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WO2021230392A1 - Alliage à entropie élevée et procédé de fabrication d'un tel alliage - Google Patents

Alliage à entropie élevée et procédé de fabrication d'un tel alliage Download PDF

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Publication number
WO2021230392A1
WO2021230392A1 PCT/KR2020/006209 KR2020006209W WO2021230392A1 WO 2021230392 A1 WO2021230392 A1 WO 2021230392A1 KR 2020006209 W KR2020006209 W KR 2020006209W WO 2021230392 A1 WO2021230392 A1 WO 2021230392A1
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WIPO (PCT)
Prior art keywords
melting
entropy alloy
iron
copper
melting point
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Ceased
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PCT/KR2020/006209
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English (en)
Korean (ko)
Inventor
신현권
오진목
강남석
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LG Electronics Inc
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LG Electronics Inc
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Priority to PCT/KR2020/006209 priority Critical patent/WO2021230392A1/fr
Priority to EP20934927.3A priority patent/EP4151766A4/fr
Priority to US17/924,450 priority patent/US20230183846A1/en
Publication of WO2021230392A1 publication Critical patent/WO2021230392A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper

Definitions

  • the present embodiment relates to a high-entropy alloy and a method for manufacturing the same, and more particularly, to a high-entropy alloy with improved composition and process, and a method for manufacturing the same.
  • a high-entropy alloy having high fluidity and wettability while simultaneously implementing opposing characteristics, such as excellent workability and strength, has been developed.
  • a high-entropy alloy is an alloy having a single-phase structure of a face-centered cubic structure (FCC) or a body-centered cubic structure (BCC) having a high mixed entropy by including a plurality of elements in a predetermined amount or more.
  • the conventional high-entropy alloy is vulnerable to galvanic corrosion due to the difference in potential and melting point because different double phases are located in equal ratios, and segregation occurs during the casting process or extraction or cracking of the low-temperature phase occurs during the hot rolling process.
  • the present embodiment is intended to provide a high-entropy alloy having excellent strength and wear resistance while having excellent corrosion resistance, castability and workability, and a method for manufacturing the same.
  • an object of the present invention is to provide a high-entropy alloy that can have various properties according to a change in composition, have excellent productivity or can be manufactured by a simple manufacturing process, and a method for manufacturing the same.
  • the high entropy alloy according to this embodiment is a high entropy alloy having an iron-rich phase and a copper-rich phase (Cu-rich phase).
  • the common conductivity solid solution metal may include nickel (Ni).
  • the melting point lowering element may include at least one of carbon (C), silicon (Si), phosphorus (P), and manganese (Mn).
  • the high entropy alloy may further include at least one of aluminum (Al), manganese (Mn), and chromium (Cr).
  • the high entropy alloy may be 15 to 80 at% iron, 1 to 30 at% copper, 1 to 20 at% nickel, 5 to 20 at% aluminum, 0 to 20 at% manganese, 0 to 15 at% chromium, 0 to 5 at% carbon, 0 to 2 at% silicon, 0 to 2 at% phosphorus, and other unavoidable impurities.
  • the content of the copper in the iron-rich phase may be 1 to 30 at%.
  • the iron-rich phase may be included in a larger volume ratio than the copper-rich phase to exist as a main phase, and the copper-rich phase may be partially present.
  • a method of manufacturing a high entropy alloy includes: melting an iron-containing material including a melting point lowering element and iron to form a molten metal; A high melting point material melting step of melting by adding a high melting point element having a melting point higher than that of the iron-containing material into the molten metal; A copper melting step of melting by putting copper into the molten metal; and melting a low-melting-point material by inputting and melting a low-melting-point material having a melting point lower than that of copper.
  • the iron-containing material may include pig iron.
  • the melting point lowering element may include at least one of carbon, silicon, phosphorus, and manganese.
  • At least two of the first melting temperature of the iron melting step, the second melting temperature of the high melting point material melting step, the third melting temperature of the copper melting step and the fourth melting temperature of the low melting point material melting step than the temperature are mutually It may have a different temperature.
  • the second melting temperature may be higher than the first melting temperature
  • the third melting temperature may be lower than the second melting temperature
  • the fourth melting temperature may be lower than the third melting temperature.
  • the high melting point material may include a common conductivity solid solution metal in which iron and copper are each electrified.
  • the high melting point material may include at least one of nickel and chromium.
  • the low melting point material may include aluminum.
  • the aluminum ingot may be melted by pushing it into the bottom portion of the molten metal.
  • a method of manufacturing a high-entropy alloy includes the basic steps of adding a plurality of materials including iron, copper, and a common conductivity solid-solute metal in which the iron and copper are each electrified; forming an inert gas atmosphere after vacuum; and a melting step of melting the plurality of materials.
