KR102136455B1 - Self-healable trip superalloys and manufacturing method for the same - Google Patents

Abstract

복합 구조를 가지도록 하여 초고온에서 지속가능하게 활용할 수 있는 초합금을 제조하는 것에 관한 것이다. 본 발명에 의한 초합금은 침입형 고용 원자인 B, C, N, O을 주요 합금화 원소로 포함하기 때문에 고온에서 크랙 주변에 우선 확산을 통한 화합물 (Boride, Carbide, Nitride 및 Oxide 등) 형성으로 크랙 형성에 저항함으로써 자가 치유 특성을 나타낼 수 있을 뿐만 아니라, 낮은 SFE를 가지는 합금으로 설계되어 변형시 TRIP 특성을 나타내 우수한 소성 변형 특성을 동시에 나타낸다.
본 발명의 TRIP 특성을 가지는 고온 자가 치유 특성의 초합금은 기존 초합금의 한계인 연성의 문제를 극복하였을 뿐만 아니라, 초합금이 활용되는 초고온 영역에서 쉽게 균열을 치유할 수 있는 자가 치유 특성을 가지기 때문에, 우수한 고온 크립 특성 및 고온강도가 요구되는 발사체 추진부, 원자력 압력용기, 피복관, 고효율 차세대 화력 발전용 터빈 블레이드 등의 고온 극한환경 대응 구조소재로 응용될 수 있는 효과가 있다.The present invention enables self-healing by controlling the constituent elements and processes of the Co-based alloy

It relates to the manufacture of a superalloy that can be used at a very high temperature and sustainable by having a composite structure. Since the superalloy according to the present invention contains B, C, N, and O as intrusive solid atoms as main alloying elements, it forms cracks by forming compounds (Boride, Carbide, Nitride, Oxide, etc.) through diffusion first around the crack at high temperatures. In addition to being able to exhibit self-healing properties by resisting, it is designed with an alloy having a low SFE and exhibits TRIP properties during deformation, thereby simultaneously exhibiting excellent plastic deformation properties.
The superalloy of the high temperature self-healing property having the TRIP property of the present invention not only overcomes the problem of ductility, which is the limitation of the existing superalloy, but also has excellent self-healing properties that can easily heal cracks in the ultra-high temperature region where the superalloy is utilized. There is an effect that can be applied as a structural material for high temperature extreme environments such as a projectile propulsion unit, a nuclear pressure vessel, a sheath tube, and a high-efficiency next-generation thermal power turbine blade that require high temperature creep characteristics and high temperature strength.

Description

Metamorphic organic calcined superalloy with self-healing properties and its manufacturing method {SELF-HEALABLE TRIP SUPERALLOYS AND MANUFACTURING METHOD FOR THE SAME}

) 상과 FCC 결정 구조 내에 원자간 특별한 오더링 (ordering)을 가지는 L1₂ 구조의

상간의 복합구조를 가지면서도, 구성 원소 비를 제어하여 적층 결함 에너지 (SFE, Stacking fault energy)를 낮춤으로써 오스테나이트 (

) 상의 변형 시 변태 유기 소성 (TRIP, Transformation induced plasticity) 특성이 나타는 것을 특징으로 한다. 이때, 상기 합금에 B, C, N 및 O 등을 포함하는 침입형 고용 원자를 첨가함으로써 고온 사용 환경에서 발생된 균열 (Crack) 주변으로의 빠른 확산을 통한 화합물 (Boride, Carbide, Nitride 및 Oxide 등)의 형성을 도모하여 초기 균열의 성장을 방해함으로써, 자가 치유 특성을 발현할 수 있는 합금 및 그 제조 방법에 관한 것이다. The present invention relates to a metamorphic organic calcined superalloy having self-healing properties and a method for manufacturing the same, austenite having a face centered cubic (FCC) crystal structure (

) L1 ₂ structure with special ordering between atoms in the phase and FCC crystal structure

Austenite by reducing the stacking fault energy (SFE) by controlling the ratio of constituent elements while having a complex structure between phases.

It is characterized by the appearance of metamorphic organic plasticity (TRIP, Transformation induced plasticity) when transforming. At this time, by adding an interstitial solid atom containing B, C, N, and O to the alloy, compounds (Boride, Carbide, Nitride, Oxide, etc.) through rapid diffusion into cracks generated in a high-temperature use environment are added. ) By preventing the growth of the initial crack by promoting the formation of an alloy and a method for manufacturing the same.

As various studies have been conducted to solve the challenges of ultra-high temperature extreme environments, including high-efficiency power generation such as nuclear fusion, space, etc., the development of materials that can be used in new complex extreme environments is also required. It is necessary to develop new materials that surpass the characteristics of superalloys. Incidentally, inconel, which is based on Ni or the like, which is classified as a high-melting-point alloy, has escaped, and in recent years, superalloy development, such as Co-based alloys, is also rapidly progressing for use at higher operating temperatures.

복합 구조를 가지는 초합금의 경우에는 복합 구조의 특성상 연성 저하라는 문제를 지니고 있었다. 특히, 초고온에서 활용되는 한계로 인해, 한번 미소 단위의 크랙이 발생하게 되면, 쉽게 대 단위의 크랙으로 발전하는 등의 문제가 구조 재료로의 활용에 큰 문제로 대두되고 있다. 종합하면, 초합금의 지속적 활용 (Sustainability)을 위해서는 1) 복합 구조에 의해 발생하는 연성의 저하 문제는 물론, 극한 환경에서 활용되는 만큼 2) 소재 스스로가 미소 단위 크랙을 치유할 수 있는 자가 치유 (Self healing) 특성을 가지도록 하는 것이 필요하다.Meanwhile, the existing

In the case of a superalloy having a composite structure, due to the characteristics of the composite structure, there was a problem of reduced ductility. In particular, due to limitations utilized at ultra-high temperatures, once micro-scale cracks are generated, problems such as easily developing into large-scale cracks have emerged as a big problem in utilization as a structural material. Taken together, for continuous use of superalloy (Sustainability) 1) as well as the problem of deterioration of ductility caused by the complex structure, as well as being utilized in extreme environments 2) self-healing that allows the material itself to heal micro cracks (Self healing).

