predetermined ratio while maintaining the austenite structure at high temperature and adding niobium (Nb) and tungsten ,
  • the tensile strength at room temperature is 400 MPa or more (490 MPa or more in one embodiment), and the tensile strength at room temperature is controlled by controlling the content of chromium (Cr) while minimizing the formation of ferrite phase to maintain the ratio of the carbide phase at 1.5 to 4%
  • the austenitic steel according to the present invention can obtain a significant cost reduction effect as compared with a conventional austenitic steel containing nickel (Ni) in an amount of 20% by weight or more, and at the same time, the strength at room temperature and high temperature strength can be improved.
  • Example 1 is a microstructure image of austenite steel produced according to Example 2 and Comparative Example 1 of the present invention.
  • Example 2 shows the XRD measurement results of the austenitic steel produced according to Example 2 and Comparative Example 1 of the present invention.
  • Example 3 is a microstructure image of austenitic steel produced according to Example 2 of the present invention and Comparative Example 1 after high temperature tensile test at 900 ° C.
  • the present inventors have studied alloys capable of achieving high temperature strength capable of withstanding high temperature environments of 900 ° C or higher while maintaining price competitiveness.
  • Ni nickel
  • Mo molybdenum
  • Mo molybdenum
  • the present invention can reduce the area ratio of carbide to 4% or less, It is characterized by the design.
  • the austenitic steel according to the present invention contains 0.35 to 0.5 wt% of carbon (C), 1.0 to 2.0 wt% of silicon (Si), 5.0 to 8.0 wt% of manganese (Mn), 13.5 to 16.5 (C) content of said alloying elements, wherein said chromium (Cr) content is from 20 to 24% by weight, said molybdenum (Mo) is from 0.5 to less than 1.5% (Cr) content, and C Cr / C C is 50 to 60.
  • P not more than 0.04% by weight
  • S not more than 0.04% by weight of the impurities.
  • the reason for limiting the components of the austenitic steel according to the present invention is as follows.
  • Carbon (C) is known as a strong austenite stabilizing element, and it also plays an important role in the strength at high temperature due to strengthening in the base structure. In addition, it forms carbides with alloy elements such as chromium (Cr) included in the present invention to improve the main composition of the liquid phase and improve the high temperature strength. In order to obtain the effect of carbon (C), 0.35 wt% or more of carbon is required. When it exceeds 0.5 wt%, the overall mechanical property and creep resistance may be deteriorated due to coarsening of carbide. Do.
  • Silicon (Si) has the effect of improving the oxidation resistance at high temperature and serves as a reducing agent in the molten alloy. Silicon (Si) improves oxidation resistance by helping to prevent oxidation by chromium (Cr). Silicon oxide particles formed by silicon (Si) are precipitated under the coating formed on the alloy surface by chromium (Cr), which helps formation of a passive film and suppresses unnecessary escape of chromium (Cr) ions. This effect of silicon (Si) is further enhanced at high temperatures. If it is less than 1.0% by weight, it is difficult to sufficiently obtain the effect of silicon (Si). If silicon (Si) is added excessively, not only low temperature creep resistance is lowered but also silicon (Si) is a ferrite stabilizing element. It should be added in an amount of 2.0 wt% or less, since it destabilizes the knitted base structure.
  • Manganese (Mn) acts as an austenite stabilizing element and acts as a reducing agent in the melt, similar to silicon (Si).
  • the content of nickel (Ni), which is an austenite stabilizing element is less than that of the conventional alloy. Therefore, when the content of manganese (Mn) is less than 5.0 wt%, the austenite base structure is made unstable A ferrite phase may be formed. When it exceeds 8.0 wt%, the oxidation resistance at high temperature and the high temperature moldability are deteriorated, so that it is kept at 8.0 wt% or less.
  • the content of manganese (Mn) is more preferably 7.0 to 8.0% by weight.
  • Nickel (Ni) is an element that stabilizes austenite and is an essential element for improving all mechanical properties including toughness and corrosion resistance and oxidation resistance. When it is less than 13.5% by weight, the strength at high temperature is lowered. When it exceeds 16.5% The effect of reducing the manufacturing cost is reduced, which is not desirable.
  • the content of nickel (Ni) is more preferably 13.5 to 14.5% by weight.
  • Cr (Cr) is the most important element of the excellent oxidation resistance and corrosion resistance of stainless steel. It forms a stable passive film of Cr 2 O 3 type on the surface of the alloy and improves the corrosion resistance. The higher the content of chromium (Cr), the higher the corrosion resistance and also contributes to the oxidation resistance and the corrosion resistance at high temperatures. In order to improve the corrosion resistance, it is preferable that chromium (Cr) is added by 20 wt% or more.
  • chromium (Cr) is excessively added as a ferrite stabilizing element, and a ferrite phase can be formed and an amount of carbon (C) in the austenite base is reduced due to an increase in the proportion of chromium carbide, And a large amount of carbide can be formed, so that it is limited to not more than 24% by weight.
  • the content of chromium (Cr) is more preferably 20 to 22 wt%.
  • Molybdenum acts as a ferrite stabilizing element or carbon to promote the formation of M 7 C 3 phase, and it enhances the room temperature and high temperature strength simultaneously by generating solid solution strengthening effect in the austenite base.
  • the M 7 C 3 phase is less likely to be formed and the strengthening effect is difficult to obtain.
