JP6372512B2 - Metal powder for powder metallurgy, compound, granulated powder, sintered body and heat-resistant parts - Google Patents

Description

  The present invention relates to a metal powder for powder metallurgy, a compound, a granulated powder, a sintered body, and a heat-resistant component.

  In the powder metallurgy method, a composition including a metal powder and a binder is molded into a desired shape to obtain a molded body, and then the molded body is degreased and sintered to produce a sintered body. In the manufacturing process of such a sintered body, an atomic diffusion phenomenon occurs between the particles of the metal powder, and thereby the compact is gradually densified, resulting in sintering.

  For example, Patent Document 1 proposes a magneto-optical recording medium target obtained by sintering an alloy powder containing 15 to 30 atomic% of a rare earth metal and the balance being a transition metal. And it is disclosed that this target adds Ti, V, Nb, Ta, etc. at 15 atomic% or less as an element which improves corrosion resistance. Thereby, in the invention described in Patent Document 1, the mechanical strength of the target is improved.

  On the other hand, Patent Document 2 proposes a metal powder for powder metallurgy comprising Zr and Si, with the balance being at least one selected from the group consisting of Fe, Co and Ni and an inevitable element. According to such a metal powder for powder metallurgy, a high-density sintered body can be easily manufactured by improving the sinterability. In recent years, such sintered bodies have been widely used for various machine parts and structural parts.

  However, depending on the application of the sintered body, further densification may be required. In such a case, the density is increased by performing additional processing such as hot isostatic pressing (HIP processing) on the sintered body. The cost cannot be avoided.

  Therefore, there is an increasing expectation for the realization of a metal powder capable of producing a high-density sintered body without performing additional processing.

JP-A-8-302463 JP 2012-87416 A

  The objective of this invention is providing the metal powder for powder metallurgy which can manufacture a high-density sintered compact, a compound, and a granulated powder, and a high-density sintered compact and a heat-resistant component.

The above object is achieved by the present invention described below.
The metal powder for powder metallurgy of the present invention is mainly composed of Co,
Cr is contained in a proportion of 10% by mass to 25% by mass,
Ni is contained in a proportion of 5% by mass or more and 40% by mass or less,
At least one of Mo and W is included in a ratio of 2% by mass to 20% by mass in total,
Si is contained in a proportion of 0.3% by mass or more and 1.5% by mass or less,
C is included in a proportion of 0.05% by mass or more and 0.8% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a proportion of 0.01% by mass to 0.5% by mass,
The second element is contained in a proportion of 0.01% by mass or more and 0.5% by mass or less.
The metal powder for powder metallurgy of the present invention is mainly composed of Co,
Cr is contained at a ratio of 15% by mass or more and 24% by mass or less,
Ni is contained in a ratio of 7% by mass to 32% by mass,
At least one of Mo and W is included in a ratio of 5% by mass to 18% by mass in total,
Si is contained at a ratio of 0.4% by mass or more and 1.2% by mass or less,
C is contained in a proportion of 0.2% by mass or more and 0.6% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a ratio of 0.03% by mass to 0.2% by mass,
The second element is contained in a proportion of 0.03% by mass or more and 0.2% by mass or less.
The metal powder for powder metallurgy of the present invention is mainly composed of Co,
Cr is contained in a proportion of 18% by mass to 23% by mass,
Ni is contained in a proportion of 9% by mass to 36% by mass,
At least one of Mo and W is included in a ratio of 7% by mass to 16% by mass in total,
Si is contained in a proportion of 0.5% by mass or more and 1% by mass or less,
C is contained in a proportion of 0.3% by mass or more and 0.5% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a proportion of 0.05% by mass or more and 0.1% by mass or less,
The second element is contained in a proportion of 0.05% by mass or more and 0.1% by mass or less.

  Thereby, optimization of an alloy composition is achieved and densification at the time of sintering of the metal powder for powder metallurgy can be promoted. As a result, a metal powder for powder metallurgy capable of producing a high-density sintered body without additional processing is obtained.

In the metal powder for powder metallurgy of the present invention, it is preferable that Fe is further contained in a proportion of 0.5% by mass or more and 5% by mass or less.
In the metal powder for powder metallurgy of the present invention, it is preferable that Fe is further contained in a proportion of 0.8 mass% to 3 mass%.
In the metal powder for powder metallurgy of the present invention, it is preferable that Fe is contained in a proportion of 1% by mass or more and 2.5% by mass or less.
Thereby, the mechanical characteristic of the sintered compact manufactured can be improved more.

In the metal powder for powder metallurgy of the present invention, the value obtained by dividing the content of the first element by the atomic weight of the first element is X1, and the value obtained by dividing the content of the second element by the atomic weight of the second element Is X2, X1 / X2 is preferably 0.3 or more and 3 or less.
In the metal powder for powder metallurgy of the present invention, the value obtained by dividing the content of the first element by the atomic weight of the first element is X1, and the value obtained by dividing the content of the second element by the atomic weight of the second element When X is X2, X1 / X2 is preferably 0.5 or more and 2 or less.
In the metal powder for powder metallurgy of the present invention, the value obtained by dividing the content of the first element by the atomic weight of the first element is X1, and the value obtained by dividing the content of the second element by the atomic weight of the second element Is X2, X1 / X2 is preferably 0.75 or more and 1.3 or less.

  Thereby, when the metal powder for powder metallurgy is fired, it is possible to optimize the difference in timing between the precipitation of the first element carbide and the like and the precipitation of the second element carbide and the like. As a result, since the voids remaining in the molded body can be sequentially discharged from the inside and discharged, the voids generated in the sintered body can be minimized. Therefore, a metal powder for powder metallurgy capable of producing a sintered body having high density and excellent sintered body characteristics can be obtained.

In the metal powder for powder metallurgy according to the present invention, the total content of the first element and the content of the second element is preferably 0.05% by mass or more and 0.6% by mass or less.
In the metal powder for powder metallurgy of the present invention, the total content of the first element and the content of the second element is preferably 0.10% by mass or more and 0.48% by mass or less.
In the metal powder for powder metallurgy of the present invention, the total content of the first element and the content of the second element is preferably 0.12% by mass or more and 0.24% by mass or less.
As a result, the density of the sintered body to be manufactured becomes necessary and sufficient.

  In the metal powder for powder metallurgy of the present invention, the average particle size is preferably 0.5 μm or more and 30 μm or less.

  Thereby, since the void | holes which remain | survive in a sintered compact become very few, the sintered compact which was especially high-density and excellent in the mechanical characteristic can be manufactured.

The compound of the present invention includes the metal powder for powder metallurgy of the present invention.
Thereby, the compound which can manufacture a high-density sintered compact is obtained.

The granulated powder of the present invention comprises the metal powder for powder metallurgy of the present invention.
Thereby, the granulated powder which can manufacture a high-density sintered compact is obtained.

The sintered body of the present invention is mainly composed of Co,
Cr is contained in a proportion of 10% by mass to 25% by mass,
Ni is contained in a proportion of 5% by mass or more and 40% by mass or less,
At least one of Mo and W is included in a ratio of 2% by mass to 20% by mass in total,
Si is contained in a proportion of 0.3% by mass or more and 1.5% by mass or less,
C is included in a proportion of 0.05% by mass or more and 0.8% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a proportion of 0.01% by mass to 0.5% by mass,
The second element is contained in a proportion of 0.01% by mass or more and 0.5% by mass or less.
Thereby, a high-density sintered compact is obtained, without performing an additional process.

The heat-resistant component of the present invention includes the sintered body of the present invention.
As a result, a heat-resistant component having high density and excellent heat resistance can be obtained without additional treatment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a side view showing a turbocharger nozzle vane to which a first embodiment of a heat-resistant component of the present invention is applied (a view when a blade is viewed in plan). It is a top view of the nozzle vane shown in FIG. It is a rear view of the nozzle vane shown in FIG. It is a perspective view which shows the compressor blade | wing to which 2nd Embodiment of the heat-resistant component of this invention is applied.

