Ni-based alloy powder for additive manufacturing and method for manufacturing ni-based alloy molding

Abstract

A molding in which cracking does not occur can be obtained by this method for powder melt additive manufacturing using a Ni-based alloy powder for additive manufacturing comprising, in terms of mass%, 6-12% Cr, 1-4% Mo, 4-8% Al, 6-11% Co, 7-12% W, 1-5% Ta, 1.5-7% Fe, 0.1-0.25% C, no more than 0.5% Ti, no more than 0.2% Zr, no more than 0.1% B, no more than 0.5% Nb, and no more than 0.5% Hf, the remainder being Ni and unavoidable impurities.

Description

Ni-based alloy powder for additive manufacturing and method for manufacturing Ni-based alloy shaped objects

[0001] The present invention relates to Ni-based alloy powders for additive manufacturing and methods for producing Ni-based alloy shaped articles.

[0002] Additively manufactured parts used at high temperatures, such as aircraft gas turbines and turbines for automotive turbochargers, require Ni (nickel)-based alloys with excellent heat resistance and high-temperature oxidation resistance.

[0003] For example, Patent Document 1 discloses a composition of such a Ni-based alloy, containing Ni as the main component and the following amounts by mass: Fe (iron): 2 to 8, Al (aluminum): 6.1 to 6.8, Cr (chromium): 12.5 to 15, W (tungsten): 1.5 to 4.5, Ta (tantalum): 2.5 to 5.5, Hf (hafnium): 1.2 to 2, C (carbon): 0.03 to 0.13, B (boron): 0.005 to 0.02, Zr (zirconium): 0.005 to 0.02, and Si (silicon): 0.005 to 0.02. The invention described in Patent Document 1 is said to provide a nickel-based alloy with excellent thermal and mechanical strength, oxidation resistance, and workability.

[0004] Special Publication No. 2021-504564

[0005] The alloy disclosed in the aforementioned Patent Document 1 is intended to produce additively manufactured products with excellent high-temperature strength and oxidation resistance. However, the Ni-based alloy composition disclosed in Patent Document 1 has a problem of proneness to solidification cracking, which is not taken into consideration. The occurrence of cracking leads to a decrease in high-temperature strength, creep properties, and oxidation resistance.

[0006] Therefore, the present invention aims to provide a method for manufacturing a Ni-based alloy shaped object that can suppress the occurrence of cracks during melting and solidification, and a Ni-based alloy powder for additive manufacturing that can be used to manufacture the Ni-based alloy shaped object.

[0007] The first invention is a Ni-based alloy powder for additive manufacturing containing, as additive elements, at least, in mass %, Cr: 6% to 12%, Mo: 1% to 4%, Al: 4% to 8%, Co (cobalt): 6% to 11%, W: 7% to 12%, Ta: 1% to 5%, Fe: 1.5% to 7%, and C: 0.1% to 0.25%, with the remainder being Ni and unavoidable impurities.

[0008] Furthermore, the Ni-based alloy powder for additive manufacturing preferably contains, as an additive element, B: more than 0% and 0.1% or less.

[0009] In addition, the Ni-based alloy powder for additive manufacturing preferably contains at least one of Nb (niobium): more than 0% and 0.5% or less, and Hf: more than 0% and 0.5% or less as an additive element.

[0010] Furthermore, the Ni-based alloy powder for additive manufacturing preferably contains, as additive elements, Ti (titanium): more than 0% and 0.5% or less, and Zr: more than 0% and 0.2% or less.

[0011] The B content is preferably 0.005% or more and 0.05% or less.

[0012] The Zr content is preferably 0.02% or more and 0.15% or less.

[0013] The second invention is a method for producing a Ni-based alloy shaped product, which comprises supplying a Ni-based alloy powder for additive manufacturing containing, in mass %, at least 6% to 12% Cr, 1% to 4% Mo, 4% to 8% Al, 6% to 11% Co, 7% to 12% W, 1% to 5% Ta, 1.5% to 7% Fe, and 0.1% to 0.25% C as additive elements, with the balance being Ni and unavoidable impurities; selectively irradiating the supplied Ni-based alloy powder with laser light to melt and solidify it; and performing a powder fusion additive manufacturing method to obtain a Ni-based alloy shaped product, in which the steps of supplying the Ni-based alloy powder and melting and solidifying it are repeated.

[0014] Furthermore, the Ni-based alloy powder for additive manufacturing preferably contains, as an additive element, B: more than 0% and 0.1% or less.

[0015] In addition, the Ni-based alloy powder for additive manufacturing preferably contains at least one of Nb (niobium): more than 0% and 0.5% or less, and Hf: more than 0% and 0.5% or less as an additive element.

[0016] Furthermore, the Ni-based alloy powder for additive manufacturing preferably contains, as additive elements, Ti (titanium): more than 0% and 0.5% or less, and Zr: more than 0% and 0.2% or less.

[0017] Furthermore, it is preferable that the boundary width of the primary dendrite structure in the cross-sectional structure of the Ni-based alloy shaped article is 0.4 μm or less.

[0018] It is also preferable to have a heat treatment step of subjecting the Ni-based alloy shaped article to a heat treatment after the additive manufacturing step.