  • the content of molybdenum (Mo) is more than 1.5% by weight, the ferrite phase can be stabilized and formed in large amounts. Do.
  • the ratio of the chromium (Cr) content (wt%) to the carbon (C) content (wt%) in the alloy element is less than 50 or more than 60, the base strengthening effect due to carbon solubility is not sufficiently obtained, Is too small to reduce the strength, it is desirable to maintain the above range.
  • Phosphorus (P) 0.04% by weight or less
  • Phosphorus (P) is a component which is inevitably incorporated as an impurity. It may be segregated in the alloy and may adversely affect the physical properties of the alloy, so that it is preferable to maintain the phosphorus (P) at 0.04% by weight or less, more preferably 0.03% .
  • the sulfur (S) forms a sulfide such as MnS in the alloy to improve the workability of the alloy, but the formed sulfide deteriorates the overall physical properties of the alloy.
  • the content of carbon (C) in the matrix of the austenite steel is less than 0.35% by weight, the solid solution strengthening effect is not sufficient and it is difficult to increase the tensile strength at room temperature.
  • the carbon (C) content exceeds 0.45% It is not preferable because the high-temperature tensile strength may be lowered, and it is preferable to maintain 0.35 to 0.45 wt%.
  • the area fraction (%) occupied by the carbide phase in the microstructure of the austenite steel is preferably 1.5 to 4% or less, because it is not preferable to improve the room temperature and high temperature strength when the area fraction is less than 1.5% or exceeds 4%.
  • the austenitic steel is characterized in that at least a part of the carbide in the form of M 7 C 3 (M means a metal alloy element) at the time of high-temperature stretching at 900 ° C is M 23 C 6 (M means metal alloy element) Type carbide to form a fine secondary carbide.
  • M 7 C 3 type carbide is decomposed into a fine carbide of the M 23 C 6 type in a high temperature environment, the high temperature strength can be further improved, which is preferable.
  • the austenitic steel may have a tensile strength at room temperature of 400 MPa or higher (more preferably 480 MPa or higher) and a tensile strength at 900 ⁇ ⁇ of 140 MPa or higher (more preferably 145 MPa or higher).
  • the area fraction of the ferrite phase is preferably 1% or less since the stability is deteriorated at high temperature.
  • the austenitic steel according to the present invention can also be used for turbo housing.
  • Table 1 shows the compositions of Comparative Examples 1 to 4 in which the addition ratios of nickel (Ni) and chromium (Cr) are different for comparison with Examples 1, 2 and Examples of austenitic steel according to the present invention .
  • Example 1 0.40 1.2 7.9 0.04 0.04 14 25 One Honey. Comparative Example 2 0.40 1.2 7.9 0.04 0.04 14 19 One Honey. Example 1 0.40 1.2 7.9 0.04 0.04 14 23 One Honey. Example 2 0.40 1.2 7.9 0.04 0.04 14 21 One Honey. Comparative Example 3 0.40 1.2 7.9 0.04 0.04 14 21 0 Honey. Comparative Example 4 0.40 1.2 7.9 0.04 0.04 14 21 2 Honey.
  • Fig. 1 shows the results of an optical microscope analysis of austenitic steel according to Example 2 and Comparative Example 1 of the present invention.
  • Example 2 shows the results of XRD analysis of austenitic steel according to Example 2 and Comparative Example 1 of the present invention and austenitic steel after 900 ° C high temperature tensile test.
  • Example 3 shows electron microscopic analysis results of the austenitic steel according to Example 2 and Comparative Example 1 after the high temperature tensile test at 900 ° C.
  • Table 2 shows the results of measuring the fraction occupied by the ferrite phase and the carbides (M 7 C 3 phase and M 23 C 6 phase) in the microstructure of the steel, which is identified in FIGS. 1 and 2, using EBSD.
  • Examples 1 and 2 of the present invention are comparative examples 1 and 2 including chromium (Cr) contents of 19 wt% and 25 wt%, respectively, and molybdenum (Mo) % And 2% by weight, respectively, as compared with Comparative Examples 3 and 4.
  • the austenitic matrix structure was stabilized by reducing chromium (Cr), which is a ferrite stabilizing element, and the carbide fraction was adjusted to 1.5 to 4% As a result, the tensile strength at room temperature and the elongation were both increased.
  • Cr reducing chromium
  • the carbide fraction should be adjusted to 1.5 to 4% in order to simultaneously enhance the solid solution strength and the strength improvement effect by the carbide.
  • Examples 1 and 2 showed a decrease in the high temperature stability of the carbide due to the reduced chromium (Cr) content.
  • the initial M 7 C 3 carbide was decomposed into M 23 C 6 carbide, and fine M 23 C 6 carbide was further precipitated in the matrix.
  • the hardness of the base plays a major role in improving the strength. As shown in Table 2 above, in Examples 1 and 2, excellent base hardness was secured even at high temperature through precipitation of fine M 23 C 6 carbide in the matrix, thereby improving high temperature strength.
  • the carbide fraction was less than 1% as in the room temperature tensile characteristic, so that the effect of strengthening with carbide was low and the high temperature tensile strength was low.
  • Comparative Example 4 since the carbide fraction was as high as 6%, the effect of improving the strength by the carbide was large, but it was difficult to obtain the effect of increasing the strength by the known solid solution strengthening. Compared with Examples 1 and 2 utilized, Comparative Example 4 has a low high temperature strength.
  • the present invention relates to a high-performance gasoline engine having a task specific number S2340875, which is supported by the 'Small and Medium Business Administration (ministry name)', and 'Korea-Industry Technology Development Agency (R & Development of engine based supercharger based technology to improve low speed performance and to cope with high exhaust temperature above 950 °C (Research title) ".