  Hereinafter, the metal powder for powder metallurgy, compound, granulated powder, sintered body and heat-resistant component of the present invention will be described in detail.

[Metal powder for powder metallurgy]
First, the metal powder for powder metallurgy according to the present invention will be described.

  In powder metallurgy, a composition including a metal powder for powder metallurgy and a binder is molded into a desired shape, and then degreased and sintered to obtain a sintered body having a desired shape. Such a powder metallurgy technique has an advantage that a sintered body having a complicated and fine shape can be manufactured with a near net (a shape close to the final shape) as compared with other metallurgical techniques.

  As metal powder for powder metallurgy used for powder metallurgy, attempts have been conventionally made to increase the density of a sintered body produced by appropriately changing the composition. However, since pores are easily formed in the sintered body, it was necessary to further increase the density of the sintered body in order to obtain mechanical properties equivalent to the melted material.

  Therefore, conventionally, the obtained sintered body may be further densified by performing additional processing such as hot isostatic pressing (HIP processing). However, such additional processing involves a lot of labor and cost, and is an obstacle when expanding the use of the sintered body.

  In view of the above problems, the present inventor has intensively studied the conditions for obtaining a high-density sintered body without performing additional processing. As a result, it has been found that the density of the sintered body can be increased by optimizing the composition of the alloy constituting the metal powder, and the present invention has been completed.

  Specifically, the metal powder for powder metallurgy of the present invention is mainly composed of Co, Cr is contained in a proportion of 10% by mass to 25% by mass, and Ni is a proportion of 5% by mass to 40% by mass. And at least one of Mo and W is included in a ratio of 2% by mass to 20% by mass in total, Si is included in a ratio of 0.3% by mass to 1.5% by mass, and C is 0 0.05% by mass or more and 0.8% by mass or less, the first element described later is included by 0.01% by mass or more and 0.5% by mass or less, and the second element described later is 0.01%. It is contained at a ratio of not less than mass% and not more than 0.5 mass%. According to such a metal powder, as a result of optimization of the alloy composition, densification during sintering can be particularly enhanced. As a result, a high-density sintered body can be manufactured without performing additional processing.

  And the sintered compact which was excellent in mechanical characteristics will be obtained by densifying a sintered compact. Such a sintered body can be widely applied to applications in which an external force (load) is applied, such as a machine part or a structural part.

  The first element is one element selected from the group consisting of seven elements of Ti, V, Y, Zr, Nb, Hf, and Ta. The second element is one element selected from the group consisting of the seven elements, and the element in the periodic table is larger than the first element, or selected from the group consisting of the seven elements. And the group in the periodic table of the elements is the same as the first element, and the period in the periodic table of the elements is larger than the first element.

  Hereinafter, the alloy composition of the metal powder for powder metallurgy according to the present invention will be described in more detail. In the following description, the metal powder for powder metallurgy may be simply referred to as “metal powder”.

(Cr)
Cr (chromium) is an element that imparts corrosion resistance and oxidation resistance to the sintered body to be produced. By using a metal powder containing Cr, a sintered body that can maintain high mechanical properties over a long period of time is obtained. It is done. For this reason, for example, a structural component capable of maintaining its function even when exposed to high temperatures can be realized.

  The Cr content in the metal powder is 10% by mass or more and 25% by mass or less, preferably 15% by mass or more and 24% by mass or less, and more preferably 18% by mass or more and 23% by mass or less. When the Cr content is lower than the lower limit, depending on the overall composition, the corrosion resistance of the sintered body to be produced becomes insufficient, and the heat resistance decreases. On the other hand, if the Cr content exceeds the upper limit, depending on the overall composition, the sinterability may be reduced, making it difficult to increase the density of the sintered body. Thereby, it becomes difficult to improve the corrosion resistance (heat resistance) of the sintered body to be manufactured.

(Ni)
When Ni (nickel) is added together with Cr, the rate of progress of pitting corrosion and corrosion of the chromium oxide layer formed on the surface of the sintered body is lowered, and the strength (heat resistance) of the sintered body at high temperatures is reduced. ). Moreover, since austenitization is achieved, the crystalline phase in the sintered body can be stabilized even at high temperatures, so that the heat resistance of the sintered body can also be achieved from this viewpoint.

  The Ni content in the metal powder is 5% by mass or more and 40% by mass or less, preferably 7% by mass or more and 37% by mass or less, and more preferably 9% by mass or more and 36% by mass or less. When the Ni content is lower than the lower limit, the corrosion resistance and heat resistance are lowered. On the other hand, when the Ni content exceeds the upper limit, the content of Cr and Co is relatively lowered, so that the corrosion resistance and heat resistance are lowered.

(Mo and W)
Mo (molybdenum) and W (tungsten) reinforce the heat resistance of the sintered bodies to be produced. Mo and W are each bonded to C to form a carbide, which is considered to increase the high temperature strength. Moreover, by using in combination with Cr, the mechanical strength and hardness of the sintered body can be increased even at high temperatures. Therefore, the heat resistance of the sintered body can be increased.

  The metal powder contains at least one of Mo and W. The content of Mo and W in the metal powder is 2% by mass to 20% by mass in total of Mo and W, preferably 5% by mass to 18% by mass, and more preferably 7% by mass. % To 16% by mass. If the total content of Mo and W is below the lower limit, the heat resistance of the sintered body may not be sufficiently increased. On the other hand, if the total content of Mo and W exceeds the upper limit, a large amount of intermetallic compounds may be formed and the sintered body may be embrittled.

  When the metal powder contains both Mo and W, the ratio of Mo and W is not particularly limited, but is preferably 10:90 or more and 90:10 or less in terms of mass ratio, and 20:80 or more and 80:20. The following is more preferable.

(Si)
Si (silicon) acts to improve the corrosion resistance and mechanical properties of the sintered body to be produced. Addition of Si reduces oxides of metal elements such as Co in the alloy, while silicon oxide in which a part of Si is oxidized is generated. Examples of silicon oxide include SiO and SiO ₂ . Such silicon oxide inhibits the metal crystal from becoming significantly enlarged when the metal crystal grows during sintering of the metal powder. For this reason, in the alloy to which Si is added, the particle size of the metal crystal is kept small, and the corrosion resistance and mechanical properties of the sintered body can be further enhanced. In particular, when a Si atom substitutes a Co atom as a substitutional element, the crystal structure is slightly distorted and the Young's modulus is increased. Therefore, by adding Si, excellent mechanical properties, particularly excellent Young's modulus can be obtained. As a result, a sintered body having higher deformation resistance even at high temperatures can be obtained.

  The Si content in the metal powder is 0.3% by mass or more and 1.5% by mass or less, preferably 0.4% by mass or more and 1.2% by mass or less, more preferably 0.5% by mass or more. It is more preferably 1% by mass or less. If the Si content is lower than the lower limit, depending on the firing conditions, the amount of silicon oxide becomes too small, and the metal crystals may tend to enlarge during the sintering of the metal powder. On the other hand, when the Si content exceeds the upper limit, depending on the firing conditions, the amount of silicon oxide becomes excessive, so that a region in which silicon oxide is spatially continuously distributed tends to occur. In this region, there is a high possibility that the mechanical characteristics will deteriorate.

(C)
When C (carbon) is used in combination with the first element and the second element described later, the sinterability can be particularly improved and the density can be increased. Specifically, each of the first element and the second element combines with C to generate a carbide. By dispersing and precipitating the carbide, an effect of preventing remarkable growth of crystal grains occurs. The clear reason why such an effect is obtained is unknown, but as one of the reasons, the dispersed precipitates become an obstacle and inhibit the remarkable growth of the crystal grains, so that the variation in the size of the crystal grains can be suppressed. It is possible. As a result, voids are less likely to occur in the sintered body, and enlargement of crystal grains is prevented, so that a sintered body having a high density and high mechanical properties can be obtained.