[0019] The heat treatment step preferably includes a solution heat treatment and an aging heat treatment.

[0020] In addition, it is preferable that the area ratio of carbides in the cross-sectional structure of the Ni-based alloy shaped article is 5% or more and 12% or less.

[0021] According to the present invention, it is possible to provide a method for manufacturing a Ni-based alloy shaped object that can suppress the occurrence of cracks during melting and solidification, and a Ni-based alloy powder for additive manufacturing that can be used to manufacture a Ni-based alloy shaped object.

[0022] FIG. 1 is a cross-sectional photograph of a shaped object showing an example of a crack; FIG. 2 is a schematic diagram of powder bed fusion; FIG. 3 is a cross-sectional photograph of a primary dendrite of a shaped object in which no cracks occurred; FIG. 4 is a cross-sectional photograph of a secondary dendrite that occurred near a crack; FIG. 5 is an STEM image of Example 2 after additive manufacturing; FIG. 6 is a cross-sectional photograph of the shaped object of Example 2 after a heat treatment process; FIG. 7 is a photograph of gamma-prime precipitates in Example 1 after a heat treatment process; FIG. 8 is a photograph of gamma-prime precipitates in Example 3 after a heat treatment process.

[0023] An embodiment of the present invention will be described below. Powder fusion additive manufacturing (hereinafter simply referred to as additive manufacturing) is an additive manufacturing method in which heat source energy, such as a laser or electron beam, is supplied only to a very small, limited area of ​​a metal powder. The heat source energy is then transferred at high speed to melt and solidify the metal powder, instantly melting the fine metal powder and then solidifying it by heat dissipation. It is known that the solidification rate of the molten metal powder is extremely fast. Therefore, when some Ni-based alloy compositions are used for molding, cracks occur during solidification in additive manufacturing. A cross-sectional photograph of a molded object showing an example of cracking is shown in Figure 1. It can be seen that a long, thin crack 20 has occurred in the molding direction. The mechanism behind this is that during solidification, phase transformation occurs. At high temperatures, the entire material is in a liquid phase, and as the temperature decreases, the liquid and solid phases coexist, and as the temperature decreases further, only the solid phase remains. However, in additive manufacturing, the cooling rate is extremely fast, so low-melting-point segregation occurs at the grain boundaries, and shrinkage during cooling causes cracks at the grain boundaries. Therefore, as shown in Figure 1, cracks progress in the layering direction, which is the direction of cooling. Based on the above, the following describes an embodiment of the present invention, in which a new composition of a Ni-based alloy that does not crack when manufactured using additive manufacturing methods, and a method for manufacturing a molded object using additive manufacturing methods using a powder material made of that composition.

[0024] An embodiment of the present invention will be described below. First, a Ni-based alloy powder for additive manufacturing (hereinafter simply referred to as Ni-based alloy powder) will be described. Next, a Ni-based alloy shaped object produced by additive manufacturing using this Ni-based alloy powder and a method for producing the same will be described. However, the present invention is not limited to the embodiment described here, and appropriate combinations and improvements can be made without departing from the technical concept of the invention.

[0025] [Ni-Based Alloy Powder] The Ni-based alloy powder according to a first embodiment of the present invention is characterized by containing, by mass%, Cr: 6% to 12%, Mo: 1% to 4%, Al: 4% to 8%, Co: 6% to 11%, W: 7% to 12%, Ta: 1% to 5%, Fe: 1.5% to 7%, C: 0.1% to 0.25%, and the balance being Ni and unavoidable impurities. Hereinafter, Cr, Mo, Al, Co, W, Ta, Fe, and C are referred to as essential additive elements. It is also preferable to add one or more of B: 0% to 0.1%, Nb: 0% to 0.5%, Hf: 0% to 0.5%, Ti: 0% to 0.5%, and Zr: 0% to 0.2%. Hereinafter, B, Nb, Hf, Ti, and Zr are referred to as optional additive elements. This Ni-based alloy powder is used for additive manufacturing, which will be described later.

[0026] <Alloy Composition> The reasons for limiting each compositional component in the Ni-based alloy powder of this embodiment will be explained below. First, the essential additive elements will be explained, followed by the optional additive elements. In the following explanation, % indicates mass %. Furthermore, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limit values. Furthermore, the upper limit value and the lower limit value can be combined arbitrarily.

[0027] (Essential Added Elements) (Cr: 6% or More and 12% or Less) Cr is effective in improving oxidation resistance and is an important main component for obtaining good oxidation resistance at high temperatures. 6% or more is necessary to improve oxidation resistance through the Cr oxide film. On the other hand, if more than 12% is added, the amount of other alloy elements added must be reduced, resulting in a decrease in high-temperature strength and high-temperature creep properties. 7 to 11% is preferable. 8 to 9% is more preferable.

[0028] (Mo: 1% or more and 4% or less) Mo needs to be 1% or more to improve high-temperature strength and high-temperature creep properties through solid solution strengthening (the interaction between solid solution in crystals and dislocations prevents dislocation movement, resulting in strengthening mainly in improved tensile strength), and to improve oxidation resistance. On the other hand, if added in excess, it is necessary to reduce the amounts of other alloy elements added, so the content is set to 4% or less. Preferably, it is 1.5 to 3.5% or less. More preferably, it is 2 to 3%.