  • the plurality of materials may further include at least one of carbon, silicon, phosphorus, aluminum, manganese, and chromium, and the common conductivity solid solution metal may include nickel.
  • the iron may include pig iron or pure iron.
  • the potential difference and the melting point difference between the iron-rich phase and the copper-rich phase may be reduced by including the common conductivity solid solution metal in the high entropy alloy having the dual phase structure of the iron-rich phase and the copper-rich phase.
  • galvanic corrosion can be prevented or minimized, and segregation formation during casting, extraction of a low-temperature phase during hot rolling, or cracking can be effectively prevented.
  • strength, fluidity, wettability, corrosion resistance, workability, and castability can all be improved.
  • the material cost can be reduced by lowering the relatively expensive copper content and increasing the relatively inexpensive iron content. In this case, it is possible to manufacture a high-entropy alloy having various desired properties only by changing the composition, thereby improving productivity and quality.
  • the high-entropy alloy according to this embodiment has excellent castability, it can fill a 2mm mesh channel, so it can be applied to casting parts that require miniaturization and weight reduction, and various performances can be improved by increasing the degree of design freedom.
  • Such a high entropy alloy may be manufactured by melting under atmospheric conditions by controlling the input sequence and melting temperature to improve productivity, or may be manufactured by melting in a process using a vacuum to simplify the manufacturing process.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a high entropy alloy according to an embodiment of the present invention.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a high entropy alloy according to another embodiment of the present invention.
  • FIG. 3 is a field emission scanning electron microscope (FE-SEM) photograph of the high entropy alloy according to Example 1.
  • FIG. 3 is a field emission scanning electron microscope (FE-SEM) photograph of the high entropy alloy according to Example 1.
  • Example 4 is a photograph of performing a salt spray test on the high entropy alloy according to Example 1.
  • Example 6 is a photograph of performing a salt spray test on the high entropy alloy according to Example 2.
  • Example 7 is a photograph of performing a salt spray test on the high entropy alloy according to Example 3.
  • Example 8 is a photograph of a plate material formed by processing the high entropy alloy according to Example 1.
  • FIG. 9 is a photograph of an Oldham ring having a thickness of 1.7 mm manufactured using the high entropy alloy according to Example 1.
  • the high-entropy alloy is a term used to distinguish it from a low-entropy alloy, and may collectively refer to an alloy having an entropy of a certain level or higher.
  • the high-entropy alloy has an entropy of 1.5R or more, and generally has an entropy of 1.0R or more as well as an alloy called a high entropy alloy (high entropy alloy).
  • high entropy alloy may include an alloy called That is, the high-entropy alloy according to the present embodiment may have an entropy of 1.0R or more.
  • the high-entropy alloy according to the present embodiment is a high-entropy alloy having an iron-rich phase and a copper-rich phase, and includes a common electrical conductivity solid solution metal that is electrically dissolved in iron and copper or forms a complete solid solution with each of iron and copper. can do.
  • the common conductivity solid solution metal may include nickel (Ni).
  • the iron-rich phase may mean a phase having the highest iron content (eg, at%) among a plurality of materials (eg, elements) constituting the same, and the copper-rich phase is a plurality of materials constituting the same. It may refer to a phase having the highest iron content (eg, at%) among (eg, elements).
  • the high-entropy alloy may further include at least one of aluminum, manganese, and chromium.
  • it may further include a melting point lowering element (melting point lowering material) for lowering the melting point of the high entropy alloy, the melting point lowering element may include carbon, silicon, phosphorus, manganese, and the like.
  • Iron is inexpensive and has excellent strength and ductility, and since strength and hardness vary greatly depending on the phase structure, high entropy alloys can be easily adjusted to have desired properties.
  • Copper has a low melting point and has good electrical and thermal conductivity.
  • copper is not mixed with iron and forms a double-phase structure of an iron-rich phase and a copper-rich phase, and thus is suitable for forming a high-entropy alloy capable of improving both iron and copper properties.
  • the high entropy alloy according to the present embodiment contains iron and copper that do not mix well with each other, unless other metals are included, they do not mix with each other, making it difficult to form an alloy. Accordingly, in order to prevent phase separation of iron and copper, an alloy including aluminum, manganese, etc. having a predetermined or higher solubility in each of iron and copper may be formed. Accordingly, the high-entropy alloy has an iron-rich phase and a copper-rich phase, but the ratio of the iron-rich phase and the copper-rich phase may vary depending on the content of iron and copper.
  • it may form a complete solid solution with iron, form a perfect solid solution with copper having a high solid solubility in iron, or include a common conductivity solid solution metal having a high solid solubility in copper.
  • nickel having a high solubility in copper or a high solid solubility in iron, or nickel having a high solid solubility may be used as a common solid solution metal.