  The content of C in the metal powder is 0.05% by mass or more and 0.8% by mass or less, preferably 0.2% by mass or more and 0.6% by mass or less, more preferably 0.3% by mass. % To 0.5 mass%. If the C content is less than the lower limit, depending on the overall composition, crystal grains are likely to grow, and the mechanical properties of the sintered body become insufficient. On the other hand, when the C content exceeds the upper limit, C increases excessively depending on the entire composition, and the sinterability deteriorates.

(First element and second element)
The first element and the second element precipitate carbides and oxides (hereinafter collectively referred to as “carbides and the like”). And this precipitated carbide | carbonized_material etc. are thought to inhibit the remarkable growth of a crystal grain, when a metal powder sinters. As a result, as described above, voids are less likely to occur in the sintered body, and the enlargement of crystal grains is prevented, and a sintered body having a high density and high mechanical properties can be obtained.

  In addition, as will be described in detail later, the precipitated carbides and the like promote the accumulation of silicon oxide at the grain boundaries, and as a result, the sintering is promoted and the density is increased while suppressing the enlargement of the crystal grains. .

  By the way, the first element and the second element are two elements selected from the group consisting of Ti, V, Y, Zr, Nb, Hf, and Ta. It is preferable that an element belonging to the group (Ti, Y, Zr, Hf) is included. By including an element belonging to Group 3A or Group 4A as at least one of the first element and the second element, oxygen contained in the metal powder as an oxide is removed during sintering, and the metal powder is sintered. The sex can be particularly enhanced.

  Further, as described above, the first element may be one element selected from the group consisting of Ti, V, Y, Zr, Nb, Hf, and Ta. The element belongs to Group 3A or Group 4A of the periodic element periodic table. The elements belonging to Group 3A or Group 4A in the group can remove oxygen contained as an oxide in the metal powder and can particularly enhance the sinterability of the metal powder. Thereby, the oxygen concentration remaining in the crystal grains after sintering can be reduced. As a result, the oxygen content of the sintered body can be reduced and the density can be increased. Moreover, since these elements are highly active elements, it is considered that rapid atomic diffusion is brought about. For this reason, this atomic diffusion becomes a driving force, the distance between the particles of the metal powder is efficiently reduced, and densification of the compact is promoted by forming a neck between the particles. As a result, the sintered body can be further densified.

  On the other hand, as described above, the second element is one element selected from the group consisting of Ti, V, Y, Zr, Nb, Hf and Ta, and is an element different from the first element. Preferably, it is an element belonging to group 5A of the long-period element periodic table in the group. The element belonging to Group 5A in the group particularly efficiently precipitates the above-described carbides and the like, and therefore can effectively inhibit the remarkable growth of crystal grains during sintering. As a result, the generation of fine crystal grains can be promoted, and the density of the sintered body can be increased and the mechanical properties can be improved.

  In addition, in the combination of the 1st element and 2nd element which consist of the above elements, each effect is exhibited, without mutually inhibiting. For this reason, such a metal powder containing the first element and the second element can produce a particularly high-density sintered body.

  More preferably, a combination in which the first element is an element belonging to Group 4A and the second element is Nb is employed.

More preferably, a combination in which the first element is Zr or Hf and the second element is Nb is employed.
By adopting such a combination, the above-described effect becomes more remarkable.

  Of these elements, Zr is a ferrite-forming element, so that a body-centered cubic lattice phase is precipitated. This body-centered cubic lattice phase is excellent in sinterability compared to other crystal lattice phases, and thus contributes to higher density of the sintered body.

  The content ratio of the first element in the metal powder is 0.01% by mass or more and 0.5% by mass or less, preferably 0.03% by mass or more and 0.2% by mass or less, and more preferably 0.8% by mass. It is set to 05 mass% or more and 0.1 mass% or less. When the content of the first element is below the lower limit, depending on the entire composition, the effect of adding the first element becomes dilute, so that the density of the sintered body to be manufactured becomes insufficient. On the other hand, if the content of the first element exceeds the upper limit, depending on the overall composition, the first element will be too much, so that the ratio of the above-described carbides will be too much, and the densification will be impaired. .

  The content ratio of the second element in the metal powder is 0.01% by mass or more and 0.5% by mass or less, preferably 0.03% by mass or more and 0.2% by mass or less, and more preferably 0.8% by mass. It is set to 05 mass% or more and 0.1 mass% or less. If the content ratio of the second element is less than the lower limit, depending on the entire composition, the effect of adding the second element becomes dilute, so that the density of the sintered body to be manufactured becomes insufficient. On the other hand, if the content ratio of the second element exceeds the upper limit, depending on the entire composition, the second element becomes too much, so that the ratio of the above-mentioned carbides and the like becomes too large, and the densification is impaired. .

  As described above, the first element and the second element each precipitate carbide or the like. However, as described above, the element belonging to the 3A group or the 4A group is selected as the first element, and the second element is described above. Thus, when an element belonging to the group 5A is selected, it is assumed that the timing at which the carbide of the first element precipitates and the timing at which the carbide of the second element precipitates are different from each other when the metal powder is sintered. . Since the timing of precipitation of carbides and the like is shifted in this way, the sintering proceeds gradually, so that it is considered that the formation of pores is suppressed and a dense sintered body can be obtained. That is, it is considered that the presence of both the first element carbide and the second element carbide makes it possible to suppress the enlargement of crystal grains while achieving higher density.

The ratio between the content ratio of the first element and the content ratio of the second element is preferably set in consideration of the atomic weight of the element selected as the first element and the atomic weight of the element selected as the second element. .

Specifically, when the first element is E1 and the second element is E2, the value obtained by dividing the content (% by mass) of the first element E1 by the atomic weight of the first element is the index X1, and the second element When the value obtained by dividing the E2 content (mass%) by the atomic weight of the second element is index X2, the ratio X1 / X2 of the index X1 to the index X2 is preferably 0.3 or more and 3 or less. It is more preferably 5 or more and 2 or less, and further preferably 0.75 or more and 1.3 or less. By setting X1 / X2 within the above range, when the metal powder is fired, the difference between the timing of precipitation of carbides of the first element and the timing of precipitation of carbides of the second element is optimized. Can do. Thereby, since the void | hole remaining in a molded object can be discharged | emitted as it sweeps out sequentially from an inner side, the void | hole produced in a sintered compact can be suppressed to the minimum. Therefore, by setting X1 / X2 within the above range, a sintered body having high density and excellent mechanical properties can be obtained. Further, since the balance between the number of atoms of the first element and the number of atoms of the second element is optimized, the effect brought about by the first element and the effect brought about by the second element are exhibited synergistically, A sintered body having a density can be obtained.

  Here, about the example of a specific combination of the first element and the second element, based on the range of the ratio X1 / X2, the content ratio of the first element E1 with respect to the content ratio (mass%) of the second element E2 ( (Mass%) ratio E1 / E2 is also calculated.

For example, when the first element E1 is Zr and the second element E2 is Nb, the atomic weight of Zr is 91.2 and the atomic weight of Nb is 92.9, so E1 / E2 is 0.29. The above is preferably 2.95 or less, and more preferably 0.49 or more and 1.96 or less.

Further, when the first element E1 is Hf and the second element E2 is Nb, the atomic weight of Hf is 178.5 and the atomic weight of Nb is 92.9, so E1 / E2 is 0.58. It is preferably 5.76 or less and more preferably 0.96 or more and 3.84 or less.

When the first element E1 is Ti and the second element E2 is Nb, the atomic weight of Ti is 47.9 and the atomic weight of Nb is 92.9, so E1 / E2 is 0.15. It is preferably 1.55 or less and more preferably 0.26 or more and 1.03 or less.