[0029] (Al: 4% or more and 8% or less) Al combines with Ni after the aging heat treatment described below to form gamma-prime precipitates. The formation of gamma-prime precipitates improves high-temperature strength and high-temperature creep properties. For this reason, 4% or more is necessary. Excessive addition of Al increases the NiAl ２ The content is set to 8% or less because brittle compounds such as Cr are formed. The content is preferably 5 to 7%, and more preferably 5.5 to 6.5%.

[0030] (Co: 6% or more and 11% or less) Co is required to be 6% or more to improve high-temperature strength and high-temperature creep properties through solid solution strengthening. If added excessively, it will be difficult to increase the amount of other added elements, so the content is set to 11% or less. The preferred range is 7 to 10%, and the more preferred range is 8 to 9%.

[0031] (W: 7% or more and 12% or less) W needs to be 7% or more to improve high-temperature strength and high-temperature creep properties through solid solution strengthening and carbide formation. If added in excess, it becomes difficult to increase the amount of other added elements and an embrittlement phase is formed, so the W content is set to 12% or less. The preferred range is 8 to 11%, and the more preferred range is 7 to 10%.

[0032] (Ta: 1% or more and 5% or less) Ta combines with Ni after the aging heat treatment described below to form gamma-prime precipitates. The formation of gamma-prime precipitates improves high-temperature strength and high-temperature creep properties. For this reason, 1% or more is required. If added in excess, it becomes difficult to increase the amount of other added elements, so the content is set to 5% or less. Preferably, it is 1.2 to 4%. More preferably, it is 1.3 to 3%.

[0033] (Fe: 1.5% or more and 7% or less) Addition of Fe is effective in preventing cracking. Because Fe reduces high-temperature strength and high-temperature creep properties, it is not generally added to Ni-based alloys, which have excellent high-temperature properties. However, in the present invention, it has been revealed that Fe is effective in preventing cracking. Furthermore, it has been revealed that a small amount of Fe reduces high-temperature properties only slightly. Therefore, 1.5% or more is necessary to prevent cracking. However, excessive addition significantly reduces high-temperature strength and high-temperature creep properties, so it must be 7% or less. Preferably, it is 2 to 6%. More preferably, it is 2.5 to 5.0%.

[0034] (C: 0.1% or more and 0.25% or less) In Ni-based alloys, the greater the amount of C added, the more effective it is in preventing cracking. Furthermore, it has been revealed that forming carbides at grain boundaries can improve high-temperature creep properties, and forming carbides within grains is also effective in improving high-temperature strength. The carbides formed at grain boundaries and within grains are all composite carbides of W, Mo, and Ta. The amount of C added is set to 0.1% or more to contribute to preventing cracking and improving high-temperature strength and high-temperature creep properties. However, excessive addition of C increases the amount of carbides too much, resulting in a decrease in toughness and a decrease in high-temperature fatigue strength, so it is set to 0.25% or less. The preferred range is 0.12 to 0.22%, and the more preferred range is 0.15 to 0.2%.

[0035] (Optional Added Elements) (B: ​​More than 0% but 0.1% or Less) B forms compounds with Cr and Mo at grain boundaries, suppressing grain boundary sliding and improving high-temperature creep properties. However, excessive B addition can actually degrade high-temperature creep properties, so even if added, it must be added in small amounts. Therefore, B is an optional added element, and if added, it is set to more than 0% but 0.1% or less. Preferably, it is 0.005 to 0.05%. Adding 0.005% or more precipitates B compounds uniformly and throughout the grain boundaries, improving high-temperature creep properties. Adding 0.05% or less prevents degradation of high-temperature creep properties due to excessive addition, even if uneven B concentration occurs. More preferably, it is 0.01 to 0.04%. Since B is unlikely to increase the likelihood of cracking even when added, it is recommended that it be added preferentially among optional added elements.

[0036] (Nb: more than 0% and not more than 0.5%) Nb is an element that improves high-temperature strength and high-temperature creep properties through solid solution strengthening. However, the addition of Nb makes cracks more likely to occur, so even if added, it must be small. Therefore, Nb is an optional element, and if added, it is set to more than 0% and not more than 0.5%. Preferably, it is 0.05% or more and not more than 0.2%.

[0037] (Hf: more than 0% and not more than 0.5%) Hf is an element that improves high-temperature creep properties by segregating at grain boundaries when molten metal powder solidifies. However, the addition of Hf makes cracks more likely to occur, so even if added, it must be small. Therefore, Hf is an optional element, and if added, it is set to more than 0% and not more than 0.5%. Preferably, it is 0.05% or more and not more than 0.2%.

[0038] (Zr: More than 0% and 0.2% or less) Zr is an element that improves high-temperature creep properties by forming carbides at grain boundaries and suppressing grain boundary sliding after the aging heat treatment described below. However, adding excessive Zr can actually reduce creep properties and make cracks more likely to occur, so even if Zr is added, it must be added in small amounts. Therefore, Zr is an optional element, and if added, it is set to more than 0% and 0.2% or less. Preferably, it is 0.02 to 0.15%. Adding 0.02% or more disperses and precipitates Zr carbides uniformly and throughout the grain boundaries, improving high-temperature creep properties, while adding 0.15% or less prevents cracking even when complex shapes are formed. More preferably, it is 0.05 to 0.13%.