  • the inclusion of a common conductivity solid solution metal increases the solubility of copper in the iron-rich phase in a high entropy alloy having a dual-phase structure of an iron-rich phase and a copper-rich phase, and increases the solubility of copper in the copper-rich phase.
  • the potential difference and the melting point difference between the iron-rich phase and the copper-rich phase can be reduced. Accordingly, it is possible to prevent or minimize galvanic corrosion that may occur due to a potential difference between the iron-rich phase and the copper-rich phase. In addition, it is possible to effectively prevent segregation formation that may occur during casting due to the difference in melting point between the iron-rich phase and the copper-rich phase, and extraction or cracking of the low-temperature phase during hot rolling. Accordingly, casting or hot rolling is easy. Moreover, nickel has excellent corrosion resistance, which can improve the corrosion resistance of high-entropy alloys.
  • the high solubility of copper in the iron-rich phase including nickel increases, thereby reducing the copper content in the entire high-entropy alloy. Accordingly, it is possible to reduce the material cost by lowering the relatively expensive copper content and increasing the relatively inexpensive iron content. In addition, it is possible to lower the melting temperature in the process of manufacturing a high entropy alloy and improve corrosion resistance.
  • a dual-phase structure including an iron-rich phase and a copper-rich phase may be provided, but the ratios may not be equal.
  • the iron-rich phase is contained in a larger volume ratio than the copper-rich phase and is present as the main phase, and the copper-rich phase is partially present to prevent segregation, resulting in high strength, workability, and castability.
  • the high entropy alloy may have a uniform composition due to wettability.
  • the content of copper in the iron-rich phase may be 5 to 30 at% (eg, 10 to 25 at%). This is in consideration of the content of nickel included in the high entropy alloy, but the present invention is not limited thereto and may have various values.
  • the content of copper in the iron-rich phase that does not include nickel may be less than 5 at% (for example, 3 at% or less).
  • aluminum is a lightweight element (hard material) and is mixed with iron as a low melting point element (low melting point material) to form a body-centered cubic structure.
  • Aluminum can improve hardness, abrasion resistance, strength, etc. while reducing ductility.
  • manganese is included in iron, strength and ductility can be improved at the same time.
  • manganese has a lower melting point than iron and can act as a kind of melting point lowering element that lowers the melting point of a high entropy alloy. Accordingly, it is possible to improve the fluidity and castability of the high entropy alloy.
  • chromium is included in iron, it is possible to additionally improve corrosion resistance by forming a chromium oxide film on iron or iron-rich. Chromium may or may not be included in the high entropy alloy.
  • the melting point when the melting point is lowered by a melting point lowering element such as carbon, silicon, phosphorus, or manganese, it has excellent fluidity and wettability and low high temperature viscosity during the manufacturing process of a high entropy alloy to improve castability.
  • a melting point lowering element such as carbon, silicon, phosphorus, or manganese
  • the melting temperature during the production of the molten metal is low, even if it contains a low-melting-point material such as copper or aluminum, it can be cast under atmospheric conditions. Accordingly, the quality of the high-entropy alloy can be improved.
  • silicon when silicon is included as a low melting point element, castability can be improved and corrosion resistance can be improved by forming an oxide.
  • carbon is included as a low-melting-point element, the melting point can be effectively lowered. If phosphorus is included as a low-melting-point element, the melting point can be effectively lowered even with a small amount.
  • the high entropy alloy may be 15 to 80 at% iron, 1 to 30 at% copper, 1 to 20 at% nickel, 5 to 20 at% aluminum, 0 to 20 at% (e.g., 0.1 to 20 at%, eg, 5 to 20 at%) manganese, 0 to 15 at% (eg, 2 to 15 at%) chromium, 0 to 5 at% (eg, 3 to 5 at%) %) carbon, 0 to 2 at% silicon (eg 1 to 2 at%), 0 to 2 at% (eg 0 to 1 at%) phosphorus, other elements or unavoidable impurities can do.
  • the content of iron is less than 15 at%, strength, ductility, etc. may be reduced, and if the content of iron exceeds 80 at%, the content of other metals decreases, making it difficult to improve various properties in a high entropy alloy.
  • the content of copper is less than 1 at%, the effect of lowering the melting point and improving electrical conductivity or thermal conductivity by copper may not be sufficient. It can be difficult to improve various properties.
  • the content of nickel is less than 1 at%, the above-described effect by nickel may not be sufficient, and if the content of nickel exceeds 20 at%, the content of iron, copper, etc. is not sufficient, improving various properties in high entropy alloys It can be difficult to do.
  • Manganese may or may not be included in the high entropy alloy. When manganese is included in the high entropy alloy, for example, manganese may be included in an amount of 0.1 to 20 at% (eg, 5 to 20 at%). This is to improve the effect of manganese while sufficiently maintaining the content of iron, copper, and the like.