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

Selon la présente invention, l'acier austénitique pour les températures élevées est caractérisé en ce qu'il contient de 0,35 à 0,5 % en poids de carbone (C), de 1,0 à 2,0 % en poids de silicium (Si), de 5,0 à 8,0 % en poids de manganèse (Mn), de 13,5 à 16,5 % en poids de nickel (Ni), de 20 à 24 % en poids de chrome (Cr), de 0,5 à moins de 1,5 % en poids de molybdène (Mo), le reste étant du fer (Fe) et les impuretés inévitables, le rapport entre la teneur en chrome (Cr) et la teneur en carbone (C), CCr/CC, dans les éléments d'alliage étant de 50 à 60.
PCT/KR2018/008541 2017-11-28 2018-07-27 Acier austénitique ayant une résistance à la température ambiante et à haute température par une réduction du chrome (cr) Ceased WO2019107699A1 (fr)

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KR1020170159874A KR101974815B1 (ko) 2017-11-28 2017-11-28 크롬(Cr) 저감을 통한 상온 및 고온강도가 우수한 오스테나이트강
KR10-2017-0159874 2017-11-28

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KR102292016B1 (ko) 2019-11-18 2021-08-23 한국과학기술원 균일하게 분포하는 나노 크기의 석출물을 다량 함유한 오스테나이트계 스테인리스강 및 이의 제조방법

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JPH06228712A (ja) * 1993-02-03 1994-08-16 Hitachi Metals Ltd 高温強度および被削性の優れたオーステナイト系耐熱鋳鋼およびそれからなる排気系部品
JPH0741910A (ja) * 1993-07-30 1995-02-10 Nippon Steel Corp 分散強化型耐熱材料とその製造方法
JPH07113143A (ja) * 1993-10-18 1995-05-02 Toyota Motor Corp オーステナイト系耐熱鋳鋼
US20170088910A1 (en) * 2015-09-29 2017-03-30 Exxonmobil Research And Engineering Company Corrosion and cracking resistant high manganese austenitic steels containing passivating elements
KR20170036833A (ko) * 2015-09-18 2017-04-03 현대자동차주식회사 오스테나이트계 내열볼트 및 그 제조방법

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JPH06228712A (ja) * 1993-02-03 1994-08-16 Hitachi Metals Ltd 高温強度および被削性の優れたオーステナイト系耐熱鋳鋼およびそれからなる排気系部品
JPH0741910A (ja) * 1993-07-30 1995-02-10 Nippon Steel Corp 分散強化型耐熱材料とその製造方法
JPH07113143A (ja) * 1993-10-18 1995-05-02 Toyota Motor Corp オーステナイト系耐熱鋳鋼
KR20170036833A (ko) * 2015-09-18 2017-04-03 현대자동차주식회사 오스테나이트계 내열볼트 및 그 제조방법
US20170088910A1 (en) * 2015-09-29 2017-03-30 Exxonmobil Research And Engineering Company Corrosion and cracking resistant high manganese austenitic steels containing passivating elements

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