[0039] (Ti: more than 0% but not more than 0.5%) Ti is an element that forms gamma-prime precipitates, which are compounds with Ni, after the aging heat treatment described below, improving high-temperature strength and high-temperature creep properties. However, the addition of Ti makes cracks more likely to occur, so even if Ti is added, it must be kept to a small amount. Therefore, Ti is an optional element, and if added, its content is set to more than 0% but not more than 0.5%. Preferably, it is 0.05% or more but not more than 0.2%. More preferably, it is 0.05% or more but not more than 0.1%.

[0040] Among the optional elements, B is an optional element, but its addition does not promote cracking, and a small amount can improve creep properties. Nb and Hf are also optional elements, but a small amount prevents cracking and can improve creep properties. Similarly, a small amount of Zr and Ti does not cause cracking, and can improve creep properties by aging heat treatment.

[0041] (Inevitable impurities) Furthermore, the balance includes unavoidable impurities. Inevitable impurities refer to trace amounts of impurities that are difficult to remove technically due to factors such as trace elements mixed into the raw materials or reactions with various components that come into contact during the manufacturing process. Of these impurities, impurities that should be particularly limited include P, S, O, and N. P is preferably 0.01% or less, S is preferably 0.01% or less, O is preferably 0.1% or less, and N is preferably 0.1% or less. Of course, the content of these unavoidable impurities is preferably low, and even better if it is 0%.

[0042] Furthermore, the balance may further contain trace elements such as Mn and Si, which have a deoxidizing effect. The content of each of these trace elements is preferably 1.0% or less, and more preferably 0.5% or less. The composition of the alloy powder can be analyzed, for example, using inductively coupled plasma (ICP) optical emission spectrometry.

[0043] <Particle Size Distribution of Ni-Based Alloy Powder> Regarding the particle size distribution of the Ni-based alloy powder of this embodiment, if the particle size is too small, the fluidity will be poor, and conversely, if the particle size is too large, the precision of the molded product will be poor and the defect rate will be high. Therefore, in the cumulative distribution curve showing the relationship between the particle size determined by laser diffraction and the volume cumulative from each particle size, the particle size D50 (average particle size) corresponding to a cumulative frequency of 50% is preferably 10 μm or more and 100 μm or less. More preferably, it is 20 μm or more and 50 μm or less. Such Ni-based alloy powder can be produced by gas atomization, water atomization, disk atomization, etc., but gas atomization is preferred because it is easy to obtain spherical powder and has low production costs.

[0044] [Method for manufacturing additive manufactured product] A method for manufacturing a Ni-based alloy shaped product according to a second embodiment of the present invention is characterized in that a Ni-based alloy powder for additive manufacturing is supplied, the Ni-based alloy powder containing, in mass %, at least 6% to 12% Cr, 1% to 4% Mo, 4% to 8% Al, 6% to 11% Co, 7% to 12% W, 1% to 5% Ta, 1.5% to 7% Fe, and 0.1% to 0.25% C as additive elements, with the balance being Ni and unavoidable impurities; the supplied Ni-based alloy powder is selectively irradiated with heat source energy to partially melt and solidify the Ni-based alloy powder; and the supply and melting and solidifying steps are repeated to obtain a Ni-based alloy shaped product by powder fusion additive manufacturing. The Ni-based alloy powder for additive manufacturing preferably contains one or more of B: more than 0.1% to 0.5%, Nb: more than 0% to 0.5%, Hf: more than 0% to 0.5%, Ti: more than 0% to 0.5%, and Zr: more than 0% to 0.2%. Laser light is preferably used as the heat source energy.

[0045] An embodiment of a method for manufacturing a Ni-based alloy shaped product using the Ni-based alloy powder described above will be described. The method for manufacturing a Ni-based alloy shaped product according to this embodiment is an additive manufacturing method that includes supplying the Ni-based alloy powder described above, selectively irradiating the supplied Ni-based alloy powder with a laser beam to partially melt and solidify the powder, and repeating the steps of supplying and melting and solidifying the Ni-based alloy powder. Additive manufacturing methods that use metal powder as a raw material can generally be broadly divided into powder bed fusion (PBF) and directed energy deposition (DED). Either method can be applied to the method for manufacturing a Ni-based alloy shaped product according to this embodiment.

[0046] Figure 2 shows a schematic diagram of powder bed fusion as an example of this embodiment. Powder 1 in a powder supply container 9 is pushed up by raising the powder supply stage 2, and is supplied onto a modeling box 10 by moving a recoater 3 in the X direction. Any remaining powder 1 is collected in a powder recovery box 11. Next, the laser beam 5 emitted from a laser oscillator 4 is irradiated at a predetermined irradiation area 7, and the irradiation position is controlled (scanned) by a galvano scanner 6, thereby melting and solidifying the powder 1. Next, the modeling stage 8 is lowered. This process is repeated to produce a three-dimensional model.

