WO2019112234A1 - Alliage à base de chrome-nickel destiné à un tube radiant, possédant une excellente résistance à la déformation à température élevée et une excellente résistance à la fissuration, et procédé de fabrication s'y rapportant - Google Patents

Alliage à base de chrome-nickel destiné à un tube radiant, possédant une excellente résistance à la déformation à température élevée et une excellente résistance à la fissuration, et procédé de fabrication s'y rapportant Download PDF

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Publication number
WO2019112234A1
WO2019112234A1 PCT/KR2018/014833 KR2018014833W WO2019112234A1 WO 2019112234 A1 WO2019112234 A1 WO 2019112234A1 KR 2018014833 W KR2018014833 W KR 2018014833W WO 2019112234 A1 WO2019112234 A1 WO 2019112234A1
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Prior art keywords
yttrium
less
resistance
based alloy
content
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PCT/KR2018/014833
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English (en)
Korean (ko)
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박재현
양명모
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주식회사 포스코
재단법인 포항산업과학연구원
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Publication of WO2019112234A1 publication Critical patent/WO2019112234A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • 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

Definitions

  • the present invention relates to a Cr-Ni-based alloy for a radiator, which is excellent in high temperature deformation and crack resistance, and a method for producing the same.
  • a radiant tube is installed in an annealing furnace for heating a cold-rolled steel sheet for plating or post-processing in a steel mill, and the inside of the radiating tube is heated by a flame, The steel sheet is heated by an indirect heating method by radiant heat.
  • This radiating tube is used by welding a heat-resistant material with a straight tube portion, which is a centrifugal casting or a plate-shaped tube welded with a curved tube portion.
  • Such a radiating tube for example, when applied to the production of an electric steel sheet, has a use temperature of 1000 ° C or higher, so that creep deformation and cracking resistance at high temperatures are very important factors determining the life of the product.
  • nickel-based heat-resistant alloys such as Super22H containing 25 to 35% of Cr and 40 to 50% of Ni have been mainly used in these radiation tubes.
  • creep characteristics such as cracking during deformation for a long period of time or creep due to deformation
  • deformation at a given stress and a long time at a high temperature Resulting in shortening the service life and shortening the life span.
  • Patent Document 1 is a technique using powder having a particle size of 100 ⁇ or less as a rare earth additive material. Due to the nature of rare earths, it is difficult to alloy due to the rapid oxidation reaction upon contact with a high temperature molten metal, In addition, since the radiation tube is still used at a high temperature of 1000 ⁇ or more, it is vulnerable to deformation.
  • Patent Document 1 Korean Patent Registration No. 10-1018211
  • An aspect of the present invention is to provide a Cr-Ni-based alloy for a radiator which is excellent in high temperature deformation resistance and crack resistance and a method of manufacturing the same.
  • An embodiment of the present invention relates to a method for manufacturing a semiconductor device, which comprises 0.17 to 0.3% of carbon (C), 30 to 35% of chromium (Cr), 45 to 55% of nickel (Ni) (Si): 1% or less, the sum of one or two of niobium (Nb) and vanadium (V): 1 to 3%, tungsten (W): 5 to 18%, tantalum (Ta) , The balance Fe and other unavoidable impurities, and the average spacing between the coagulated dendrites (Dendrite), 0.1 to 1.5% of hafnium (Hf), 0.001 to 0.02% of boron (B), 0.05 to 1.5% of yttrium (Y)
  • C carbon
  • Cr chromium
  • Ni nickel
  • V vanadium
  • W tungsten
  • Ta tantalum
  • the balance Fe and other unavoidable impurities and the average spacing between the coagulated dendrites (Dendrite), 0.1
  • a method of manufacturing a semiconductor device which comprises 0.17 to 0.3% of carbon (C), 30 to 35% of chromium (Cr), 45 to 55% of nickel (Ni) (Si): 1% or less, the sum of one or two of niobium (Nb) and vanadium (V): 1 to 3%, tungsten (W): 5 to 18%, tantalum (Ta) (Fe), 0.1 to 1.5% hafnium (Hf), 0.001 to 0.02% boron (B), the balance Fe and other unavoidable impurities; Tapping the molten metal onto the ladle; And a step of obtaining a Cr-Ni-based alloy by casting the molten molten metal, wherein yttrium is continuously introduced into the molten metal so that the yttrium (Y) content of the molten metal is 0.05 to 1.5%
  • the yttrium has a massive shape with an average diameter of 5 to
  • the present inventors have found that, in addition to controlling the composition of an alloy, it is possible to appropriately add elements such as tantalum (Ta), hafnium (Hf) and boron (B)
  • elements such as tantalum (Ta), hafnium (Hf) and boron (B)
  • the inventors of the present invention have proposed that the addition of cerium (Y) can achieve an excellent high temperature deformation resistance and crack resistance by reducing the average interval between solidification dendrites.
  • the unit of the content of the alloy composition described in the present invention is% by weight.
  • Carbon (C) is an essential element that affects the strength improvement. If the content is less than 0.17%, the effect of improving the strength is insignificant. On the other hand, when the content exceeds 0.3%, the strength increases sufficiently, but the elongation rate is lowered and the possibility of cracks is increased, and weldability is poor when welding the centrifugal tube and the sand mold product, which is not preferable. Therefore, it is preferable that the content of C is in the range of 0.17 to 0.3%.
  • the lower limit of the C content is more preferably 0.20%, and still more preferably 0.22%.