Therefore, in the present invention, in order to develop a new material having high sustainability in an extreme environment, a Co-based metamorphic organic calcined superalloy having a self-healing property and a manufacturing method thereof were developed. In other words, the present invention proposes an alloy composition capable of forming a Co-based superalloy structure that can be utilized at a higher temperature than the existing Ni-based superalloy through composition and process control, and also controls SFE to control transformational organic plasticity (TRIP, Transformation induced) Plasticity) was made possible to increase the ductility compared to existing materials. Particularly, by expressing the TRIP characteristic, which is a concept previously used for structural metal materials such as steel, the purpose was to improve the plastic deformation characteristics of an alloy system having a problem of reduced ductility.

In addition, by adding intrusive solid solution atoms including B, C, N, and O, which have a very high diffusion rate, to the developed alloy composition, microcracks generated when the material is used at high temperatures are filled with compounds by rapid diffusion. Healing mechanisms were made possible. Simultaneous realization of the low SFE and self-healing mechanism of the developed alloy can significantly improve creep resistance, a representative index of ultra-high temperature properties, and is thus highly applicable to high-temperature materials.

Glass corrosion-resistant cobalt superalloy with high strength KR 10-0089177-0000

Science 312, 2006. "Cobalt-Base High-Temperature Alloys" J. Sato, 6 persons, 90-92 pages, 2006

복합 구조의 약점으로 지적되었던 소성 변형 특성의 극대화를 도모한다. The present invention is to solve the problems of the prior art described above, and relates to a Co-based superalloy that can be utilized in an extremely high temperature extreme environment including high efficiency power generation and space. In particular, when designing the alloy composition of a Co-based superalloy, SFE performs precise calculation through thermodynamic simulation and optimizes the composition so that TRIP characteristics are expressed.

It seeks to maximize the plastic deformation characteristics that were pointed out as a weakness of the composite structure.

In addition, even in the case of ultra-high temperature extreme environment, even if micro cracks, which are almost impossible to observe, occur, there is a possibility that it is easily generated as a large crack due to creep and fatigue stress. Did. To this end, a small amount of intrusive solid atoms having a significantly higher diffusion rate than other alloying elements is added, and even if a crack is formed at a high temperature, the compound can be easily moved to a corresponding defect through rapid diffusion to form a compound. Spontaneous healing of defects is possible.

To achieve the above object, the superalloy of the high temperature self-healing property having TRIP properties according to the present invention is a base alloy that controls Co and Cr, Ti forming a precipitated phase, and lattice misfit between the phases forming a complex structure. Preparing an alloying element (B, C, N, and O) having a large atomic radius containing Mo and the like and a self-healing property that diffuses rapidly to the formation of cracks and has self-healing properties at high temperature; Dissolving the prepared alloy element and proceeding with solution treatment; It is manufactured through the step of forming a precipitate by aging the solution-treated alloy.

In addition, it is possible to select a composition capable of exhibiting TRIP properties by calculating the effect of each alloying element on the lamination defect energy of the entire alloy based on the thermodynamic database and evaluating the influence of each alloying element.

복합 구조를 가지는 것으로써, 초고온에서 활용되던 기존의 소재를 대체할 수 있다. 이때,

복합 구조는 합금의 용체화 처리 이후 에이징 (Aging) 등의 열처리 공정의 제어를 통해서 제조 가능하며, 이에 따라 다양한 형상의 미세구조의 확보가 가능하다.As described above, the superalloy of high temperature self-healing properties having TRIP properties is

By having a composite structure, it is possible to replace the existing material that was used at ultra-high temperatures. At this time,

The composite structure can be manufactured through the control of a heat treatment process such as aging after solution treatment of the alloy, and accordingly, it is possible to secure a microstructure of various shapes.

In addition, the present invention can 1) have a low SFE and secure TRIP characteristics that show easy phase transformation by stress, that is, improve the plastic deformation characteristics, and 2) high temperature through alloying of intrusive solid-solution atoms having a fast diffusion rate. At the time of crack formation in, the atom rapidly spreads around the crack to form a compound to simultaneously fill and self-healing properties. Having the developed material with low SFE and defect self-healing mechanism can significantly improve creep resistance, which is pointed out as the biggest problem in the use of ultra-high temperature of existing superalloys, and is actively utilized as a new concept ultra-high temperature component material in the future. It is expected to be possible.

값의 변화를 나타낸 도면이며, 이때 Cr을 1 at.% 합금화 할 때마다 상기 물리량이 54.34 J/mol 만큼 감소함을 도시한 것이다.
도 5는 본 발명의 비교예 2 에 의한 Co₃Cr 합금에 Ti, Mo 및 B을 각각 합금화 함에 따른

값의 변화를 나타낸 도면이며, 이때 각 원소를 1 at.% 합금화 할 때마다 상기 물리량이 각각 +471.96, -26.17 및 -83.12 J/mol 만큼 변화함을 도시한 것이다.
도 6은 본 발명의 실시예 1 합금을 정밀한 공정 제어를 통해 제조한 경우 형성되는

복합 구조를 나타내는 주사 전자 현미경 (SEM, Scanning electron microscope) 이미지이다.
도 7은 본 발명의 실시예 11 합금을 정밀한 공정 제어를 통해 제조한 경우 형성되는

복합 구조를 나타내는 주사 전자 현미경 (SEM, Scanning electron microscope) 이미지이다.
도 8은 본 발명의 실시예 1 및 실시예 11 에 의한 합금을 제조하고, 이를 압축 시험한 결과를 나타내는 도면이다.
도 9는 본 발명의 실시예 1 합금의 변형 전후의 X선 회절 분석 (XRD, X-ray diffraction)을 통해 상분석을 진행한 결과를 나타내는 것이다.
도 10은 본 발명의 실시예 1 합금의 변형 전후의 전자 후방 산란 회절 (EBSD, Electron backscattered diffraction)을 통해 상분석을 진행한 결과를 나타내는 것이다.
도 11은 본 발명의 실시예 11 합금의 변형 전후의 X선 회절 분석 (XRD, X-ray diffraction)을 통해 상분석을 진행한 결과를 나타내는 것이다.
도 12는 본 발명의 실시예 11 합금의 변형 전후의 전자 후방 산란 회절 (EBSD, Electron backscattered diffraction)을 통해 상분석을 진행한 결과를 나타내는 것이다.1 is a thermodynamically calculated binary state diagram between cobalt (Co) and chromium (Cr).
Figure 2 shows a pseudo (Pseudo) binary system state diagram between the Co ₃ Cr alloy and titanium (Ti) according to Comparative Example 2 of the present invention.
FIG. 3 is a scanning electron microscope (SEM) image showing that a B-based compound may be formed by excess B when the alloy of Example 17 of the present invention is prepared.
Figure 4 shows the alloying of Cr to Co