Further, when the first element E1 is Nb and the second element E2 is Ta, the atomic weight of Nb is 92.9 and the atomic weight of Ta is 180.9. Therefore, E1 / E2 is 0.15 It is preferably 1.54 or more and more preferably 0.26 or more and 1.03 or less.

When the first element E1 is Y and the second element E2 is Nb, the atomic weight of Y is 88.9, and the atomic weight of Nb is 92.9, so E1 / E2 is 0.29. It is preferably 2.87 or less and more preferably 0.48 or more and 1.91 or less.

When the first element E1 is V and the second element E2 is Nb, the atomic weight of V is 50.9, and the atomic weight of Nb is 92.9. Therefore, E1 / E2 is 0.16 It is preferable that it is 1.64 or more and more preferably 0.27 or more and 1.10 or less.

When the first element E1 is Ti and the second element E2 is Zr, the atomic weight of Ti is 47.9, and the atomic weight of Zr is 91.2. Therefore, E1 / E2 is 0.16 It is preferably 1.58 or more and more preferably 0.26 or more and 1.05 or less.

When the first element E1 is Zr and the second element E2 is Ta, the atomic weight of Zr is 91.2 and the atomic weight of Ta is 180.9, so E1 / E2 is 0.15 It is preferably 1.51 or more and more preferably 0.25 or more and 1.01 or less.

Further, when the first element E1 is Zr and the second element E2 is V, the atomic weight of Zr is 91.2 and the atomic weight of V is 50.9. Therefore, E1 / E2 is 0.54. It is preferably 5.38 or less and more preferably 0.90 or more and 3.58 or less.

  In addition, E1 / E2 can be calculated in the same manner as described above for combinations other than those described above.

  Further, when the total content of the first element E1 and the content of the second element E2 is E1 + E2, E1 + E2 is preferably 0.05% by mass or more and 0.6% by mass or less, and 0.10% by mass. The content is more preferably 0.48% by mass or less, and further preferably 0.12% by mass or more and 0.24% by mass or less. By setting the sum of the content ratio of the first element and the content ratio of the second element within the above range, an amount for the first element or the second element to sufficiently act when the metal powder is fired is ensured. Therefore, the density of the sintered body to be manufactured becomes necessary and sufficient.

  Further, when the ratio of the total content of the first element E1 and the content of the second element E2 to the Si content is (E1 + E2) / Si, (E1 + E2) / Si is 0.03 or more and 2 or less. Is more preferably 0.05 or more and 1 or less, and further preferably 0.1 or more and 0.5 or less. By setting (E1 + E2) / Si within the above range, the reduction in toughness when Si is added is sufficiently compensated by the addition of the first element and the second element. As a result, a sintered body having excellent mechanical properties such as toughness and excellent corrosion resistance derived from Si can be obtained despite its high density.

  In addition, by adding appropriate amounts of the first element and the second element, the carbide of the first element, the carbide of the second element, and the like become “nuclei” at the grain boundaries in the sintered body, and the silicon oxide Accumulation is thought to occur. Since silicon oxide accumulates at the crystal grain boundaries, the oxide concentration in the crystal grains decreases, so that sintering is promoted. As a result, it is considered that the densification of the sintered body is further promoted.

  Furthermore, since the precipitated silicon oxide easily moves to the triple point of the grain boundary during the accumulation process, crystal growth at this point is suppressed (pinning effect). As a result, remarkable growth of crystal grains is suppressed, and a sintered body having finer crystals can be obtained. Such a sintered body has particularly high mechanical properties.

  Furthermore, when the ratio of the total content of the first element E1 and the content of the second element E2 to the content of C is (E1 + E2) / C, (E1 + E2) / C is 0.05 to 3 Preferably, it is 0.1 or more and 2 or less, more preferably 0.2 or more and 1 or less. By setting (E1 + E2) / C within the above range, it is possible to achieve both an increase in hardness and a decrease in toughness when C is added and an increase in density caused by the addition of the first element and the second element. Can do. As a result, a sintered body excellent in mechanical properties such as tensile strength and toughness can be obtained.

  The metal powder only needs to contain two elements selected from the group consisting of Ti, V, Y, Zr, Nb, Hf, and Ta. Further, an element different from these two kinds of elements may be further contained. That is, the metal powder may contain three or more elements selected from the above group. As a result, the effect described above can be further enhanced, although it differs somewhat depending on the combination.

(Other elements)
The metal powder for powder metallurgy of the present invention may further contain at least one of Fe, B, Mn, and S, if necessary, in addition to the elements described above. In addition, these elements may be contained unavoidable.
Fe (iron) imparts high mechanical properties to the sintered body to be produced.
The content of Fe in the metal powder is not particularly limited, but is preferably 0.5% by mass or more and 5% by mass or less, more preferably 0.8% by mass or more and 3% by mass or less, and 1% by mass. More preferably, it is 2.5 mass% or less. By setting the content of Fe in the metal powder within the above range, the mechanical properties of the sintered body to be manufactured can be further enhanced.

  In addition, when the content rate of Fe is less than the said lower limit, there exists a possibility that the mechanical characteristic of a sintered compact cannot fully be improved depending on the whole composition. On the other hand, if the Fe content exceeds the upper limit, the corrosion resistance and oxidation resistance of the sintered body may be lowered depending on the overall composition.

B (boron) strengthens the crystal grain boundary and improves the high-temperature strength and ductility of the sintered body.
The content of B in the metal powder is not particularly limited, but is preferably 0.002% by mass or more and 0.1% by mass or less, and more preferably 0.004% by mass or more and 0.05% by mass or less. More preferably, the content is 0.006% by mass or more and 0.02% by mass or less. By setting the B content within the above range, a sintered body excellent in heat resistance and elongation can be obtained.

  In addition, when the content rate of B is less than the said lower limit, there exists a possibility that the heat resistance of the sintered compact manufactured may fall or brittleness may increase depending on the whole composition. On the other hand, if the B content exceeds the upper limit, the heat resistance and ductility may be lowered.

Mn (manganese), like Si, imparts corrosion resistance and high mechanical properties to the sintered body to be produced.
The Mn content in the metal powder is not particularly limited, but is preferably 0.005% by mass to 0.3% by mass, and more preferably 0.01% by mass to 0.1% by mass. . By setting the Mn content within the above range, a sintered body having a high density and excellent mechanical properties can be obtained. In addition, an increase in brittleness at high temperatures (during red heat) can be suppressed.

  If the Mn content is less than the lower limit, depending on the overall composition, the corrosion resistance and mechanical properties of the sintered body to be produced may not be sufficiently improved, whereas the Mn content is If the upper limit is exceeded, corrosion resistance and mechanical properties may be deteriorated.

S (sulfur) improves the machinability of the sintered body to be produced.
Although the content rate of S in a metal powder is not specifically limited, It is preferable that it is 0.5 mass% or less, and it is more preferable that it is 0.01 mass% or more and 0.3 mass% or less. By setting the S content within the above range, the machinability of the manufactured sintered body can be further improved without causing a significant decrease in the density of the manufactured sintered body.

  In addition, N, Al, P, Se, Te, Pd, or the like may be added to the metal powder for powder metallurgy of the present invention. In that case, although the content rate of these elements is not specifically limited, It is preferable that it is 0.05 mass% or less, respectively, and it is preferable that it is less than 0.2 mass% in total. In addition, these elements may be contained unavoidable.