  • Chromium may or may not be included in the high entropy alloy. When chromium is included in the high entropy alloy, for example, chromium may be included in an amount of 2 at% to 15 at%. This is to improve the effect of chromium while sufficiently maintaining the content of iron, copper, and the like.
  • the content of silicon exceeds 2 at%, a precipitate may be formed in the high entropy alloy to cause cracks in the casting.
  • silicon is included in an amount of 1 at% or more, the effect of silicon can be sufficiently realized.
  • the content of carbon exceeds 5 at%, it may be difficult to sufficiently maintain the content of iron, copper, etc., and the melting point of the high entropy alloy may be increased.
  • the high-entropy alloy contains carbon, the melting point can be effectively lowered when the carbon content is 3 to 5 at%.
  • phosphorus may be included in an amount of 2 at% or less so as not to significantly affect other properties while effectively lowering the melting point.
  • the present invention is not limited to the elements and contents described above. Accordingly, elements or materials other than the above-described elements or materials may be further included, and the content of each element or material may be variously modified in consideration of the characteristics of a desired high-entropy alloy.
  • the high entropy alloy according to the present embodiment may be used in the manufacture of various products. That is, the high-entropy alloy according to this embodiment has both excellent fluidity and copper wettability, and thus has superior castability than cast iron, so it can fill a 2mm mesh channel and can be applied to cast parts requiring refinement. In addition, weight reduction may be realized by thinly forming parts that require weight reduction. In addition, various performances can be improved by increasing the degree of freedom in the design of the cast product due to the castability of the precise design. In this case, it is possible to manufacture a high-entropy alloy having various desired properties only by changing the composition.
  • Oldham Ring that prevents the scroll from rotating in the scroll compressor and enables only left and right revolutions.
  • Oldham Ring needs to be lightweight in order to reduce noise and improve efficiency during operation.
  • the Oldham ring must be manufactured to weigh less than 100g, and the key part that holds the scroll in order to combine with the scroll in the Oldham ring must be precisely processed to have an error of only ⁇ 5mm.
  • the high-entropy alloy according to this embodiment has castability that can fill the 2mm mesh channel, so it is possible to manufacture an Oldham ring with a thickness of 2mm or less, and the specific gravity can also be adjusted to 7.2 or less, so it is made of a general iron alloy. It can be lighter than Oldham Ring.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a high entropy alloy according to an embodiment of the present invention.
  • the method of manufacturing a high entropy alloy includes an iron melting step (S10), a high melting point material melting step (S12), a homogenizing step (S14), a copper melting step (S16), a low melting point It may include a material melting step (S18) and an impurity removal step (S20).
  • S10 iron melting step
  • S12 high melting point material melting step
  • S14 homogenizing step
  • S16 copper melting step
  • S16 low melting point
  • It may include a material melting step (S18) and an impurity removal step (S20).
  • the molten metal may be formed by introducing an iron-containing material including iron into the molten metal manufacturing equipment and melting it.
  • an iron-containing material including iron into the molten metal manufacturing equipment and melting it.
  • Various known equipment may be used as the molten metal manufacturing equipment.
  • the iron-containing material may include iron and a melting point lowering element.
  • pig iron or pig iron and manganese may be used together as the iron-containing material. Since pig iron contains a melting point lowering element such as carbon, silicon, manganese, and phosphorus along with iron, pig iron can be used as it is and the melting point lowering element can be added together.
  • pig iron may include 5 at% (eg, 3 to 5 at%) of carbon, 1 to 2 at% of silicon, manganese, phosphorus, and the like.
  • the melting point lowering element is melted together with iron to lower the melting point of iron to effectively lower the first melting temperature.
  • the fourth melting temperature in the low melting point material melting step (S18) performed after adding a low melting point element such as aluminum or copper having a low melting point later can be lowered. Accordingly, it is possible to prevent oxidation of aluminum, copper, etc. at a high temperature (eg, 1600°C or higher, for example, more than 1520°C) in the low-melting-point material melting step (S18). This will be described in more detail later in the melting step (S18) of the low-melting-point material.
  • the first melting temperature of the iron melting step (S10) may be 1450 to 1520 °C. In this temperature range, the iron-containing material can be stably melted, and the burden in the high-temperature process can be reduced.
  • the present invention is not limited thereto, and the melting temperature of the iron melting step S10 may be variously modified.
  • a high melting point material having a higher melting point than the iron-containing material may be introduced into the molten metal to be melted.
  • the high-melting-point material may include a common conductivity-solute metal that is electrically-dissolved in iron and copper, respectively.
  • nickel may be included as the common conductivity solid solution metal.