It is a diagram showing a change in value, and it is shown that the physical quantity decreases by 54.34 J/mol every time Cr is alloyed at 1%.
Figure 5 according to the alloying of each of Ti, Mo and B in the Co ₃ Cr alloy according to Comparative Example 2 of the present invention

It is a diagram showing a change in value, and it is shown that the physical quantity changes by +471.96, -26.17 and -83.12 J/mol, respectively, each time each element is alloyed with 1 at.%.
6 is formed when the alloy of Example 1 of the present invention is manufactured through precise process control

It is a scanning electron microscope (SEM) image showing a complex structure.
7 is formed when the alloy of Example 11 of the present invention is manufactured through precise process control

It is a scanning electron microscope (SEM) image showing a complex structure.
8 is a view showing the results of manufacturing an alloy according to Example 1 and Example 11 of the present invention, and compression test it.
Figure 9 shows the results of the phase analysis through X-ray diffraction analysis (XRD, X-ray diffraction) before and after deformation of the alloy of Example 1 of the present invention.
Figure 10 shows the results of the phase analysis through the electron back scattering diffraction (EBSD, Electron backscattered diffraction) before and after deformation of the Example 1 alloy of the present invention.
Figure 11 shows the results of the phase analysis through X-ray diffraction analysis (XRD, X-ray diffraction) before and after deformation of the Example 11 alloy of the present invention.
FIG. 12 shows the results of phase analysis through electron backscattered diffraction (EBSD) before and after deformation of the Example 11 alloy of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. In the drawings, parts not related to the description are omitted in order to clearly describe the present invention, and the same reference numerals are used for the same or similar components throughout the specification. In the case of well-known technology, detailed description thereof will be omitted.

In this case, when a certain part of the specification "includes" a certain component, this means that other components may be further included instead of excluding other components unless otherwise specified.

복합 구조 초합금의 SFE를 조절하여 향상된 소성 변형 특성을 획득할 수 있을 뿐만 아니라, 침입형 고용 원소들의 제어를 통해 고온에서의 자가 치유 특성을 발현할 수 있다. The present invention relates to a superalloy having a high temperature self-healing property having a TRIP property and a method of manufacturing the same, and secured through controlling the composition and post-treatment process of the alloy.

By adjusting the SFE of the composite structure superalloy, it is possible to obtain improved plastic deformation properties, and to express self-healing properties at high temperatures through control of intrusive solid solution elements.

Selection of superalloy composition

복합구조를 가져 매우 우수한 기계적 물성을 가지는 것으로 알려져 있으며, 기존에 알려진 초합금의 조성은 Inconel을 대표로하는 Ni계 및 Co계 합금 등이 보고되어 있다. 특히 1768 K 의 녹는점을 가지는 Co를 기지로 하는 Co계 초합금에, 2180 K 의 녹는점을 갖는 Cr을 합금화함으로써 더욱 녹는점을 높일 수 있다. 이때, Co 및 Cr은 같은 전이 원소계 금속으로써 쉽게 합금화 되어 FCC 결정구조의 합금을 구성하며, 도 1에 도시된 바와 같이 특정 조성 이하 (40.5 at.% Cr)에서는 FCC 결정구조의 전율 고용체를 이루는 것으로 알려져 있다. 본 열역학 계산은 Thermo-Calc 소프트웨어를 통해 계산되었으며, 상기 계산은 SSOL 6 데이터베이스를 기반으로 확인되었다. 추가로, 하기에서 활용되는 열역학 계산은 모두 상기의 데이터베이스와 소프트웨어를 토대로 확보된 결과이다. In general, superalloy

It is known to have a very good mechanical property with a composite structure, and the composition of the super alloy known in the past has been reported to include Ni-based and Co-based alloys representing Inconel. In particular, the melting point can be further increased by alloying Cr having a melting point of 2180 K to a Co-based superalloy based on Co having a melting point of 1768 K. At this time, Co and Cr are easily alloyed as the same transition element-based metal to form an alloy of the FCC crystal structure, and as shown in FIG. 1, below a certain composition (40.5 at.% Cr), forming a throttle solid solution of the FCC crystal structure It is known. This thermodynamic calculation was calculated using Thermo-Calc software, and the calculation was confirmed based on the SSOL 6 database. In addition, all of the thermodynamic calculations utilized below are the results obtained based on the above database and software.

In addition to this, it is possible to contain 15 at.% or less of at least one element selected from the group consisting of Fe, Mn, Ni, and V as Co and Cr, and 15 at.% or less compared to Co and Cr. If it is included in excess, the properties of the Co-based superalloy are lost, which is undesirable.

복합 구조 형성을 위해서는 FCC 결정 구조 내에 특별한 화학적 오더링을 가지는 L1₂ 상 (

)을 형성 시켜야 한다. 이를 위해 본 발명에서는 전이 금속에 합금화 되어 쉽게 오더링을 형성하는 것으로 알려진 Ti을 선택하였다. 이때, Ti은 쉽게 금속간 화합물인

상을 형성하기 때문에, 과량 합금화 하는 경우에는 본 발명의 최종 목적인

복합 구조 형성이 어려울 수 있다. 따라서 초합금을 구성하는 기지 합금 대비 Ti 조성의 한정은 매우 중요하다. 이 문제의 해결을 위하여 본 발명에서는 도 2에 도시된 바와 같이, 본 발명에 의한 비교예 2의 Co₃Cr 합금과 Ti 간의 의사 2원계 상태도의 계산을 통해 그 한계 조성 (8.0 at.%)을 확인하였다.Meanwhile, superalloy

For the formation of complex structures, the L1 ₂ phase with special chemical ordering within the FCC crystal structure (

). To this end, in the present invention, Ti known to be easily alloyed to a transition metal to form ordering was selected. At this time, Ti is an easily intermetallic compound

Since it forms a phase, in the case of excessive alloying, the final object of the present invention

Complex structure formation can be difficult. Therefore, it is very important to limit the Ti composition compared to the base alloy constituting the superalloy. In order to solve this problem, in the present invention, as shown in FIG. 2, the limit composition (8.0 at.%) is calculated through calculation of a pseudo binary system state diagram between Co ₃ Cr alloy and Ti of Comparative Example 2 according to the present invention. Confirmed.