  The metal powder for powder metallurgy of the present invention may contain impurities. Examples of the impurities include all elements other than the elements described above. Specifically, for example, Li, Be, Na, Mg, K, Ca, Sc, Zn, Ga, Ge, Ag, In, Sn, Sb , Os, Ir, Pt, Au, Bi and the like. The amount of these impurities mixed is preferably controlled so that each element is less than the content of each of the essential elements described above. The amount of these impurities mixed is preferably set so that each element is less than 0.03% by mass, and more preferably set to be less than 0.02% by mass. Further, the total amount is preferably less than 0.3% by mass, and more preferably less than 0.2% by mass. In addition, as long as the content rate is in the above range, these elements may be intentionally added because the effects as described above are not inhibited.

  On the other hand, O (oxygen) may be added intentionally or inevitably mixed, but the amount is preferably about 0.8% by mass or less, and about 0.5% by mass or less. More preferably. By keeping the amount of oxygen in the metal powder at this level, the sinterability becomes high, and a sintered body having a high density and excellent mechanical properties can be obtained. The lower limit is not particularly set, but is preferably 0.03% by mass or more from the viewpoint of ease of mass production.

  Co (cobalt) is a component (main component) having the highest content in the alloy constituting the metal powder for powder metallurgy of the present invention, and has a great influence on the properties of the sintered body. The Co content is not particularly limited, but is preferably 45% by mass or more, and more preferably 50% by mass or more.

  The composition ratio of the metal powder for powder metallurgy is, for example, iron and steel-atomic absorption spectrophotometry specified in JIS G 1257 (2000), iron and steel-ICP emission spectroscopy specified in JIS G 1258 (2007). Analytical method, iron and steel as defined in JIS G 1253 (2002), spark discharge optical emission spectrometry, iron and steel as defined in JIS G 1256 (1997), fluorescent X-ray analysis, JIS G 1211-G 1237 Can be specified by the weight, titration, absorptiometry, etc. defined in the above. Specifically, for example, a solid emission spectroscopic analyzer manufactured by SPECTRO (spark discharge optical spectroscopic analyzer, model: SPECTROLAB, type: LAVMB08A) and an ICP apparatus (CIROS120 type) manufactured by Rigaku Corporation are exemplified.

JIS G 1211 to G 1237 are as follows.
JIS G 1211 (2011) Iron and steel-carbon determination method JIS G 1212 (1997) Iron and steel-silicon determination method JIS G 1213 (2001) Manganese determination method in iron and steel JIS G 1214 (1998) Iron and steel -Phosphorus determination method JIS G 1215 (2010) Iron and steel-sulfur determination method JIS G 1216 (1997) Iron and steel-nickel determination method JIS G 1217 (2005) Iron and steel-chromium determination method JIS G 1218 (1999) Iron And steel-molybdenum determination method JIS G 1219 (1997) Iron and steel-copper determination method JIS G 1220 (1994) Iron and steel-tungsten determination method JIS G 1221 (1998) Iron and steel-vanadium determination method JIS G 1222 (1999) ) Iron and steel-Cobalt determination method JIS G 1223 (1997) Iron and steel-titanium determination method JIS G 1224 (2001) Aluminum and iron in steel determination method JIS G 1225 (2006) Iron and steel-arsenic determination method JIS G 1226 (1994) Iron and steel Tin determination method JIS G 1227 (1999) Boron determination method in iron and steel JIS G 1228 (2006) Iron and steel-nitrogen determination method JIS G 1229 (1994) Steel-lead determination method JIS G 1232 (1980) In steel JIS G 1233 (1994) Steel-selenium quantification method JIS G 1234 (1981) Tellurium quantification method in steel JIS G 1235 (1981) Antimony quantification method in iron and steel JIS G 1236 (1992) Tantalum determination method JIS G 1237 ( 1997) Iron and steel-niobium determination method

  Further, when specifying C (carbon) and S (sulfur), in particular, an oxygen stream combustion (high frequency induction furnace combustion) -infrared absorption method defined in JIS G 1211 (2011) is also used. Specifically, a carbon / sulfur analyzer manufactured by LECO, CS-200 may be mentioned.

  Furthermore, when specifying N (nitrogen) and O (oxygen), in particular, a method for determining nitrogen in iron and steel specified in JIS G 1228 (2006), oxygen in a metal material specified in JIS Z 2613 (2006). A quantitative method is also used. Specific examples include an oxygen / nitrogen analyzer manufactured by LECO, TC-300 / EF-300.

  The average particle size of the metal powder for powder metallurgy of the present invention is preferably 0.5 μm or more and 30 μm or less, more preferably 1 μm or more and 20 μm or less, and further preferably 2 μm or more and 10 μm or less. By using the metal powder for powder metallurgy having such a particle size, the number of voids remaining in the sintered body is extremely reduced, and thus a sintered body having a particularly high density and excellent mechanical properties can be produced. .

  The average particle size is obtained as the particle size when the cumulative amount is 50% from the small diameter side in the cumulative particle size distribution on a mass basis obtained by the laser diffraction method.

  In addition, when the average particle size of the metal powder for powder metallurgy is below the lower limit value, there is a possibility that the moldability is lowered when forming a shape that is difficult to mold, and the sintered density is lowered, and the upper limit value is exceeded. In this case, the gap between the particles becomes large at the time of molding, so that the sintered density may also be lowered.

  The particle size distribution of the metal powder for powder metallurgy is preferably as narrow as possible. Specifically, when the average particle size of the metal powder for powder metallurgy is within the above range, the maximum particle size is preferably 200 μm or less, and more preferably 150 μm or less. By controlling the maximum particle size of the metal powder for powder metallurgy within the above range, the particle size distribution of the metal powder for powder metallurgy can be narrowed, and the density of the sintered body can be further increased.

  The maximum particle size refers to the particle size when the cumulative amount is 99.9% from the small diameter side in the cumulative particle size distribution on a mass basis obtained by the laser diffraction method.

  Further, when the short diameter of the metal powder metal powder powder powder is S [μm] and the long diameter is L [μm], the average aspect ratio defined by S / L is about 0.4 or more and 1 or less. It is preferable that it is about 0.7 or more and 1 or less. Since the metal powder for powder metallurgy having such an aspect ratio has a shape that is relatively close to a spherical shape, the filling rate when formed is increased. As a result, the sintered body can be further densified.

  The major axis is the maximum length that can be taken in the projected image of the particle, and the minor axis is the maximum length that can be taken in the direction orthogonal to the major axis. Moreover, the average value of aspect ratio is calculated | required as an average value of the value of the aspect ratio measured about 100 or more particle | grains.

Moreover, the tap density of the metal powder for powder metallurgy of the present invention is preferably 3.5 g / cm ³ or more, more preferably 4 g / cm ³ or more. When the metal powder for powder metallurgy has such a large tap density, the filling property between the particles is particularly high when obtaining a compact. For this reason, a particularly dense sintered body can be finally obtained.

The specific surface area of the metal powder for powder metallurgy of the present invention is not particularly limited, but is preferably 0.1 m ² / g or more, and more preferably 0.2 m ² / g or more. Thus, if it is a metal powder for powder metallurgy with a large specific surface area, since surface activity (surface energy) will become high, it can sinter easily even if provision of less energy. Therefore, when the molded body is sintered, a difference in sintering speed hardly occurs between the inside and the outside of the molded body, and it is possible to suppress a decrease in the sintered density due to remaining voids on the inside. .

  Further, the metal powder for powder metallurgy of the present invention may be a powder (pre-alloyed powder) consisting of particles having a single composition, but a mixed powder (pre-mixed) obtained by mixing a plurality of types of particles having different compositions. Mixed powder). In the case of the premix powder, it is sufficient that the composition ratio as described above is satisfied as a whole. Thereby, premix powder brings about the same effect as mentioned above, and enables manufacture of a high-density sintered compact.

  Specific examples of the premix powder include, for example, a mixed powder of a powder obtained by subtracting C (carbon) from the composition ratio described above and C powder (carbon powder), and a first element and a second element from the composition ratio described above. Examples thereof include a mixed powder of reduced powder, first element powder, and second element powder. In addition, the combination of the multiple types of powder in the mixed powder is not particularly limited and may be any combination.