  • the high melting point material may further include chromium or the like.
  • the second melting temperature of the high melting point material melting step ( S12 ) may be higher than the first melting temperature of the iron melting step ( S10 ).
  • the second melting temperature of the high melting point material melting step (S12) may be 1650 to 1750 °C. In such a temperature range, a material including chromium, nickel, etc. may be stably melted, and a burden due to a high-temperature process may be reduced.
  • the present invention is not limited thereto, and the second melting temperature of the high melting point material melting step (S12) may be variously modified.
  • the homogenization step (S14) may be performed at a homogenization temperature lower than the second melting temperature.
  • the flux used to remove impurities may include Al 2 O 3 , CaO, SiO 2 , and the like.
  • the present invention is not limited thereto, and whether or not the flux is input, the material of the flux, etc. can be variously modified.
  • the homogenization temperature of the homogenization step (S14) may be 1450 to 1520 °C. In this temperature range, homogenization and stabilization are stably possible, and impurities can be removed.
  • the homogenization step (S14) or the impurity removal process included therein may be performed for 1 minute to 10 minutes (eg, 2 minutes to 3 minutes). In this time range, impurities can be stably removed, and productivity can be prevented from being reduced due to excessively long process time.
  • the present invention is not limited thereto, and the homogenization temperature and/or process time of the homogenization step S14 may be variously modified.
  • copper may be added to the molten metal to be melted.
  • the third melting temperature of the copper melting step (S16) is equal to or higher than the first melting temperature of the iron melting step (S10) and the homogenization temperature of the homogenizing step (S14), respectively, and the second melting point of the high melting point material melting step (S12) It may be equal to or lower than the melting temperature.
  • the third melting temperature may be higher than the first melting temperature of the iron melting step ( S10 ) and the homogenization temperature of the homogenizing step ( S14 ), respectively, and lower than the second melting temperature of the high melting point material melting step ( S12 ).
  • the third melting temperature of the copper melting step (S16) may be 1520 to 1650 °C.
  • the molten metal in the copper melting step (S16) contains a relatively low melting point (ie, 1150 degrees C or less, for example, 900 degrees C. It can have a melting point of 1100 degrees Celsius) d. If the third melting temperature is defined as described above in consideration of the melting efficiency along with the melting point, copper can be stably melted after the copper is added, and the burden in the high-temperature process can be reduced.
  • the present invention is not limited thereto, and the melting temperature of the copper melting step S16 may be variously modified.
  • iron or a low-melting-point material having a lower melting point than that of an iron-containing material may be introduced into the molten metal and melted.
  • the low-melting-point material include aluminum.
  • aluminum can be melted or melted by pushing the aluminum into the bottom part of the molten metal in the form of an ingot. Accordingly, it is possible to minimize or prevent aluminum oxide formed by oxidation of aluminum from floating on the surface of the molten metal.
  • the fourth melting temperature of the low-melting-point material melting step (S18) may be the same as or higher than the temperature of the copper melting step (S16).
  • the fourth melting temperature of the low melting point material melting step (S18) may be lower than the temperature of the copper melting step (S16). This is to minimize problems such as oxidation of low-melting-point materials.
  • the fourth melting temperature of the low-melting-point material melting step (S18) may be 1500 degrees C or less (for example, 1200 to 1400 degrees C).
  • the fourth melting temperature exceeds 1500 degrees Celsius (for example, 1400 degrees Celsius)
  • aluminum is oxidized at the same time as melting to form slag composed of aluminum oxide on the molten metal, and a process of removing it must be added.
  • the fourth melting temperature is 1200 degrees C or less, a homogeneous molten metal may not be formed.
  • the present invention is not limited thereto, and the melting temperature of the low solubility material melting step (S18) may be variously modified.
  • impurities eg, oxides and slag present on the surface of the molten metal
  • the flux used to remove impurities may include Al 2 O 3 , CaO, SiO 2 , and the like.
  • the present invention is not limited thereto. Therefore, the impurity removal step S20 may not be performed, and whether or not the flux is input in the impurity removal step S20 , the material of the flux, etc. may be variously modified.
  • the final molten metal from which impurities are removed is tapped at a constant tapping temperature (for example, 1400 to 1600 degrees C, for example, 1500 degrees C) and processed to have a desired shape (for example, using a mold having a desired shape) can be cast).
  • a constant tapping temperature for example, 1400 to 1600 degrees C, for example, 1500 degrees C
  • a desired shape for example, using a mold having a desired shape
  • the present invention is not limited thereto, and the tapping temperature may be variously modified.
  • the manufacturing method of the high entropy alloy according to this embodiment can be processed or cast under normal pressure conditions (ie, general atmospheric pressure conditions) rather than under vacuum conditions, thereby reducing manufacturing costs and can be used for manufacturing various parts of desired shapes.