복합 구조 형성을 위해서는 각

상과

상 간의 격자 미스핏 의 고려가 매우 중요하다. 일반적으로, 전이 금속 대비 큰 원자 반지름을 갖는 Ti (1.76 Å)이 고용 이후, 석출에 의해 형성되는

상의 격자 상수 (Lattice parameter)는 기지 상인

상 대비 큰 값을 갖게 된다. 이 경우, 각 상간의 격자 미스핏이 발생하게 되어

의 석출이 저해될 수 있다. 따라서 본 발명에서는 아래 표 1과 같이 Ti 보다 더 큰 원자 반지름을 가지며, 전이 금속에 쉽게 고용될 수 있는 합금 원소로써 Mo을 합금화 하였다. 이때, 발생할 수 있는 격자 상수의 증가량을 산술적으로 계산하여 Co 및 Cr 의 원자 반지름의 평균 길이 대비, Mo은 약 16%, Ti은 9% 정도 큰 값을 보인다. 즉, Ti에 의한 격자 미스핏을 보전하기 위해 투입하는 원소인 Mo은 각 상간의 원자 반경 길이가 역전되지 않도록 전체 Ti의 투입량의 최대 50% 까지만 합금화 할 수 있도록 한정하였다. 이에 추가하여, Mo 과 비슷한 원자 반경을 가지며, Co 및 Cr 합금에 쉽게 고용되어 복합 구조 간의 격자 미스핏을 줄일 수 있는 Nb, Ta, W 및 Re으로 이루어진 군에서 선택된 1종 이상의 원소를 Mo 대비 30% 이하로 포함하는 것이 가능하나, 30% 이상 포함하는 경우 격자 미스핏이 다시 증가하여 바람직하지 않다.Also,

In order to form a complex structure, each

Prize

It is very important to consider the lattice misfit between phases. Generally, Ti (1.76 Å) having a larger atomic radius than the transition metal is formed by precipitation after solid solution.

The lattice parameter of the phase is the base merchant.

It has a large value compared to the phase. In this case, a lattice misfit between each phase occurs.

Precipitation may be inhibited. Therefore, in the present invention, Mo is alloyed as an alloying element having a larger atomic radius than Ti, and can be easily employed in a transition metal, as shown in Table 1 below. At this time, the increase in the lattice constant that can occur is calculated by arithmetic, the average length of the atomic radius of Co and Cr, Mo is about 16%, Ti is about 9% larger. That is, Mo, which is an element that is input to preserve the lattice misfit due to Ti, is limited to alloying up to 50% of the total Ti input so that the atomic radius between each phase is not reversed. In addition, one or more elements selected from the group consisting of Nb, Ta, W, and Re, which have an atomic radius similar to Mo, and are easily employed in Co and Cr alloys to reduce lattice misfit between composite structures, compared to Mo 30 It is possible to include less than %, but if it contains more than 30%, the lattice misfit increases again, which is undesirable.

element Atomic Radius (Å) Co 1.52 Cr 1.66 Co-Cr 1.59 Mo 1.90 Ti 1.76

Lastly, it was selected from the group of elements containing B, C, O and N as elements capable of forming self-healing properties by forming a compound around the crack due to rapid diffusion at high temperature as a chipped atom. At this time, when the intrusion-type atom is added in excess of 2 at.%, even if it is not exposed to a high temperature atmosphere, as in the case of the B-based compound shown in FIG. 3, during the solidification process, the B-based compound inside the base is second phase. It forms excessively, which is undesirable because it promotes embrittlement. In general, the role of the interstitial atom in the alloy is similar, and thus, its role is systematically described with reference to B.

In summary, the alloy composition according to the present invention is as shown in Chemical Formula 1 below.

(However, I is one or more alloying elements selected from the group containing invasive solid atoms B, C, O and N, 0≤a≤40.5, 0≤b≤8.0, 0≤c≤0.5b and 0≤ d≤2.0 at.%.)

Calculation of stacked defect energy (SFE) for expression of TRIP properties

On the other hand, this alloy is an alloy having a composite structure between two phases having an FCC crystal structure, and due to the properties of the composite structure alloy, it is inevitable to suffer damage in plastic deformation characteristics including stretching. Therefore, the present invention was intended to solve the above problems through the expression of transformation organic plasticity (TRIP, Transformation induced plasticity) characteristics, which are known to maximize the plastic deformation characteristics of materials.

상의 SFE 값이 낮은 것이 유리하다. SFE 의 감소를 위해서는 다종의 원소가 합금화 되는 것이 좋으며, 특히 SFE를 감소시키는 것으로 알려진 합금화 원소의 합금화가 필수적이다. 이때, SFE는 적층 결함에 의해 발생할 수 있는 상인 HCP 상과 원래의 모상인 FCC 상간의 계면 에너지와 각 상간의 깁스 자유에너지 차이 (

)에 큰 영향을 받는다. 다만, 특정한 합금 원소로만 구성된 본 발명에 의한 합금은 조성 변화가 크지 않기 때문에 조성에 큰 영향을 받는, 계면 에너지 역시 큰 변화가 없을 것으로 예상된다. 즉,

값만을 고려하여도 적층 결함 에너지의 예측이 가능한 것으로 알려져 있기 때문에, 하기에서는

와 SFE 값이 선형적으로 비례한다고 가정하고, 두 개념을 혼용하여 사용할 수 있다.In general, for the expression of TRIP properties, the FCC crystal structure acting as the matrix phase of the alloy

It is advantageous that the SFE value of the phase is low. In order to reduce the SFE, it is preferable to alloy a plurality of elements, and in particular, alloying of an alloying element known to reduce SFE is essential. At this time, SFE is the difference between the interfacial energy between the HCP phase, which is a phase that may be caused by a stacking defect, and the FCC phase, which is the original mother phase, and the Gibbs free energy difference between each phase (

). However, the alloy according to the present invention composed of only a specific alloy element is expected to have no significant change in interface energy, which is greatly influenced by the composition because the composition change is not large. In other words,

Since it is known that the lamination defect energy can be predicted by considering only the value, in the following

Assuming that the and SFE values are linearly proportional, the two concepts can be used interchangeably.