[0047] By subjecting the Ni-based alloy shaped article thus produced immediately after additive manufacturing to a heat treatment process consisting of a solution heat treatment and an aging heat treatment, the high-temperature strength can be further improved.

[0048] Solution heat treatment is typically performed to homogenize the composition, and also to eliminate the boundaries 23 of the primary dendrite structure that solidification segregation occurs in the Ni-based alloy shaped product of this embodiment. If the solution heat treatment temperature is too low, the diffusion rate is slow and the boundaries 23 of the primary dendrites do not disappear, while if the temperature is too high, the Ni-based alloy shaped product melts. Therefore, the heat treatment temperature is preferably 1160°C or higher and 1300°C or lower. Furthermore, if the solution heat treatment time is too short, the boundaries 23 of the primary dendrites do not disappear, while if it is too long, the crystal grains become coarse and the high-temperature strength decreases. Therefore, the heat treatment time is preferably 1 hour or higher and 20 hours or lower. The solution heat treatment in this embodiment can be summarized as a process in which the Ni-based alloy shaped product after additive manufacturing is held in a furnace set at a heat treatment temperature of 1160°C or higher and 1300°C or lower for a heat treatment time of 1 hour or higher and 20 hours or lower, and then removed from the furnace and rapidly cooled. In this case, it is preferable to use a vacuum or nitrogen atmosphere during the solution heat treatment and rapid cooling, as this can prevent oxidation of the Ni-based alloy shaped article.

[0049] In addition, aging heat treatment is performed on Ni, which is called γ'. ３ Al or Ni ３The aging heat treatment is performed after the solution heat treatment to precipitate fine gamma-prime precipitates of Ta. As described above, the intragranular precipitation of gamma-prime precipitates by the aging heat treatment can improve high-temperature strength. If the aging heat treatment temperature is too low and the time is too short, the aging heat treatment is insufficient and the high-temperature strength is not improved. On the other hand, if the aging heat treatment temperature is too high and the time is too long, over-aging occurs, resulting in coarsening of the gamma-prime precipitates and a decrease in high-temperature strength. Therefore, the aging heat treatment temperature is preferably 840°C or higher and 1100°C or lower, and the heat treatment time is preferably 5 hours or higher and 30 hours or lower. The aging heat treatment in this embodiment can be summarized as a process of holding the Ni-based alloy shaped product after the solution heat treatment in a furnace set at a heat treatment temperature of 840°C or higher and 1100°C or lower for a heat treatment time of 5 hours or higher and 30 hours or lower, and then removing it from the furnace and cooling it. In this case, it is preferable to use a vacuum or nitrogen atmosphere during the solution heat treatment and rapid cooling, as this can prevent oxidation of the Ni-based alloy shaped article.

[0050] [Ni-based alloy shaped product] The Ni-based alloy shaped product obtained by the above-described method for manufacturing a Ni-based alloy shaped product contains, by mass%, at least the following additive elements: Cr: 6% to 12%, Mo: 1% to 4%, Al: 4% to 8%, Co: 6% to 11%, W: 7% to 12%, Ta: 1% to 5%, Fe: 1.5% to 7%, and C: 0.1% to 0.25%, with the balance being Ni and unavoidable impurities. Furthermore, the Ni-based alloy powder for additive manufacturing preferably contains one or more of B: 0% to 0.1%, Nb: 0% to 0.5%, Hf: 0% to 0.5%, Ti: 0% to 0.5%, and Zr: 0% to 0.2%. The chemical composition and content of the Ni-based alloy shaped product are the same as those of the Ni-based alloy powder, and therefore will not be described here.

[0051] <Structure of Ni-based alloy shaped product after additive manufacturing> The Ni-based alloy shaped product of this embodiment has a dendritic structure as shown in FIG. 3 . In this case, the boundary width between the primary dendritic structures 21 is preferably 0.4 μm or less. As described above, in shaped products manufactured by conventional additive manufacturing methods using Ni-based alloy powder, solidification segregation occurs at grain boundaries during rapid solidification in the additive manufacturing process, resulting in tensile stress and cracking. Cracking is particularly prevalent in Ni-based alloy shaped products having an alloy composition that forms gamma-prime precipitates. By appropriately selecting the composition of the Ni-based alloy powder used as the raw material as described above, the Ni-based alloy shaped product of this embodiment can narrow the boundary width 23 between the primary dendritic structures 21 and prevent cracking. More preferably, the Ni-based alloy shaped product does not have a secondary dendritic structure. This reduces segregation at the grain boundaries (boundaries 23), thereby preventing cracking of the shaped product.