  • normal pressure conditions ie, general atmospheric pressure conditions
  • pig iron with low purity may be used, and impurities may be easily removed, so that the quality of the manufactured high-entropy alloy may be excellent.
  • the final molten metal is sequentially injected into the prepared mold to manufacture a large number of castings together, thereby reducing costs.
  • the high-entropy alloy can have a uniform composition by adjusting the input order and melting temperature in consideration of the different melting points of a plurality of substances or elements included in the high-entropy alloy, so that the high-entropy alloy has a uniform composition. It is possible to improve the quality by preventing occurrence.
  • oxidation of a low-melting-point element for example, aluminum
  • oxidation of a low-melting-point element occurs during molten metal production, resulting in non-uniform composition or oxides entering the mold when molten metal is injected. This may cause problems such as cracking.
  • the high-entropy alloy according to the present embodiment has excellent fluidity and wettability including a melting point lowering element, so that it can be stably injected into the mold even by maintaining a temperature level of about 1400°C.
  • FIG. 2 is a flowchart illustrating a method of manufacturing a high entropy alloy according to another embodiment of the present invention.
  • the present embodiment may include a preparation step ( S30 ), a step of forming an inert gas atmosphere after vacuum ( S32 ), and a melting step ( S34 ).
  • all materials for manufacturing a high entropy alloy may be input to the molten metal manufacturing equipment.
  • the iron may be pure iron or pig iron.
  • an inert gas atmosphere may be formed while a cleaning operation in the chamber is performed by repeatedly introducing an inert gas after creating a vacuum atmosphere.
  • the inert gas atmosphere may be, for example, an argon (Ar) gas atmosphere.
  • the molten metal may be prepared by melting at a constant melting temperature.
  • the melting temperature of the melting step (S34) is 1750 degrees C or less (for example, 1650 degrees C or less), more specifically, 1200 degrees to 1750 degrees C (for example, 1400 degrees to 1650 degrees C) seeds, for example, 1450°C to 1520°C).
  • the melting temperature of the melting step (S34) may be variously modified depending on the material constituting the high entropy alloy.
  • the melting step (S34) When the melting step (S34) is completed, it is tapped at a constant tapping temperature (eg, 1400 to 1600 degrees Celsius, for example, 1500 degrees Celsius) and processed to have a desired shape (eg, using a mold having a desired shape) can be cast).
  • a constant tapping temperature eg, 1400 to 1600 degrees Celsius, for example, 1500 degrees Celsius
  • the tapping temperature may be variously modified.
  • the melting step ( S34 ) is performed in an inert gas atmosphere after vacuum to effectively prevent a loss (eg, loss of aluminum) due to oxidation of the low-melting-point material.
  • a loss eg, loss of aluminum
  • the manufacturing process can be simplified by a single melting step (S34). Accordingly, a high-entropy alloy having a desired composition can be easily manufactured through a simple process.
  • a high-entropy alloy having a composition according to Table 1 and a chemical formula of Al 15 Ni 15 Cr 10 (CuFe) 50 Mn 10 was prepared using the manufacturing method shown in FIG. 1 .
  • the iron-containing material 4.67 at% carbon, 1.35 at% silicon, 0.27 at% manganese, 0.11 at% phosphorus, 0.02 at% sulfur, 0.08 at% titanium, 0.01 at% vanadium, the rest Pig iron containing iron and additional manganese were used.
  • a high-entropy alloy was prepared in the same manner as in Example 1, having the chemical formula of Al 15 Ni 5 Cr 10 Cu 10 Fe 43 Mn 15 Si 2 .
  • a high-entropy alloy was prepared in the same manner as in Example 1 to prepare a point having a chemical formula of Al 15 Ni 5 Cr 10 Cu 10 Fe 40 Mn 13 Si 2 .
  • Al 15 Ni 5 Cr 10 Cu 10 Fe 40 Mn 20 A high entropy alloy was prepared in the same manner as in Example 1 after preparing the point having a chemical formula of Al 15 Ni 5 Cr 10 Cu 10 Fe 40 Mn 20 .
  • Al 17 Ni 3 Cr 5 Cu 15 Fe 45 Mn 15 A high-entropy alloy was prepared in the same manner as in Example 1 to prepare a point having a chemical formula of Al 17 Ni 3 Cr 5 Cu 15 Fe 45 Mn 15 .
  • a high-entropy alloy was prepared in the same manner as in Example 1, having the chemical formula of Al 13 Ni 3 Cr 6 Cu 8 Fe 55 Mn 15 .
  • a single melting process was performed in vacuum to prepare a high entropy alloy having a composition according to Table 2 and a chemical formula of Al 10 Cr 20 (CuFe) 60 Mn 10 .