값을 도시한 것이다. 도면에 도시 된 것과 같이 본 발명에 의한 초합금의 주 원소인 Co에 Cr을 합금화 하는 경우 빠른 속도로 SFE가 감소할 것으로 예상할 수 있다. 이때, SFE 값의 감소가 Cr의 함량에 비례해 일차식에 의해 감소한다고 가정하면, 전체 합금 대비 Cr의 첨가에 따른 변화는

와 같이 예상할 수 있다. 4 shows alloying Cr to Co

It shows the value. As shown in the figure, when alloying Cr to Co, which is the main element of the superalloy according to the present invention, it can be expected that SFE will decrease rapidly. At this time, assuming that the decrease of the SFE value is decreased by the linear equation in proportion to the content of Cr, the change according to the addition of Cr compared to the entire alloy is

Can be expected as

값의 변화를 나타내었다. 이때, 기지 합금은 FCC 결정구조를 가지는 Co와 Cr 간의 합금으로써, 본 발명의 비교예 2인 Co₃Cr 조성의 합금으로 가정하여 계산하고, 각 원소의 합금화에 따른 변화량은 도면에 도시하였다. 추가적으로, 해당 계산 결과는 아래의 표 2에 자세히 상술하였다.In addition, in FIG. 5, alloying of representative additional elements such as Ti, Mo and B, which are representative alloying elements according to the present invention, to a base alloy composed of Co and Cr

Changes in values are shown. At this time, the base alloy is an alloy between Co and Cr having an FCC crystal structure, and is calculated by assuming an alloy having a Co ₃ Cr composition, Comparative Example 2 of the present invention, and the amount of change due to alloying of each element is illustrated in the drawings. Additionally, the calculation results are detailed in Table 2 below.

Element: Elemental fraction Energy (J/mol) Error
(%) Co Cr Ti Mo B FCC G HCP G ΔG
_Calcluation ΔG fitting (1) Co-Cr alloy ΔG = -394.76-54.34 X _cr 100.00 0.00 0.00 0.00 0.00 -8769.17 -9012.18 -243.01 -394.8 38.4 95.00 5.00 0.00 0.00 0.00 -7407.05 -8022.93 -615.88 -666.5 7.6 90.00 10.00 0.00 0.00 0.00 -6122.88 -7086.33 -963.45 -938.2 2.7 85.00 15.00 0.00 0.00 0.00 -5036.06 -6321.79 -1285.73 -1209.9 6.3 80.00 20.00 0.00 0.00 0.00 -4187.27 -5770.00 -1582.73 -1481.6 6.8 75.00 25.00 0.00 0.00 0.00 -3617.35 -5471.79 -1854.44 -1753.3 5.8 70.00 30.00 0.00 0.00 0.00 -3398.12 -5498.96 -2100.84 -2025.0 3.7 65.00 35.00 0.00 0.00 0.00 -3370.26 -5692.23 -2321.97 -2296.7 1.1 60.00 40.00 0.00 0.00 0.00 -3319.44 -5837.22 -2517.78 -2568.4 2.0 55.00 45.00 0.00 0.00 0.00 -3235.71 -5924.02 -2688.31 -2840.1 5.3 (2) Co ₃ Cr-Ti alloy ΔG = -1788.11 + 471.96 X _Ti 75.00 25.00 0.00 0.00 0.00 -3617.35 -5471.79 -1854.44 -1753.3 5.8 74.25 24.75 1.00 0.00 0.00 -4673.06 -6012.84 -1339.78 -1267.7 5.7 73.50 24.50 2.00 0.00 0.00 -5673.28 -6511.58 -838.30 -782.2 7.2 72.75 24.25 3.00 0.00 0.00 -6640.00 -6989.52 -349.52 -296.6 17.8 72.00 24.00 4.00 0.00 0.00 -7578.26 -7451.25 127.01 188.9 32.8 71.25 23.75 5.00 0.00 0.00 -8490.63 -7898.95 591.68 674.5 12.3 70.50 23.50 6.00 0.00 0.00 -9406.54 -8333.88 1072.66 1160.0 7.5 69.75 23.25 7.00 0.00 0.00 -10303.60 -8756.91 1546.69 1645.6 6.0 69.00 23.00 8.00 0.00 0.00 -11169.70 -9168.64 2001.06 2131.1 6.1 68.25 22.75 9.00 0.00 0.00 -12005.70 -9569.50 2436.20 2616.6 6.9 67.50 22.50 10.00 0.00 0.00 -12812.60 -9959.87 2852.73 3102.2 8.0 (3) Co ₃ C-Mo alloy ΔG = -1861.50-26.17 X _Mo 75.00 25.00 0.00 0.00 0.00 -3617.35 -5471.79 -1854.44 -1753.3 5.8 74.63 24.88 0.00 0.50 0.00 -3680.48 -5551.64 -1871.16 -1759.6 6.3 74.25 24.75 0.00 1.00 0.00 -3727.12 -5614.57 -1887.45 -1765.8 6.9 73.88 24.63 0.00 1.50 0.00 -3768.13 -5671.28 -1903.15 -1772.1 7.4 73.50 24.50 0.00 2.00 0.00 -3805.87 -5724.02 -1918.15 -1778.4 7.9 73.13 24.38 0.00 2.50 0.00 -3841.53 -5773.81 -1932.28 -1784.7 8.3 72.75 24.25 0.00 3.00 0.00 -3875.86 -5821.25 -1945.39 -1791.0 8.6 72.38 24.13 0.00 3.50 0.00 -3909.44 -5866.71 -1957.27 -1797.3 8.9 72.00 24.00 0.00 4.00 0.00 -3942.75 -5910.45 -1967.70 -1803.6 9.1 71.63 23.88 0.00 4.50 0.00 -3976.28 -5952.63 -1976.35 -1809.9 9.2 71.25 23.75 0.00 5.00 0.00 -4010.48 -5993.40 -1982.92 -1816.2 9.2 (4) Co ₃ Cr Ti ₅ -Mo alloy ΔG = 599.22-7.72 X _Mo 75.00 25.00 0.00 0.00 0.00 -3617.35 -5471.79 -1854.44 -1753.3 5.8 71.25 23.75 5.00 0.00 0.00 -8490.63 -7898.95 591.68 674.5 12.3 70.88 23.63 5.00 0.50 0.00 -8543.25 -7963.51 579.74 668.2 13.2 70.50 23.50 5.00 1.00 0.00 -8580.35 -8010.96 569.39 661.9 14.0 70.13 23.38 5.00 1.50 0.00 -8613.09 -8052.03 561.06 655.6 14.4 69.75 23.25 5.00 2.00 0.00 -8639.37 -8088.94 550.43 649.3 15.2 69.38 23.13 5.00 2.50 0.00 -8660.46 -8122.75 537.71 643.0 16.4 69.00 23.00 5.00 3.00 0.00 -8677.17 -8154.04 523.13 636.7 17.8 68.63 22.88 5.00 3.50 0.00 -8690.13 -8183.20 506.93 630.4 19.6 68.25 22.75 5.00 4.00 0.00 -8699.69 -8210.47 489.22 624.1 21.6 67.88 22.63 5.00 4.50 0.00 -8706.12 -8236.04 470.08 617.8 23.9 67.50 22.50 5.00 5.00 0.00 -8709.67 -8260.05 449.62 611.5 26.5 (5) Co ₃ Cr-B alloy ΔG = -1853.66-83.12 X _B 75.00 25.00 0.00 0.00 0.00 -3617.35 -5471.79 -1854.44 -1753.3 5.8 74.63 24.88 0.00 0.00 0.50 -3368.05 -5263.58 -1895.53 -1788.0 6.0 74.25 24.75 0.00 0.00 1.00 -3101.32 -5038.05 -1936.73 -1822.8 6.3 73.88 24.63 0.00 0.00 1.50 -2827.92 -4805.95 -1978.03 -1857.6 6.5 73.50 24.50 0.00 0.00 2.00 -2550.15 -4569.57 -2019.42 -1892.3 6.7 73.13 24.38 0.00 0.00 2.50 -2269.09 -4330.00 -2060.91 -1927.1 6.9 72.75 24.25 0.00 0.00 3.00 -1985.37 -4087.89 -2102.52 -1961.9 7.2 72.38 24.13 0.00 0.00 3.50 -1699.43 -3843.65 -2144.22 -1996.6 7.4 72.00 24.00 0.00 0.00 4.00 -1411.55 -3597.60 -2186.05 -2031.4 7.6 71.63 23.88 0.00 0.00 4.50 -1121.96 -3349.95 -2227.99 -2066.2 7.8 71.25 23.75 0.00 0.00 5.00 -830.84 -3100.89 -2270.05 -2100.9 8.0