[0052] <Structure of Ni-Based Alloy Shaped Product After Heat Treatment> The Ni-based alloy shaped product of this embodiment may be subjected to the heat treatment process consisting of the solution heat treatment and aging heat treatment described above. In the structure of the Ni-based alloy shaped product subjected to the solution heat treatment, the primary dendrite structure 21 disappears, resulting in a structure of crystal grains 30 and carbides 32, as shown in FIG. 6 . At this time, carbides are preferably formed inside the crystal grains 30 and at the grain boundaries of the crystal grains 30. The carbides 31 formed inside the crystal grains 30 improve high-temperature strength by preventing dislocation migration (precipitation strengthening). Furthermore, the carbides 32 formed at the grain boundaries 24 suppress grain boundary sliding, thereby improving high-temperature creep properties. The proportion of carbides formed is preferably 5% or more, since a low carbide proportion results in a decrease in high-temperature strength and high-temperature creep properties, and is preferably 12% or less, since a high carbide proportion results in embrittlement. The ratio is more preferably 7% to 10%, and even more preferably 8% to 9%. The ratio of carbides formed can be measured by calculating the area ratio in a cross-sectional structure image. In addition, in the structure of a Ni-based alloy shaped product that has been subjected to aging heat treatment after solution heat treatment, gamma-prime precipitates are formed in the crystal grains 30. The gamma-prime precipitates are intermetallic compounds consisting of Ni and Al or Ta, and Ni３ Al or Ni ３ In addition, when the Ni-based alloy shaped article contains Ti, which is an optional added element, Ni is formed as gamma prime precipitates. ３ The formation of such gamma prime precipitates improves the high temperature mechanical properties and creep properties.

[0053] <High-Temperature Strength and Creep Properties of Ni-Based Alloy Shaped Products> Ni-based alloys in which gamma-prime precipitates are formed by heat treatment are known to have good high-temperature mechanical properties and creep properties, and have been manufactured by casting, forging, and rolling. However, when alloys of such compositions are manufactured by additive manufacturing, there is a problem that cracks occur due to rapid solidification. By additive manufacturing using powder with the composition of the present invention, it is possible to obtain a shaped product that does not generate cracks and has good high-temperature mechanical properties and creep properties, even if the alloy has a Ni-based alloy composition in which gamma-prime precipitates are formed after heat treatment. Ni ３ Al and Ni ３ The Ni-based alloy shaped product of this embodiment has excellent high-temperature mechanical properties and creep properties due to multiple factors, such as intragranular precipitation strengthening by gamma-prime precipitates such as Ta, intragranular solid solution strengthening by Mo, Co, and W, grain boundary strengthening by B and Zr, grain boundary strengthening by carbide 31, and intragranular precipitation strengthening by carbide 32.

[0054] <Composition of Ni-Based Alloy Powder and Evaluation of Cracks in Shaped Objects> First, the composition of the metal powder used in the shaping is shown in Table 1. These compositions are referred to as Examples 1 to 6 and Comparative Examples 1 to 3. Next, using metal powders of seven different compositions with an average particle size (D50) of 25 μm produced by gas atomization, laser powder bed fusion (LPBF) was used to produce 10 mm x 10 mm x 10 mm cubic shaped objects (samples) using a laser diameter of 75 μm, a layer thickness of 30 μm per metal powder layer, a scan interval of 0.05 mm, a laser output of 160 to 200 W, and a scan speed of 800 to 1400 mm / s. Furthermore, the cross section of each shaped object was mirror-polished to check for cracks and evaluated under a microscope. Table 1 lists all 12 printing conditions, namely, the combination of three laser power conditions (160, 180, and 200 W) and four scan speed conditions (800, 1000, 1200, and 1400 mm / s). For samples in which no cracks occurred in any of the printed objects, a "No Crack" mark is shown on the right side of the table. For samples in which cracks occurred under any one of the conditions, a "Crack" mark is shown on the right side of the table. Cross-sectional observation revealed that cracks occurred in the printed objects of Comparative Examples 1 to 3, but not in the printed objects of Examples 1 to 6. While the C content was set to 0.1% by mass or more to suppress cracking in all compositions, the high Fe content of 2% by mass or more in Examples 1 to 6 is believed to have prevented cracking. On the other hand, the cracks in Comparative Examples 1 to 3 are believed to be due to the addition of Ti in excess of 0.5% by mass in Comparative Examples 1 and 2, and the insufficient Fe content of less than 1.0% by mass in Comparative Example 3, despite the absence of Ti. From this, it was confirmed that adding 0.1 mass% or more of C, 0.5 mass% or less of Ti, and adding at least 1.5 mass% or more of Fe are effective in preventing cracking. Furthermore, since all of Examples 1 to 6 contained the same amount of B as the comparative example, but no cracks occurred, it is thought that the addition of B is unlikely to contribute to cracking and is unlikely to promote the occurrence of cracks.

[0055] In the table, "-" indicates no content.

[0056] <Structural Observation of Ni-Based Alloy Shaped Article> Figure 3 shows a 10,000x scanning electron microscope (SEM) micrograph of the structure of Example 2, taken at a cross section perpendicular to the stacking direction. Similar to the aforementioned microscopic observation, no cracks were observed in the shaped article of Example 2. Furthermore, in Figure 3, the primary dendrite structure 21 grows in the stacking direction and has a narrow shape elongated in the stacking direction, with a width of approximately 0.5 to 2 μm. No secondary dendrite structure 22 (see Figure 4 below) is observed at the boundaries 23 between the primary dendrite structures 21, and the width of the boundaries 23 is very narrow, ranging from 0.1 to 0.4 μm. Therefore, it is believed that no cracks were generated. Therefore, it is preferable to set the width of the boundaries 23 to 0.4 μm or less. It was confirmed that no secondary dendrite structure 22 was generated and the width of the boundaries 23 was narrow in all of Examples 1 to 6, in which no cracks were generated. Therefore, it was found that by appropriately selecting the composition of the Ni-based alloy powder used as the raw material, the width of the boundaries 23 between the primary dendrite structures 21 can be narrowed and cracks can be prevented.