[Method for producing sintered body]
Next, a method for producing a sintered body using such metal powder for powder metallurgy according to the present invention will be described.

  The method for producing a sintered body includes [A] a composition preparation step for preparing a composition for producing a sintered body, [B] a molding step for producing a molded body, and [C] a degreasing step for performing a degreasing treatment. And [D] a firing step for firing. Hereinafter, each process will be described sequentially.

[A] Composition Preparation Step First, the metal powder for powder metallurgy according to the embodiment described above and a binder are prepared, and these are kneaded with a kneader to obtain a kneaded product.

  This kneaded material (embodiment of the compound of the present invention) contains metal powder for powder metallurgy, which is uniformly dispersed. That is, the kneaded product includes metal powder for powder metallurgy and a binder that binds the particles. According to such a kneaded material (compound), a high-density sintered body can be easily produced.

  The metal powder for powder metallurgy of the present invention is produced by various powdering methods such as an atomizing method (for example, a water atomizing method, a gas atomizing method, a high-speed rotating water atomizing method, etc.), a reduction method, a carbonyl method, and a pulverizing method. .

  Among these, the metal powder for powder metallurgy of the present invention is preferably manufactured by an atomizing method, and more preferably manufactured by a water atomizing method or a high-speed rotating water atomizing method. The atomizing method is a method for producing a metal powder by causing molten metal (molten metal) to collide with a fluid (liquid or gas) jetted at high speed, thereby pulverizing and cooling the molten metal. By producing metal powder for powder metallurgy by such an atomizing method, extremely fine powder can be produced efficiently. Moreover, the particle shape of the obtained powder becomes close to a spherical shape due to the effect of surface tension. For this reason, a thing with a high filling rate is obtained when shape | molding. That is, a powder capable of producing a high-density sintered body can be obtained.

In addition, when the water atomizing method is used as the atomizing method, the pressure of water sprayed toward the molten metal (hereinafter referred to as “atomized water”) is not particularly limited, but is preferably 75 MPa or more and 120 MPa or less (750 kgf). / Cm ² or more and 1200 kgf / cm ² or less), more preferably 90 MPa or more and 120 MPa or less (900 kgf / cm ² or more and 1200 kgf / cm ² or less).

  The temperature of the atomized water is not particularly limited, but is preferably about 1 ° C. or higher and 20 ° C. or lower.

  Furthermore, atomized water is often sprayed in a conical shape having an apex on the molten metal drop path and the outer diameter gradually decreasing downward. In this case, the apex angle of the cone formed by the atomized water is preferably about 10 ° to 40 °, and more preferably about 15 ° to 35 °. Thereby, the metal powder for powder metallurgy having the composition as described above can be reliably produced.

  Moreover, according to the water atomization method (especially high-speed rotation water flow atomization method), a molten metal can be cooled especially rapidly. For this reason, a high quality powder is obtained in a wide alloy composition.

Further, the cooling rate when the molten metal is cooled in the atomizing method is preferably 1 × 10 ⁴ ° C./s or more, and more preferably 1 × 10 ⁵ ° C./s or more. Such rapid cooling provides a homogeneous metal powder for powder metallurgy. As a result, a high-quality sintered body can be obtained.

  In addition, you may classify with respect to the metal powder for powder metallurgy obtained in this way as needed. Examples of classification methods include sieving classification, inertia classification, dry classification such as centrifugal classification, and wet classification such as sedimentation classification.

  On the other hand, examples of the binder include polyolefins such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymers, acrylic resins such as polymethyl methacrylate and polybutyl methacrylate, styrene resins such as polystyrene, polyvinyl chloride, and polyvinylidene chloride. Various resins such as polyesters such as polyamide, polyethylene terephthalate, polybutylene terephthalate, polyether, polyvinyl alcohol, polyvinylpyrrolidone or copolymers thereof, various waxes, paraffin, higher fatty acids (eg stearic acid), higher alcohols, Examples include various organic binders such as higher fatty acid esters and higher fatty acid amides. Among these, one kind or a mixture of two or more kinds can be used.

  Further, the content of the binder is preferably about 2% by mass or more and 20% by mass or less, more preferably about 5% by mass or more and 10% by mass or less of the entire kneaded product. When the content of the binder is within the above range, a molded body can be formed with good moldability, the density can be increased, and the shape stability of the molded body can be made particularly excellent. This also optimizes the difference in size between the molded body and the degreased body, the so-called shrinkage rate, and prevents the dimensional accuracy of the finally obtained sintered body from being lowered. That is, a sintered body with high density and high dimensional accuracy can be obtained.

  Moreover, a plasticizer may be added to the kneaded material as necessary. Examples of the plasticizer include phthalic acid esters (eg, DOP, DEP, DBP), adipic acid esters, trimellitic acid esters, sebacic acid esters, and the like, and one or more of these are mixed. Can be used.

  Furthermore, in addition to the metal powder for powder metallurgy, the binder, and the plasticizer, various additives such as a lubricant, an antioxidant, a degreasing accelerator, and a surfactant may be added to the kneaded material as necessary. it can.

  The kneading conditions vary depending on various conditions such as the metal composition and particle size of the metal powder for powder metallurgy used, the composition of the binder, and the blending amount thereof. For example, kneading temperature: 50 ° C. or more and 200 ° C. Or less, kneading time: about 15 minutes or more and 210 minutes or less.

  Further, the kneaded product is formed into pellets (small lumps) as necessary. The particle size of the pellet is, for example, about 1 mm to 15 mm.

  Depending on the molding method described later, a granulated powder may be produced instead of the kneaded product. These kneaded materials, granulated powders, and the like are examples of compositions that are subjected to the molding step described later.

  An embodiment of the granulated powder of the present invention includes the metal powder for powder metallurgy according to the above-described embodiment, and is formed by binding a plurality of metal particles with a binder by subjecting the powder to a granulation treatment. It is. According to such granulated powder, a high-density sintered body can be easily produced.

  Examples of the binder used in the production of the granulated powder include polyolefins such as polyethylene, polypropylene and ethylene-vinyl acetate copolymer, acrylic resins such as polymethyl methacrylate and polybutyl methacrylate, styrene resins such as polystyrene, Various resins such as polyesters such as vinyl chloride, polyvinylidene chloride, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyether, polyvinyl alcohol, polyvinyl pyrrolidone or copolymers thereof, various waxes, paraffin, higher fatty acids (eg, stearin) Acid), higher alcohols, higher fatty acid esters, higher fatty acid amides, and other organic binders. Among these, one or a mixture of two or more can be used.

  Among these, as a binder, what contains polyvinyl alcohol or polyvinylpyrrolidone is preferable. Since these binder components have high binding properties, a granulated powder can be efficiently formed even in a relatively small amount. In addition, since it has high thermal decomposability, it can be reliably decomposed and removed in a short time during degreasing and firing.

  Further, the content of the binder is preferably about 0.2% by mass or more and 10% by mass or less, more preferably about 0.3% by mass or more and 5% by mass or less of the whole granulated powder. More preferably, it is 3 mass% or more and 2 mass% or less. When the content of the binder is within the above range, the granulated powder is efficiently produced while suppressing remarkably large particles from being granulated or from leaving a large amount of non-granulated metal particles. Can be formed. Moreover, since the moldability is improved, the shape stability of the molded body can be made particularly excellent. In addition, by setting the binder content within the above range, the difference in size between the molded body and the degreased body, the so-called shrinkage rate, is optimized to prevent the dimensional accuracy of the finally obtained sintered body from being lowered. can do.

  Furthermore, various additives, such as a plasticizer, a lubricant, an antioxidant, a degreasing accelerator, and a surfactant, may be added to the granulated powder as necessary.