값은 아래의 화학식 2를 따른다고 생각하는 것이 합리적이다.At this time, as a result of synthesizing the above results, it can be confirmed that SFE changes in a linear proportion to the composition change when Cr, Ti, Mo, and B are alloyed to the Co alloy. In particular, by comparing the formulas (3) and (4) of Table 2, it can be seen that even if the composition of the matrix alloy changes significantly from a binary system to a ternary system, a linear proportional relationship is established. Based on these results, the overall alloy

It is reasonable to think that the value follows Formula 2 below.

(However, X _Cr , X _Ti , X _Mo and X _B means the fraction of each element, 100-(X _Cr + X _Ti + X _Mo + X _B ) = X _Co. )

At this time, when comparing the values obtained by substituting the above formula 2 obtained by linearly fitting (Fitting) the values obtained according to the thermodynamics calculation, as shown in Table 2, except for some values It can be seen that most can be predicted very well with an error of 10% or less. That is, through the formula 2 devised by the present invention, the SFE of the superalloy of the self-healing properties of the present invention can be easily predicted.

On the other hand, in the case of interstitial solid atoms containing B, N, O and C, rather than constituting the lattice of the alloy in the alloy, other interstitial types such as N, O, and C because they remain in an intruded form between lattice It can be regarded that all the employed atoms behave like B. Therefore, in the above formula, X _B can be expressed by substituting one or more elements selected from the group of elements consisting of invasive solid atoms composed of N, O, and C in addition to B.

값을 가지는 실시예 1의 경우 약 1674.2 J/mol의 값을 가지는 것을 알 수 있다. 이와 같은 사실을 토대로 판단하여보면, 본 발명에 의한 Co계 합금계에서는 약 1700 J/mol 이하의 깁스 자유에너지 값을 보이는 경우에 TRIP 특성을 보인다고 판단할 수 있다.When calculating the SFE of the embodiment according to the present invention based on the fitted formula 2 above, the highest

In the case of Example 1 having a value, it can be seen that it has a value of about 1674.2 J/mol. Judging from these facts, it can be determined that the Co-based alloy system according to the present invention exhibits TRIP characteristics when the Gibbs free energy value is less than about 1700 J/mol.

복합 구조 형성을 위한 공정 최적화

Process optimization for complex structure formation

복합 구조를 가져 초고온에서 매우 우수한 기계적 물성을 보일 수 있다. 뿐만 아니라, 확산 속도가 빠른 B, C, N 및 O을 포함하는 침입형 고용원자의 첨가를 통해 고온에서 크랙의 형성시에 빠른 확산에 의한 화합물 형성으로 자가 치유 특성의 발현 역시 가능하다.Superalloy of high temperature self-healing properties having TRIP properties according to the present invention

It has a complex structure and can show very good mechanical properties at very high temperatures. In addition, it is also possible to express self-healing properties by forming compounds by rapid diffusion at the time of crack formation at high temperatures through the addition of invasive solid atoms including B, C, N and O, which have a high diffusion rate.

복합 구조의 형성을 위해서는

상의 석출을 위한 특별한 열처리 공정이 필수적이다. 본 발명에 의한 고온 자가 치유 특성의 초합금은 99.99 % 이상의 순도를 가지는 모원소를 준비하여 빠르게 벌크 형태의 균질한 고용체를 형성할 수 있는 아크 용해 (Arc-melting)법으로 제조하고, 제조된 잉곳을 1200±200℃의 온도에서 1 - 100 시간 어닐링 (Annealing)하여 용체화 처리를 진행한 후, 900±200℃의 온도에서 0.5 - 120 시간 동안 에이징 (Aging)함으로써

상을 석출시키는 것이 바람직하다. 용체화 처리시간이 1 시간 미만이면 충분한 고용이 진행되지 않으며, 100 시간을 초과할 경우 과고용 상태로 진행되기 때문에 시간 한정을 요한다. 이때,

상의 석출은 에이징 과정에서 발생하는 것이기 때문에, 에이징 온도 및 시간에 따라 그 미세구조의 형상이 조절 될 수 있으며, Co 계 초합금의 특성상 0.5 시간 미만일 경우 석출이 용이하게 진행되지 않으며, 120 시간이 초과 경우 석출상의 크기가 커지게 되어 나노 복합구조의 장점을 잃게 된다. 본 발명의 실시예에서는 1200 ℃의 온도에서 20 시간 어닐링 (Annealing)하여 용체화 처리를 진행하였다. 이후, 이를 다시 900℃의 온도에서 48 시간과 96 시간 동안 에이징 (Aging)하여

상을 석출시켰다. At this time,

For the formation of a composite structure

A special heat treatment process for the precipitation of the phase is essential. The superalloy of the high-temperature self-healing property according to the present invention is prepared by an arc-melting method capable of quickly forming a homogeneous solid solution in a bulk form by preparing a parent element having a purity of 99.99% or more, and preparing the ingot produced. After annealing for 1 to 100 hours at a temperature of 1200±200°C, a solution treatment is performed, followed by aging at a temperature of 900±200°C for 0.5 to 120 hours.