[0057] FIG. 4 shows a 5000x SEM micrograph of Comparative Example 1 taken at a cross section perpendicular to the stacking direction. In Comparative Example 1, a crack 20 has occurred vertically through the center of the image in FIG. 4 , as confirmed by visual inspection. This indicates that the crack 20 also forms in the stacking direction. Similarly to Example 2, Comparative Example 1 also showed primary dendrite structures 21 with a width of 0.5 to 2 μm growing in the stacking direction. However, secondary dendrite structures 22 were formed at the boundaries 23 between the primary dendrite structures 21 around the cracks 20, resulting in a width of approximately 0.5 to 2 μm, which was wider than that of Example 2. The formation of such secondary dendrite structures 22 is believed to be the cause of the cracks.

[0058] Furthermore, to examine the distribution of elements in Example 2, cross-section observation was performed using a scanning transmission electron microscope (STEM). Figure 5 shows a 25,000x STEM cross-sectional photograph of Example 2. Figure 5(a) shows a backscattered electron image, and Figures 5(b) to 5(l) show mapping images of the elements contained in Example 2: Ni, Cr, Al, Mo, Fe, Co, W, Ta, Zr, C, and B, respectively. In Figure 5(a), a polygonal primary dendrite structure 21 was observed because the cross section was observed on a plane perpendicular to the stacking direction. Furthermore, in Figures 5(c), (e), (h), (i), and (j), which show the distributions of Cr, Mo, W, Ta, and Zr, the boundaries 23 are whiter than the primary dendrite structures 21. This indicates that Cr, Mo, W, Ta, and Zr segregate at the boundaries 23 between the primary dendrite structures 21. This segregation reduces the mechanical properties, so heat treatment is required to eliminate the segregation.

[0059] <Structure of heat-treated Ni-based alloy shaped article> A heat treatment process consisting of a solution heat treatment and an aging heat treatment was carried out using Examples 1, 2 and 3. As mentioned above, the solution heat treatment was carried out to make the composition uniform and to eliminate the boundary 23 of the primary dendrite structure where solidification segregation occurs. The aging heat treatment was carried out to make the Ni ３ Al or Ni ３ This is performed to precipitate fine gamma-prime precipitates of Ta. Solution heat treatment was performed by holding the material at 1220°C in a vacuum for 10 hours, followed by quenching in a high-pressure nitrogen atmosphere at 0.5 MPa. The material was then heated to 870°C in a vacuum, held there for 16 hours, and quenched in a high-pressure nitrogen atmosphere at 0.5 MPa. This solution heat treatment and aging heat treatment can improve high-temperature strength and creep properties.

[0060] FIG. 6 shows a 3000x SEM cross-sectional photograph of Example 2 after the heat treatment process described above. The structure shows crystal grains 30 growing in the stacking direction, and two types of carbides were generated by the heat treatment: carbides 31 (hereinafter simply referred to as carbides 31) precipitated at the grain boundaries of crystal grains 30, and carbides 32 (hereinafter simply referred to as carbides 32) precipitated within crystal grains 30. Analysis using energy dispersive X-ray analysis with a scanning electron microscope revealed that carbides 31 and 32 were composite carbides containing W or Mo, with the same composition. Furthermore, the cross-sectional photograph was binarized to determine the proportion of the area occupied by carbides 31 and 32 in the image, which was 8.8%. Similarly, the proportions of carbides 31 and 32 were 8.7% for Example 1, 7.6% for Example 3, and 6.2% for Example 4. The carbide proportions were within the range of 5 to 12% in all Examples.

[0061] Figure 7 shows a 19,000x SEM photograph of gamma-prime precipitates in the heat-treated product of Example 1. Figure 7 confirms the formation of granular gamma-prime precipitates 33 of approximately 0.1 μm in size within the carbides 31 and crystal grains. Figure 8 shows a 30,000x SEM cross-sectional photograph of Example 3, which was heat-treated. For cross-sectional observation, phosphoric acid electrolytic etching was performed on Example 3. Because phosphoric acid electrolytic etching was performed, carbides 31 were not observed, but the formation of cubic gamma-prime precipitates 33 of 0.1 to 0.2 μm in size was confirmed. Analysis using energy dispersive X-ray analysis with a scanning electron microscope revealed that gamma-prime precipitates 33 were precipitates containing Ni, Ta, and Al, with Ni being the only element. ３ Al or Ni ３ This precipitate is thought to be Ta. This precipitate precipitates during aging heat treatment, and because it is hard and ductile, it is effective in improving high-temperature strength and creep characteristics.