  On the other hand, examples of the granulation treatment include a spray drying (spray drying) method, a rolling granulation method, a fluidized bed granulation method, and a rolling fluidization granulation method.

  In the granulation treatment, a solvent that dissolves the binder is used as necessary. Examples of such solvents include water, inorganic solvents such as carbon tetrachloride, ketone solvents, alcohol solvents, ether solvents, cellosolve solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, aromatic solvents. Organic solvent such as aromatic heterocyclic compound solvent, amide solvent, halogen compound solvent, ester solvent, amine solvent, nitrile solvent, nitro solvent, aldehyde solvent, etc. are selected from these One kind or a mixture of two or more kinds is used.

  The average particle diameter of the granulated powder is not particularly limited, but is preferably about 10 μm or more and 200 μm or less, more preferably about 20 μm or more and 100 μm or less, and further preferably about 25 μm or more and 60 μm or less. The granulated powder having such a particle size has good fluidity and can more accurately reflect the shape of the mold.

  The average particle size is obtained as the particle size when the cumulative amount is 50% from the small diameter side in the cumulative particle size distribution on a mass basis obtained by the laser diffraction method.

[B] Molding Step Next, the kneaded product or the granulated powder is molded to produce a molded body having the same shape as the intended sintered body.

  There are no particular limitations on the method of manufacturing the molded body (molding method). For example, the compacting (compression molding) method, the metal powder injection molding (MIM) method, the extrusion molding method, the three-dimensional molding method ( Various molding methods such as 3D modeling method) can be used.

Among these, the molding conditions in the case of the compacting method vary depending on various conditions such as the composition and particle size of the metal powder for powder metallurgy used, the composition of the binder, and the blending amount thereof, but the molding pressure is 200 MPa or more and 1000 MPa or less. It is preferably about (2 t / cm ² or more and 10 t / cm ² or less).

Further, although the molding conditions in the metal powder injection molding method vary depending on various conditions, the material temperature is about 80 ° C. to 210 ° C., and the injection pressure is 50 MPa to 500 MPa (0.5 t / cm ^{2 to} 5 t / cm ^2). The following is preferable.

In addition, although the molding conditions in the extrusion molding method vary depending on various conditions, the material temperature is about 80 ° C. to 210 ° C., and the extrusion pressure is 50 MPa to 500 MPa (0.5 t / cm ^{2 to} 5 t / cm ² ). It is preferable that it is about.

  The molded body thus obtained is in a state where the binder is uniformly distributed in the gaps between the plurality of particles of the metal powder.

  Specific examples of the three-dimensional forming method include a material extrusion deposition method, a material jetting method, a binder jetting method, and an optical modeling method.

  In addition, the shape dimension of the molded object produced is determined in consideration of the shrinkage | contraction part of the molded object in a subsequent degreasing process and a baking process.

[C] Degreasing process Next, the obtained molded body is subjected to a degreasing treatment (debinding treatment) to obtain a degreased body.

  Specifically, the molded body is heated to decompose the binder, thereby removing the binder from the molded body and performing a degreasing process. Examples of the degreasing treatment include a method of heating the molded body, a method of exposing the molded body to a gas that decomposes the binder, and the like.

  When using the method of heating the molded body, the heating condition of the molded body is preferably about 100 ° C. or higher and 750 ° C. or lower × 0.1 hour or longer and 20 hours or shorter, although it varies slightly depending on the composition and blending amount of the binder. 150 ° C. or more and 600 ° C. or less × 0.5 hours or more and 15 hours or less is more preferable. Thereby, degreasing | defatting of a molded object can be performed sufficiently and necessary, without sintering a molded object. As a result, it is possible to reliably prevent a large amount of binder component from remaining inside the degreased body.

  The atmosphere for heating the molded body is not particularly limited, and is a reducing gas atmosphere such as hydrogen, an inert gas atmosphere such as nitrogen or argon, an oxidizing gas atmosphere such as air, or these atmospheres. The reduced pressure atmosphere etc. which reduced pressure is mentioned.

On the other hand, examples of the gas that decomposes the binder include ozone gas.
In addition, such a degreasing process is performed by dividing into a plurality of processes (steps) having different degreasing conditions, so that the binder in the molded body can be decomposed and removed more quickly and not to remain in the molded body. Can do.

  Moreover, you may make it perform machining, such as cutting, grinding | polishing, and cutting | disconnection with respect to a degreased body as needed. Since the degreased body is relatively low in hardness and relatively rich in plasticity, it can be easily machined while preventing the shape of the degreased body from collapsing. According to such machining, a sintered body with high dimensional accuracy can be easily obtained finally.

[D] Firing step The degreased body obtained in the step [C] is fired in a firing furnace to obtain a sintered body.

  By this sintering, the metal powder for powder metallurgy is diffused at the interface between the particles, resulting in sintering. At this time, the degreased body is quickly sintered by the mechanism described above. As a result, an entirely dense and dense sintered body can be obtained.

  The firing temperature varies depending on the composition, particle size and the like of the metal powder for powder metallurgy used for the production of the molded body and the degreased body, but is about 980 ° C. or higher and 1450 ° C. or lower as an example. The temperature is preferably about 1050 ° C. or higher and 1350 ° C. or lower.

  The firing time is 0.2 hours or more and 7 hours or less, and preferably 1 hour or more and 6 hours or less.

  In the firing step, the firing temperature or the firing atmosphere described later may be changed during the firing process.

  By setting the firing conditions in such a range, it is possible to sufficiently sinter the entire degreased body while preventing the sintering from proceeding excessively to cause oversintering to enlarge the crystal structure. As a result, a sintered body having a high density and particularly excellent mechanical properties can be obtained.

  Moreover, since the firing temperature is relatively low, the heating temperature in the firing furnace can be easily controlled, and thus the temperature of the degreased body is also likely to be constant. As a result, a more uniform sintered body can be produced.

  Furthermore, since the firing temperature as described above is a firing temperature that can be sufficiently realized in a general firing furnace, an inexpensive firing furnace can be used and a running cost can be suppressed. In other words, when the firing temperature is exceeded, it is necessary to use an expensive firing furnace using a special heat-resistant material, and the running cost may be increased.

  Further, the atmosphere during firing is not particularly limited, but in consideration of preventing significant oxidation of the metal powder, a reducing gas atmosphere such as hydrogen, an inert gas atmosphere such as argon, or these atmospheres The reduced pressure atmosphere etc. which reduced pressure is preferably used.

  In addition, instead of the series of steps described above, that is, instead of the composition preparation step, the molding step, the degreasing step, and the firing step, the metal powder is irradiated with an energy beam such as a laser to be sintered. May be manufactured. In this method, a metal powder spread flatly is irradiated with an energy beam such as a laser, and the metal powder is sintered in the irradiated region, thereby producing a sintered body having an arbitrary shape according to the shape of the irradiated region. (Powder sintering additive manufacturing method). Thereby, a sintered compact can be manufactured more simply.

The sintered body thus obtained has the composition of the metal powder for powder metallurgy according to the above-described embodiment.
That is, in the sintered body according to the present embodiment, Co is the main component, Cr is included in a ratio of 10% by mass to 25% by mass, and Ni is included in a ratio of 5% by mass to 40% by mass. In addition, at least one of Mo and W is included in a ratio of 2% by mass to 20% by mass in total, Si is included in a ratio of 0.3% by mass to 1.5% by mass, and C is 0.05% by mass. % To 0.8% by mass, the first element described above is included in a ratio of 0.01% to 0.5% by mass, and the second element described above is 0.01% by mass or more. It is contained at a ratio of 0.5% by mass or less.

  Such a sintered body has a high density and excellent mechanical properties without additional processing. That is, a sintered body produced by molding a composition containing the metal powder for powder metallurgy of the present invention and a binder and then degreasing and sintering the sintered body is obtained by sintering a conventional metal powder. The relative density is higher than Therefore, according to the present invention, a high-density sintered body that could not be reached without additional processing such as HIP processing can be realized without additional processing.