It is preferred to precipitate the phase. If the solution treatment time is less than 1 hour, sufficient employment does not proceed, and if it exceeds 100 hours, time is limited because it proceeds in an over-employment state. At this time,

Since the precipitation of the phase occurs during the aging process, the shape of its microstructure can be adjusted according to the aging temperature and time, and due to the nature of the Co-based superalloy, precipitation does not proceed easily when it is less than 0.5 hours, and when it exceeds 120 hours As the size of the precipitated phase increases, the advantage of the nanocomposite structure is lost. In the embodiment of the present invention, solution treatment was performed by annealing at a temperature of 1200° C. for 20 hours. Then, it was aged for 48 hours and 96 hours at a temperature of 900° C. again.

The phase was precipitated.

In the present invention, the production of the mother alloy is performed through a commercial casting process using an induction casting method capable of producing a homogeneous alloy by melting the parent element by an electric field in addition to the arc melting method, or a resistance heating method capable of precise temperature control. It is possible to manufacture. In addition, as well as a commercial casting method capable of dissolving the raw metal, the raw material is made of powder, etc., and is subjected to high temperature/high pressure using spark plasma sintering or hot isostatic pressing using powder metallurgy. It can be manufactured by sintering. In the case of the sintering method, there is an advantage in that it is possible to more precisely control microstructure and to manufacture parts of desired shapes.

Examples and comparative examples according to the present invention prepared in the same manner as described above are detailed in Table 3 below.

division Furtherance Crystal structure After transformation
Crystal structure Aging time
(Precipitation size) Comparative Example 1 Co

- Comparative Example 2 Co ₃ Cr

- Comparative Example 3 Co ₆₃ Cr ₂₂ Ti ₁₅

- Comparative Example 4 Co ₆₁ Cr ₂₂ Ti ₁₅ Mo ₂

- Example 1 Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂

- Example 2 Co ₆₅ Fe ₄ Cr ₂₂ Ti ₇ Mo ₂

- Example 3 Co ₆₅ Mn ₄ Cr ₂₂ Ti ₇ Mo ₂

- Example 4 Co ₆₅ Ni ₄ Cr ₂₂ Ti ₇ Mo ₂

- Example 5 Co ₆₅ V ₄ Cr ₂₂ Ti ₇ Mo ₂

- Example 6 Co ₆₉ Cr ₂₂ Ti ₇ Mo _1.5 Nb _0.5

- Example 7 Co ₆₉ Cr ₂₂ Ti ₇ Mo _1.5 Ta _0.5

- Example 8 Co ₆₉ Cr ₂₂ Ti ₇ Mo _1.5 W _0.5

- Example 9 Co ₆₉ Cr ₂₂ Ti ₇ Mo _1.5 Re _0.5

- Example 10 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.9 B _0.1

- Example 11 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.8 B _0.2

48 (~50 nm) Example 12 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.5 B _0.5

- Example 13 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.5 C _0.5

- Example 14 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.5 N _0.5

- Example 15 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.5 O _0.5

- Example 16 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.0 B _1.0

- Example 17 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _98.0 B _2.0

(Boride trace formation)

- Example 18 (Co ₆₉ Cr ₂₂ Ti ₇ Mo ₂ ) _99.8 B _0.2

96 (~100 nm)

의 석출을 돕는 Ti을 첨가하자, 새로운 상이 형성된 것을 확인할 수 있다. 도 6은 본 발명에 의한 실시예 1의 표면을 FE-SEM을 통해 분석한 결과이다. 도면에 나타난 바와 같이 50 nm 이하의 매우 작은 석출물들이 고르게 분포하는 것을 확인할 수 있으며, 이를 통해 물성을 최적화 할 수 있는 복합 구조가 형성되었음을 알 수 있다.As can be seen from the above table, the alloy composed of only Co and Cr was a simple FCC structure alloy, but the alloy

When Ti is added to help precipitation, it can be confirmed that a new phase was formed. 6 is a result of analyzing the surface of Example 1 according to the present invention through FE-SEM. As shown in the figure, it can be seen that very small precipitates of 50 nm or less are evenly distributed, and through this, it can be seen that a complex structure capable of optimizing physical properties was formed.

복합구조의 초합금 구조가 형성되는 것을 확인하였다. 이는 B 첨가에 따라 석출물의 형성이 저해되지 않으며, B에 의한 자가 치유 효과는 물론, 초합금에 의한 우수한 물성을 동시에 확보할 수 있음을 의미한다.On the other hand, Figure 7 is a result of observing the surface of Example 11 according to the present invention, even if the amount of B added for self-healing properties at high temperature increases

It was confirmed that the superalloy structure of the composite structure was formed. This means that the formation of precipitates is not inhibited by the addition of B, and it is possible to simultaneously secure the self-healing effect by B and excellent physical properties by superalloy.

Experimental verification of TRIP characteristic expression

8 is a result of performing compression tests by preparing the alloys of Examples 1 and 10 and 11. As B is alloyed to 0.2 at.%, it can be confirmed that the compressive strength of the material slightly increased, which is interpreted as the effect of strengthening the solid solution of the intrusive solid solution atom.

This phenomenon can also be confirmed in Table 4 below, as compared to Example 1 in which B is not added, as shown in Table 4, it can be seen that Examples 10 and 11 slightly increased the Vickers hardness. This means that addition of B may contribute to the increase in strength by solid solution in addition to the self-healing effect.

division Vickers hardness (Hv) Example 1 370.6 Example 10 374.3 Example 11 373.2

However, even if the compressive strength is increased, it can be confirmed that there is no significant change in the maximum elongation of each example, which can be interpreted as having little effect of reducing elongation due to the addition of B.