  • the upper limit of the C content is more preferably 0.25%, and still more preferably 0.24%.
  • Chromium (Cr) is an element added to improve high-temperature strength and corrosion resistance by carbide formation. When the Cr content is less than 30%, the effect of addition is insignificant. When the Cr content exceeds 35%, Cr is an element which promotes ferrite, which is undesirable because it inhibits the formation of austenite phase which is the phase to be obtained in the present invention. Therefore, the content of Cr is preferably in the range of 30 to 35%.
  • the lower limit of the Cr content is more preferably 32%, and still more preferably 32.5%.
  • the upper limit of the Cr content is more preferably 34%, and still more preferably 33.5%.
  • Nickel (Ni) is an element added for the formation of an austenite phase and the improvement of high temperature strength.
  • the content of Ni is in the range of 45 to 55%.
  • the lower limit of the Ni content is more preferably 48%, and still more preferably 49%.
  • the upper limit of the Ni content is more preferably 53%, and still more preferably 51%.
  • Manganese (Mn) is an element added for strength improvement. However, when the Mn is more than 1%, the strength is increased but the elongation is reduced and the possibility of cracking during use is great. Therefore, it is preferable that the content of Mn is 1% or less. The Mn content is more preferably 0.95% or less, and still more preferably 0.9% or less.
  • Silicon (Si) is an element added for fluidity at the time of implantation. However, when the content of Si is more than 1%, it is preferable that Si is added in an amount of 1% or less because the fluidity is increased but it may affect deposition of carbide. Therefore, it is preferable that the content of Si is 1% or less.
  • the Si content is more preferably 0.9% or less, and still more preferably 0.8% or less.
  • Niobium (Nb) and vanadium (V) combine with carbon (C) or nitrogen (N) to form carbides or nitrides. These carbides or nitrides contribute to improvement in tensile strength, yield strength and high temperature strength. Therefore, it is necessary to add one or two of these elements. If the addition amount is less than 1%, the effect of improving the strength by precipitation strengthening and particle refinement is insignificant. On the other hand, if the addition amount exceeds 3%, the above-mentioned effect becomes saturated and the elongation rate can be rather reduced. Therefore, it is preferable that the content of the sum of one or two of Nb and V ranges from 1 to 3%. The lower limit of the total content of one or both of Nb and V is more preferably 1.5%, and still more preferably 1.8%. The upper limit of the total content of one or both of Nb and V is more preferably 2.5%, and still more preferably 2.2%.
  • Tungsten (W) together with Nb or V, contributes to improvement of high-temperature strength.
  • the content is less than 5%, the effect of improving tensile strength at high temperature is insignificant.
  • the content exceeds 18%, the strength improvement by W is sufficient, but the elongation rate is lowered to increase the risk of cracking, and weldability at the time of welding is also poor. Therefore, it is preferable that the content of W is in the range of 5 to 18%.
  • the lower limit of the W content is more preferably 7%, and even more preferably 10%.
  • the upper limit of the W content is more preferably 17%, and still more preferably 16%.
  • Tantalum (Ta) 0.1 to 1.5%
  • Tantalum is added for refinement of precipitate particles such as dendrites and carbides. For this purpose, it is necessary to add it at 0.1% or more. However, if the content exceeds 1.5%, the elongation becomes low and it becomes weak and the cost increases. Therefore, the content of Ta is preferably in the range of 0.1 to 1.5%.
  • the lower limit of the Ta content is more preferably 0.2%, and still more preferably 0.4%.
  • the upper limit of the Ta content is more preferably 1.3%, and still more preferably 1.0%.
  • Hafnium (Hf) is added to refine the precipitate particles, such as dendrites and carbides, similar to tantalum. For this purpose, it is necessary to add it at 0.1% or more. However, if the content exceeds 1.5%, the elongation becomes low and it becomes weak and the cost increases. Therefore, the Hf content is preferably in the range of 0.1 to 1.5%.
  • the lower limit of the Hf content is more preferably 0.2%, and still more preferably 0.4%.
  • the upper limit of the Hf content is more preferably 1.3%, and still more preferably 1.0%.
  • Boron (B) is also added for refinement of precipitated particles such as dendrites and carbides. For this purpose, it is necessary to add it at a content of 0.001% or more, but if the content exceeds 0.02%, the elongation rate is excessively decreased. Therefore, it is preferable that the content of B is in the range of 0.001 to 0.02%.
  • the lower limit of the B content is more preferably 0.005%, and still more preferably 0.01%.
  • Yttrium (Y) 0.05 to 1.5%
  • Yttrium is an element that improves the strength and particle size of the steel without deteriorating the elongation due to the refinement effect of the metal crystal grains.
  • the Y content is less than 0.05%, it is difficult to obtain the effect of the Y addition as described above, On the other hand, if the content exceeds 1.5%, the elongation and strength are lowered, and the cost is very disadvantageous. Therefore, it is preferable that the content of Y is in the range of 0.05 to 1.5%.
  • the lower limit of the Y content is more preferably 0.08%, and still more preferably 0.1%.
  • the upper limit of the Y content is more preferably 1.2%, and still more preferably 1.0%.
  • the remainder of the Cr-Ni alloy of the present invention is Fe, and may contain impurities inevitably contained in the manufacturing process.
  • the Cr-Ni-based alloy provided by the present invention has an average distance between coagulated dendrites appearing in the cast structure of 30 ⁇ or less.