[0062] <Mechanical Properties of Heat-Treated Ni-Based Alloy Shaped Articles> High-temperature tensile tests and creep tests were conducted on Examples 1 to 4, which had undergone the heat treatment process described above. The high-temperature tensile tests and creep tests were conducted in accordance with ASTM-E8 / E8M and ASTM-E139, respectively. Table 2 shows the results of the high-temperature tensile tests. All Examples achieved good tensile strengths of 1300 MPa or more at room temperature, 1000 MPa or more at 700°C, 900 MPa or more at 800°C, 600 MPa or more at 900°C, and 300 MPa or more at 1000°C. The elongation at room temperature was 15% or more, and the elongation at 700°C or higher was 20% or more. The reduction of area was also good, at 20% or more. Table 3 also shows the results of evaluating the creep properties of Example 1. Creep tests were conducted at a test temperature of 800°C and a creep load of 350 MPa, and it was confirmed that a satisfactory rupture time of 1,380 hours could be obtained. Furthermore, at a test temperature of 900°C and a creep load of 200 MPa, the rupture time was 302 hours, and at a test temperature of 980°C and a creep load of 100 MPa, the rupture time was 268 hours, both of which were satisfactory rupture times.

[0063]

[0064]

[0065] 1: Powder, 2: Powder supply stage, 3: Recoater, 4: Laser oscillator, 5: Laser light, 6: Galvano scanner, 7: Irradiation area, 8: Build stage, 9: Powder supply container, 10: Build box, 11: Powder recovery box, 20: Crack, 21: Primary dendritic structure, 22: Secondary dendritic structure, 23: Boundary of primary dendritic structure, 24: Grain boundary, 30: Grain, 31: Carbide precipitated at grain boundary, 32: Carbide precipitated within grain, 33: Gamma prime precipitate

Claims

1. A Ni-based alloy powder for additive manufacturing containing at least the following additive elements, by mass%, Cr: 6% to 12%, Mo: 1% to 4%, Al: 4% to 8%, Co: 6% to 11%, W: 7% to 12%, Ta: 1% to 5%, Fe: 1.5% to 7%, C: 0.1% to 0.25%, with the remainder being Ni and unavoidable impurities.

2. The Ni-based alloy powder for additive manufacturing according to claim 1, characterized in that the additive element contains, in mass%, B: more than 0% and 0.1% or less.

3. The Ni-based alloy powder for additive manufacturing according to claim 1, characterized in that the additive element contains, by mass%, at least one of the following: Nb: more than 0% and not more than 0.5%; Hf: more than 0% and not more than 0.5%.

4. The Ni-based alloy powder for additive manufacturing according to claim 1, characterized in that the additive element contains, by mass%, at least one of the following: Ti: more than 0% and not more than 0.5%; Zr: more than 0% and not more than 0.2%.

5. The Ni-based alloy powder for additive manufacturing according to claim 2, characterized in that, by mass%, the B is 0.005% or more and 0.05% or less.

6. The Ni-based alloy powder for additive manufacturing according to claim 1, characterized in that it contains, by mass%, Zr in an amount of 0.02% to 0.15%.

7. A method for manufacturing a Ni-based alloy object, comprising: supplying a Ni-based alloy powder for additive manufacturing containing, by mass%, at least the following additive elements: Cr: 6% to 12%, Mo: 1% to 4%, Al: 4% to 8%, Co: 6% to 11%, W: 7% to 12%, Ta: 1% to 5%, Fe: 1.5% to 7%, C: 0.1% to 0.25%, with the remainder being Ni and unavoidable impurities; selectively irradiating the supplied Ni-based alloy powder for additive manufacturing with laser light to melt and solidify it; and performing a powder melting additive manufacturing method in which the steps of supplying and melting and solidifying the Ni-based alloy powder for additive manufacturing are repeated to obtain a Ni-based alloy object.

8. The method for producing a Ni-based alloy shaped object according to claim 7, characterized in that the Ni-based alloy powder for additive manufacturing contains, as an additive element, in mass%, B: more than 0% and 0.1% or less.

9. The method for producing a Ni-based alloy object according to claim 7, characterized in that the Ni-based alloy powder for additive manufacturing contains, as an additive element, at least one of the following, in mass %, Nb: more than 0% and 0.5% or less, and Hf: more than 0% and 0.5% or less.

10. The method for producing a Ni-based alloy object according to claim 7, characterized in that the Ni-based alloy powder for additive manufacturing contains, as an additive element, at least one of the following, in mass %, Ti: more than 0% and 0.5% or less, and Zr: more than 0% and 0.2% or less.

11. The method for producing a Ni-based alloy shaped product according to claim 7, wherein the boundary width of the primary dendritic structure in the cross-sectional structure of the Ni-based alloy shaped product is 0.4 μm or less.

12. A method for producing a Ni-based alloy shaped article according to claim 7, further comprising a heat treatment step of subjecting the Ni-based alloy shaped article obtained by the powder fusion additive manufacturing method to a heat treatment.

13. The method for producing a Ni-based alloy shaped article according to claim 12, characterized in that the heat treatment step includes a solution heat treatment and an aging heat treatment.

14. The method for producing a Ni-based alloy shaped product according to claim 7, wherein the area ratio of carbides in the cross-sectional structure of the Ni-based alloy shaped product is 5% or more and 12% or less.

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