)의 피크들만이 인덱싱 (Indexing) 되었던 것과는 다르게, 변형 이후에는 뚜렷하게 HCP 상 (

)이 형성된 것을 확인할 수 있다. 이는 낮은 SFE를 갖는 본 합금이 변형에 의해 적층 결함을 발생시킴으로써 HCP 상이 형성되었다는 것을 의미한다. 즉, 상기 단계들에서 계산을 통해 확인한 낮은 SFE를 갖는 본 합금은 복합 구조의 초합금 미세구조를 가지는 것 뿐만 아니라, 변형 시에 기지 상의 상변태에 의한 TRIP 특성이 발현된다는 것을 알 수 있다. 실제로 도 9의 EBSD 분석 결과를 보면, 변형 전에는 모두 FCC 구조의 오스테나이트 (Austenite) 상으로 인덱싱 되었던 것이, 변형 이후에는 입계 (Grain boundary)를 중심으로 마르텐사이트 (Martensite)로 확인되는 것을 알 수 있으며, 입내에도 래스 (Lath) 형태의 마르텐사이트가 형성된 것을 확인할 수 있다.At this time, FIGS. 9 and 10 show the results of XRD analysis and EBSD analysis before and after deformation of the alloy according to Example 1. As can be seen in Figure 8, before deformation (Undeformed) FCC crystal structure (

), unlike only those peaks that were indexed, after deformation, the HCP phase (

) Can be confirmed. This means that the HCP phase was formed by the deformation of the present alloy with low SFE, resulting in lamination defects. That is, it can be seen that the present alloy having a low SFE confirmed through calculation in the above steps not only has a superalloy microstructure of a composite structure, but also exhibits TRIP characteristics due to phase transformation on the base during deformation. In fact, looking at the results of the EBSD analysis of FIG. 9, it can be seen that all of the indexes of the austenite phase of the FCC structure before deformation were confirmed as martensite around the grain boundary after deformation. , It can be confirmed that a lath (Lath) form of martensite was also formed in the mouth.

This TRIP characteristic can also be exhibited when an intrusive element such as B is added. In fact, by checking the results of Example 11 before and after modification through XRD and EBSD, it can be seen that the same TRIP behavior as Example 1 without B was added.

구조의 복합상을 가질 뿐만 아니라, 복합 구조의 단점으로 지적되던 연성의 감소 역시 TRIP 특성을 통해 개선할 수 있음을 의미한다. 이를 통해 자가 치유 특성을 나타내는 Co 계 TRIP 초합금이 개발된 것으로 확인할 수 있으며, 이는 향후 고온 구조용 소재로 적용이 가능할 수 있다.This fact is that the superalloy of the high temperature self-healing properties according to the present invention,

In addition to having a composite phase of the structure, it also means that the reduction in ductility, which was pointed out as a disadvantage of the composite structure, can also be improved through TRIP properties. Through this, it can be confirmed that a Co-based TRIP superalloy exhibiting self-healing properties has been developed, which may be applicable as a high-temperature structural material in the future.

The present invention has been described through preferred embodiments, but the above-described embodiments are merely illustrative of the technical spirit of the present invention, and various changes are possible within the scope of the present invention. Anyone with ordinary knowledge will understand. Therefore, the protection scope of the present invention should be interpreted by the matters described in the claims, not by specific embodiments, and all technical spirits within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (10)

(However, I is one or more alloying elements selected from the group containing invasive solid atoms B, C, O and N, 0<a≤40.5, 0<b≤8.0, 0<c≤0.5b and 0< d≤2 at.%.)
At the same time expressed as the composition fraction of,

(However, X _Cr , X _Ti , X _Mo and X _I means the fraction of each element, wherein X _I is at least one element selected from the group of elements consisting of invasive solid atoms consisting of B, N, O and C Is the sum of the fractions, 100-(X _Cr + X _Ti + X _Mo + X _I ) = X _Co )
Metamorphic organic calcined superalloy having self-healing properties, characterized in that it has a value of 1700 J/mol or less and, when deformed, has an effect of increasing ductility due to phase change.
The method according to claim 1,
After annealing for 1 to 100 hours at a temperature of 1200±200°C, the solution treatment is performed, followed by aging for 0.5 to 120 hours at a temperature of 900±200°C.

A metamorphic organic calcined superalloy with self-healing properties characterized by having a complex structure.
The method according to claim 2,
By changing the heat treatment conditions including the aging temperature or time

A metamorphic organic calcined superalloy with self-healing properties characterized by controlling the shape and phase fraction of the composite structure.
delete The method according to claim 1,
A metamorphic organic calcined superalloy having self-healing properties, characterized in that it contains at least 15 at.% or less of at least one element selected from the group consisting of Fe, Mn, Ni, and V compared to Co and Cr.
The method according to claim 1,
A metamorphic organic calcined superalloy having self-healing properties, characterized in that it contains 30 at.% or less of one or more elements selected from the group consisting of Nb, Ta, W, and Re compared to Mo.

(However, I is one or more alloying elements selected from the group containing invasive solid atoms B, C, O and N, 0<a≤40.5, 0<b≤8.0, 0<c≤0.5b and 0< d≤2 at.%.)
Preparing an alloy raw material represented by a composition fraction of;
Preparing an alloy by dissolving the raw material;
Annealing the alloy at a temperature of 1200±200° C. for 1 to 100 hours to proceed with solution treatment;
Comprising the step of aging (Aging) for 0.5 to 120 hours at a temperature of 900±200 ℃ the alloy,

(However, X _Cr , X _Ti , X _Mo and X _I means the fraction of each element, wherein X _I is at least one element selected from the group of elements consisting of invasive solid atoms consisting of B, N, O and C Is the sum of the fractions, 100-(X _Cr + X _Ti + X _Mo + X _I ) = X _Co )
Method of manufacturing a metamorphic organic calcined superalloy having self-healing properties, characterized in that the value of the free energy difference between phases calculated as 1700 J/mol or less.
The method according to claim 7,
By changing the heat treatment conditions including the aging temperature or time

Method of manufacturing a metamorphic organic calcined superalloy having self-healing properties, characterized by controlling the shape and phase fraction of the composite structure.
The method according to claim 7,
A method of manufacturing a metamorphic organic calcined superalloy having self-healing properties, characterized in that it contains at least 15 at.% or less of at least one element selected from the group consisting of Fe, Mn, Ni, and V compared to Co and Cr.
The method according to claim 7,
Method of manufacturing a metamorphic organic calcined superalloy having self-healing properties, characterized in that it contains 30 at.% or less of at least one element selected from the group consisting of Nb, Ta, W and Re.

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