  • a high-entropy alloy was prepared in the same manner as in Comparative Example 1, prepared by using pure iron and having a chemical formula of Al 15 Cr 5 (FeCuMn) 80 .
  • a high-entropy alloy was prepared in the same manner as in Comparative Example 1, prepared using pig iron and having a chemical formula of Al 15 Cr 5 (FeCuMn) 80 .
  • FIG. 3 A field emission scanning electron microscope (FE-SEM) image of the high entropy alloy according to Example 1 is shown in FIG. 3 , respectively.
  • the compositions according to Tables 1 and 2 were measured by energy dispersive spectrometry (EDS), and the content of each element was expressed in at%.
  • the content of copper in the iron-rich phase is 16.01 at%, and in the high entropy alloy according to Comparative Example 1 not containing nickel It can be seen that the content of copper in the iron-rich phase is significantly higher than 2.44 at%.
  • the content of iron in the copper-rich phase was 6.04 at%, and the iron in the copper-rich phase in the high entropy alloy according to Comparative Example 1 not containing nickel was iron. It can be seen that the content is higher than 3.56 at%.
  • the copper content in the iron-rich phase and the iron content in the copper-rich phase are respectively increased. Accordingly, it can be seen that in the high-entropy alloy according to Example 1, copper or iron is dissolved in the iron-rich phase and the copper-rich phase at a certain level or more, so that the corrosion potential difference between the iron-rich phase and the copper-rich phase can be reduced. .
  • FIG. 3 it can be seen that in the high-entropy alloy according to Example 1, an iron-rich phase and a copper-rich phase having different brightnesses are coexisted and located. At this time, it can be seen that the iron-rich phase is present as the main phase and the copper-rich phase is partially present.
  • a salt spray test was performed on the high entropy alloy according to Example 1 and Comparative Example 1.
  • 5wt% of sodium chloride brine was indirectly continuously sprayed with a nozzle pressure of 1.0 kg/cm 2 , and a pH of 6.5 to 7.2 and a temperature of 35°C were maintained.
  • Attached to Figure 4 (a) before the salt spray test of the high-entropy alloy according to Example 1, attaching a photograph when maintaining 24 hours while spraying salt water in (b), (c) A photograph of the case of maintaining 72 hours while spraying saline is attached.
  • FIG. 5 is attached with a photograph of a case in which the high-entropy alloy according to Comparative Example 1 was maintained for 24 hours while spraying salt water.
  • the high entropy alloy according to Example 1 containing nickel did not significantly corrode even when salt spray was performed for a long time.
  • the high-entropy alloy according to Comparative Example 1 which does not contain nickel was greatly corroded by salt spray and thus stained. Accordingly, it can be seen that the alloy according to Example 1 including nickel has excellent corrosion resistance.
  • the high entropy alloy according to Example 1 and the stainless steel according to Comparative Example 2 were subjected to a potentiostatic polarization test, and the results are shown in Table 3.
  • a 5 wt% sodium chloride aqueous solution was used, Ag/AgCl was used as a reference electrode, and the scan rate was 0.33 (dE/dt).
  • Example 1 Comparative Example 2 Corrosion potential [V] -0.37 -0.2 Dynamic Equilibrium Current Density [log (A/cm 2 )] -7.6 -7.6
  • the high-entropy alloy according to Example 1 has high corrosion resistance similar to that of the stainless steel according to Comparative Example 2 having high corrosion resistance.
  • a salt spray test was performed on the high entropy alloys according to Examples 2 and 3.
  • 5 wt% of sodium chloride brine was indirectly continuously sprayed with a nozzle pressure of 1.0 kg/cm 2 , and a pH of 6.5 to 7.2 and a temperature of 35 ° C were maintained.
  • Figure 6 (a) a photograph before the salt spray test of the high-entropy alloy according to Example 2 is attached, and in (b) a photograph when the salt spray is maintained for 24 hours is attached. And a photograph before the salt spray test of the high-entropy alloy according to Example 3 is attached to (a) of FIG.
  • the high entropy alloys according to Examples 1 and 4 and the stainless steel according to Comparative Example 3 were lathe-processed.
  • Lathe machining was performed under the conditions of a rotation speed of 10000 rpm, a moving speed of 5000 feed, a tool of 6 pie, REM (0.5R), depth of 0.7 mm (AP), and spacing (AE) of 70% of the tool diameter, Water-soluble cutting oil was used.
  • FIG. 8 A photograph of the plate material formed by processing the high entropy alloy according to Example 1 is attached to FIG. 8 .
  • a cleanly processed plate material can be manufactured using the alloy according to Example 1.
  • Example 1 even at a high machining speed, no tool breakage was observed. From this, it can be seen that it is possible to provide a cleanly processed plate material at a high processing speed.