  • product deformation at elevated temperatures for example at temperatures above 1000 ° C, is a major mechanism of creep deformation, and subsequent creep deformation occurs along the boundary between the resin phase and the carbide.
  • the average interval between the solidified dendrites to 30 ⁇ m or less, that is, by forming a large number of solidified dendrite branches formed during cooling, the size of the crystal grains is reduced, The deformation can be reduced and the fracture caused by the cracks can be reduced.
  • the average distance between the solidified dendrites in the cast structure is preferably 30 ⁇ or less.
  • the average interval between the solidified resin phases is more preferably 25 ⁇ ⁇ or less, and still more preferably 20 ⁇ ⁇ or less.
  • the Cr-Ni-based alloy provided by the present invention preferably has a single-phase austenite structure in terms of metallurgy, thereby improving the high-temperature corrosion resistance.
  • the Cr-Ni alloy of the present invention provided as described above has excellent high temperature deformation resistance and crack resistance, and can secure sufficient strength and ductility.
  • the molten metal is spouted onto the ladle. It is preferable to continuously inject yttrium into the molten metal to be spouted so that the yttrium (Y) content of the molten metal becomes 0.05 to 1.5% at the time of tapping the molten metal. This makes it possible to uniformly mix the yttrium in the molten metal and to realize the effect of decreasing the average interval between the solidified dendrites. However, there is a problem that it is difficult to uniformly mix iridium locally only in the upper, middle, or lower portion of the ladle.
  • the charged yttrium has a massive form having an average diameter of 5 to 10 mm.
  • the average diameter of the massive yttrium is less than 5 mm, it is difficult to obtain the above effect sufficiently as the amount of yttrium contributing to the decrease in the average interval between the dendrites is reduced due to the rapid oxidation reaction in the molten metal.
  • the average distance between the solidifying dendrites exceeds 10 mm, unreacted or unmelted yttrium may be generated.
  • the average diameter of the yttrium added is preferably 5 to 10 mm.
  • the lower limit of the yttrium average diameter is more preferably 6 mm, and still more preferably 6.5 mm.
  • the upper limit of the yttrium average diameter is more preferably 9 mm, and still more preferably 7.5 mm.
  • the massive yttrium may be introduced through a heat-resistant tube having a diameter of 15 mm or more.
  • the molten metal is cast to obtain a Cr-Ni alloy.
  • the casting is performed by a centrifugal casting method using a mold mold.
  • the centrifugal casting process can cool the molten metal more rapidly than the conventional casting process, thereby narrowing the average spacing between the solidified dendrites.
  • the molten metal was melted in an induction furnace to have an alloy composition as shown in Table 1 below, and the molten metal was spouted on the ladle. Thereafter, the molten metal was cast through a centrifugal casting process using a mold mold to obtain a Cr-Ni alloy .
  • the components other than yttrium were first dissolved through an induction furnace, and then yttrium having a mass of about 7 mm in average diameter was continuously introduced into molten steel leached with ladle.
  • the average interval between the dendrites was measured by observing the microstructure of the thus prepared Cr-Ni alloy, and the creep rupture test was performed at 1000 ° C according to the ASTM E 139 test method to measure the product life , And the results are shown in Table 1 below.
  • the product lifetime was evaluated as "x" when the product was broken in less than 100 hours, " ⁇ " when the product was broken in 100 to 500 hours, and " ⁇ " when the product was broken in 500 hours or more.
  • the inventive examples 1 to 6 having an average spacing of the coagulated dendrites of 30 ⁇ or less were excellent in the fracture life compared with the conventional examples.
  • Comparative Examples 1, 3 and 5 satisfied the condition that the average interval between the solidified resin phases was 30 ⁇ or less, but the life span was not good due to the content of Ta, Hf and B exceeding the condition of the present invention, 2, 4 and 6 show that the contents of Ta, Hf and B are below the conditions of the present invention and the life span is low.
  • Comparative Examples 7 and 8 are cases where the content of Y is small or excessive
  • Comparative Examples 9 and 10 are cases where the sum of Nb and V is small or excessive
  • Comparative Examples 11 and 12 are cases where the content of W is small or excessive
  • Comparative Example 13 is a case where the content of C does not satisfy the range suggested by the present invention, and it has a low level of life.
  • the molten steel was melted in an induction furnace to have a molten metal so as to have the alloy composition of Inventive Example 1 of Example 1, and then the molten metal was spouted on the ladle. Then, the molten metal was cast by a centrifugal casting method using a mold mold, Ni-based alloy. At this time, the charging method and the average diameter of yttrium were the same as those shown in Table 2 below. The average interval between the dendrites of the Cr-Ni alloy thus manufactured was measured through microstructure observation, and the creep rupture test was conducted according to the ASTM E 139 test method to measure the product life, Are shown in Table 1 below. At this time, the product lifetime was evaluated on the same basis as in Example 1.
  • Comparative Example 16 shown in Table 2 below, yttrium was added to the ladle before the molten metal was poured.
  • Comparative Example 17 yttrium was added to the ladle in the middle of pouring the molten metal. And yttrium is added to the ladle after finishing the lecture.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

La présente invention concerne un alliage à base de Cr-Ni destiné à un tube radiant, possédant une excellente résistance à la déformation à température élevée et à la fissuration, et un procédé de fabrication s'y rapportant. Selon un mode de réalisation, la présente invention concerne : un alliage à base de Cr-Ni destiné à un tube radiant, possédant une excellente résistance à la déformation à température élevée et une excellente résistance à la fissuration, l'alliage à base de Cr-Ni comprenant, en % en poids, 0,17 à 0,3 % de carbone (C), 30 à 35 % de chrome (Cr), 45 à 55 % de nickel (Ni), 1 % ou moins de manganèse (Mn), 1 % ou moins de silicium (Si), 1 à 3 % d'un élément parmi le niobium (Nb) et le vanadium (V) ou la somme des deux, 5 à 18 % de tungstène (W), 0,1 à 1,5 % de tantale (Ta), 0,1 à 1,5 % d'hafnium (Hf), 0,001 à 0,02 % de bore (B), 0,05 à 1,5 % d'yttrium (Y), et le reste de Fe et d'autres impuretés inévitables, et possédant un intervalle moyen entre des dendrites solidifiées de 30 µm ou moins ; et un procédé de fabrication s'y rapportant.
PCT/KR2018/014833 2017-12-07 2018-11-28 Alliage à base de chrome-nickel destiné à un tube radiant, possédant une excellente résistance à la déformation à température élevée et une excellente résistance à la fissuration, et procédé de fabrication s'y rapportant WO2019112234A1 (fr)

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KR1020170167229A KR101998979B1 (ko) 2017-12-07 2017-12-07 고온변형 저항성 및 균열 저항성이 우수한 복사관용 Ｃｒ-Ｎｉ계 합금 및 그 제조방법
KR10-2017-0167229 2017-12-07

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN113584350A (zh) * 2021-07-30 2021-11-02 湖北精利机电科技有限公司 一种抗高温氧化的铸造高钨镍基合金及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113584350A (zh) * 2021-07-30 2021-11-02 湖北精利机电科技有限公司 一种抗高温氧化的铸造高钨镍基合金及其制备方法

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