  • the processing speed in the high entropy alloy according to Examples 1 and 4 is significantly higher than the processing speed of the stainless steel according to Comparative Example 3.
  • the processing speed may be twice or more than the processing speed of the stainless steel according to Comparative Example 3. It is predicted that the high-entropy alloy according to Examples 1 and 4 is because the high-strength iron-rich phase and the copper-rich phase having excellent grindability or machinability are mixed or interspersed.
  • FIG. 9 A photograph of the Oldham ring having a thickness of 1.7 mm manufactured using the high entropy alloy according to Example 1 is attached to FIG. 9 . And pictures of the results of performing the 2mm mesh channel evaluation on the high entropy alloy according to Examples 5 and 6 are attached to FIGS. A photograph of the evaluation result is attached to FIG. 11 .
  • FIGS. Photographs of the results of performing wear resistance evaluation on the entropy alloy are attached to (a), (b) and (c) of FIG. 13 , respectively. And the hardness of the high-entropy alloy or cast iron according to Examples 5 and 6 and Comparative Examples 4, 5 and 6, the fillability of the 2mm microchannel, the width of the wear track, and the entropy were measured, and the results are shown in Table 5.
  • Abrasion resistance evaluation was performed using a ball made of aluminum oxide (Al 2 O 3 ) under the conditions of a normal drag of 10N, a rotational speed of 300rpm, a rotational radius of 11.5mm, and a time of 3000 seconds.
  • the high-entropy alloy according to Examples 5 and 6 has better castability than the cast iron according to Comparative Example 4 having excellent castability in the evaluation of the 2mm mesh channel. This is expected because the high-entropy alloys according to Examples 5 and 6 have high fluidity and have large wettability due to low surface energy to stably fill fine mesh channel molds. In particular, since the copper component included in the high entropy alloy according to Examples 5 and 6 may contribute to improving wettability, Examples 5 and 6 may have excellent fluidity and excellent wettability at the same time. On the other hand, the cast iron according to Comparative Example 4 has excellent fluidity but poor wettability, so it is difficult to manufacture a structure having microchannels of 2 mm or less.
  • the high-entropy alloys according to Examples 5 and 6 have excellent hardness, excellent wear resistance, and excellent castability.
  • the high entropy alloy according to Example 5 has very excellent hardness, wear resistance, and castability characteristics.
  • the high entropy alloy according to Comparative Example 5 showed excellent hardness and wear resistance, but had low fillability and non-uniform wear.
  • the high entropy alloy according to Comparative Example 5 has a very light characteristic with a small strain, a large amount of oxidation of aluminum occurs when manufactured by atmospheric casting, so that many bubbles and cracks may occur inside the casting.
  • the cast iron according to Comparative Example 4 has relatively low fillability and does not have high entropy.
  • the high entropy alloy according to Comparative Example 6 has low fillability, low hardness, and very irregular wear.

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Abstract

Selon l'invention, un alliage à entropie élevée, selon le présent mode de réalisation, est un alliage à entropie élevée ayant une phase riche en fer et une phase riche en cuivre, et comprend un métal commun en solution totalement solide qui est totalement dissous à l'état solide dans du fer et du cuivre respectivement. Par exemple, le métal commun en solution totalement solide peut comprendre du nickel.
PCT/KR2020/006209 2020-05-12 2020-05-12 Alliage à entropie élevée et procédé de fabrication d'un tel alliage Ceased WO2021230392A1 (fr)

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CN116083775A (zh) * 2022-12-22 2023-05-09 北京科技大学 一种高强高塑的富铜高熵合金及其制备方法和应用
CN116397170A (zh) * 2023-04-27 2023-07-07 西北工业大学 一种由原子团簇和纳米析出相增强的高熵合金及其制备方法
CN117127086A (zh) * 2023-07-18 2023-11-28 武汉科技大学 CrNiFeCuTiB系高强韧性高熵合金的热处理方法、得到的材料及其应用
CN117646133A (zh) * 2023-12-13 2024-03-05 江苏科技大学 一种六元高熵非晶合金成分的设计方法

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CN116083775A (zh) * 2022-12-22 2023-05-09 北京科技大学 一种高强高塑的富铜高熵合金及其制备方法和应用
CN116397170A (zh) * 2023-04-27 2023-07-07 西北工业大学 一种由原子团簇和纳米析出相增强的高熵合金及其制备方法
CN117127086A (zh) * 2023-07-18 2023-11-28 武汉科技大学 CrNiFeCuTiB系高强韧性高熵合金的热处理方法、得到的材料及其应用
CN117646133A (zh) * 2023-12-13 2024-03-05 江苏科技大学 一种六元高熵非晶合金成分的设计方法

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