  Specifically, according to the present invention, although it varies slightly depending on the composition of the metal powder for powder metallurgy, an improvement in relative density of 2% or more can be expected as an example.

  As a result, the relative density of the obtained sintered body can be expected to be 97% or more as an example (preferably 98% or more, more preferably 98.5% or more). A sintered body having a relative density in such a range is excellent in mechanical properties comparable to a smelting material, although it has a shape that is almost as close as the target shape by using powder metallurgy technology. Since it has characteristics, it can be applied to various machine parts and structural parts with little post-processing.

  In addition, the obtained sintered body has a sufficiently high density and mechanical properties without any additional treatment. In order to further increase the density and improve the mechanical properties, Additional processing may be performed.

  As this additional process, for example, an additional process for increasing the density, such as the HIP process described above, may be used. Various quenching processes, various sub-zero processes, various tempering processes, various annealing processes, etc. Good. These additional processes may be performed independently or may be performed in combination.

  In the above-described firing step and various additional treatments, the light element in the metal powder (in the sintered body) volatilizes, and the composition of the finally obtained sintered body slightly changes from the composition in the metal powder. Sometimes it is.

  For example, although C varies depending on the process conditions and processing conditions, the content in the final sintered body is within the range of 5% to 100% of the content in the metal powder for powder metallurgy (preferably 30). % In the range of not less than 100% and not more than 100%).

  O also varies depending on process conditions and processing conditions, but the content in the final sintered body is in the range of 1% to 50% of the content in the metal powder for powder metallurgy (preferably 3 % In the range of not less than 50% and not more than 50%).

  On the other hand, as described above, the manufactured sintered body may be subjected to an HIP process as part of an additional process performed as necessary. However, the sintered body obtained by the present invention has already been sufficiently densified at the end of the firing step. For this reason, even if the HIP process is further performed, it is difficult to further increase the density.

  In addition, in the HIP process, it is necessary to pressurize the workpiece (sintered body) through a pressure medium, so the workpiece is contaminated, and the composition and physical properties of the workpiece are not intended due to the contamination. There is a possibility that a change occurs or the object to be processed is discolored due to contamination. Further, when the pressure is applied, residual stress is generated or increased in the object to be processed, and as this is released over time, there is a risk of causing problems such as deformation and a decrease in dimensional accuracy.

  On the other hand, according to the present invention, since a sufficiently high density sintered body can be manufactured without performing such HIP treatment, the same high density and high strength as in the case of performing HIP treatment. It is possible to obtain a sintered body that has been made into a uniform shape. Such a sintered body has less contamination, discoloration, unintended composition and change in physical properties, etc., and less defects such as deformation and deterioration of dimensional accuracy. Therefore, according to the present invention, a sintered body having high mechanical strength and dimensional accuracy and excellent durability can be efficiently produced.

  In addition, the sintered body produced according to the present invention requires almost no additional treatment for the purpose of improving mechanical properties, and therefore the composition and crystal structure are likely to be uniform throughout the sintered body. For this reason, structural isotropy is high, and it becomes the thing excellent in the durability with respect to the load from all directions irrespective of a shape.

[Heat resistant parts]
<< First Embodiment >>
The heat-resistant component of the present invention can be applied to, for example, a turbocharger component. A supercharger component described later is a first embodiment of a heat-resistant component of the present invention, and includes a sintered body according to the present embodiment. That is, at least a part of a supercharger component described later is formed of the sintered body according to the present embodiment. Such a supercharger component becomes a heat-resistant component having high density and excellent heat resistance without additional processing.

  Examples of such a turbocharger component include a turbocharger nozzle vane, a turbocharger turbine wheel, a wastegate valve, and a turbine housing. All of these turbocharger parts are exposed to high temperatures over a long period of time, and in some cases, slide between other parts, so that wear resistance is required. As described above, since the sintered body of the present invention has a high density, it has excellent heat resistance and mechanical properties. For this reason, the supercharger component excellent in durability over a long period of time can be obtained.

  Hereinafter, a turbocharger nozzle vane (hereinafter, also referred to as “nozzle vane”) will be described as an example of a supercharger component. The nozzle vane is a valve body that is used in a variable displacement turbocharger and controls the supercharging pressure by adjusting the nozzle opening.

  FIG. 1 is a side view showing a turbocharger nozzle vane to which a first embodiment of the heat-resistant component of the present invention is applied. FIG. 2 is a plan view of the nozzle vane shown in FIG. FIG. 3 is a rear view of the nozzle vane shown in FIG.

A nozzle vane 1 shown in FIG. 1 has a shaft portion 11 and a blade portion 12.
The shaft part 11 has a circular shape with the axis 13 as the central axis in the cross-sectional shape of the main part. The shaft portion 11 is supported by a nozzle mount (not shown) so that the portion on the wing portion 12 side (left side in FIG. 1) is rotatable, and the portion on the opposite side (right side in FIG. 1) from the wing portion 12 is supported. It is fixed to a nozzle plate (not shown). Thereby, the wing | blade part 12 can be rotated around the axis line 13, the angle can be changed, and a nozzle opening degree can be adjusted.

  A center hole 14 is formed on one end surface of the shaft portion 11 (the right end surface in FIG. 1). The center hole 14 is formed so that its cross-sectional shape is circular and its center coincides with the axis 13.

  In addition, a pair of flat portions 15 (two-surface cut portions) facing each other via the axis 13 are provided on the outer peripheral surface on one end side (right side in FIG. 1) of the shaft portion 11 (see FIG. 3). .

  Each such flat part 15 is used in the state contact | abutted by the abutting surface formed in the lever plate which is not shown in figure. The rotation angle around the axis 13 of the shaft portion 11 is restricted, and the rotation angle around the axis 13 of the nozzle vane 1 can be adjusted with high accuracy. Each flat portion 15 is formed to be inclined at an angle θ with respect to the protruding direction (blade surface) of the wing portion 12 (see FIG. 3).

  On the other hand, a wing portion 12 is provided on the other end side of the shaft portion 11 (left end portion in FIG. 1). That is, the wing portion 12 is provided so as to protrude from one end portion of the shaft portion 11.

  Further, a flange portion 16 that protrudes outside the shaft portion 11 is formed on the other end side of the shaft portion 11.

  As shown in FIG. 1, the wing portion 12 has a band shape extending in a direction perpendicular to the axis 13 of the shaft portion 11 in a plan view. Moreover, the protrusion length of the wing | blade part 12 from the axial part 11 is longer than one end side (lower side in FIG. 1) than the other end side (upper side in FIG. 1).

  Further, chamfers 17 and 18 are applied to the edge portions at both end portions in the width direction (left-right direction in FIG. 1) of the wing portion 12 in plan view.

  As shown in FIGS. 2 and 3, the wing 12 is slightly curved in the thickness direction. Further, the thickness of the wing portion 12 is gradually reduced toward each end in the extending direction (projecting direction).

  The nozzle vane 1 as described above is constituted by an embodiment of the sintered body of the present invention. Since the sintered body of the present invention has a high density, the nozzle vane 1 has excellent heat resistance and mechanical properties, and is excellent in wear resistance. Moreover, even if the nozzle vane 1 has a complicated shape, the dimensional accuracy is high. As a result, it is possible to realize a supercharger that is excellent in durability over a long period of time.

<< Second Embodiment >>
The heat-resistant component of the present invention is applicable to, for example, a compressor blade that is a component for a jet engine or a component for a power generation turbine. Such a compressor blade is the second embodiment of the heat-resistant component of the present invention, and at least a part thereof is configured by the embodiment of the sintered body of the present invention.

  FIG. 4 is a perspective view showing a compressor blade to which the second embodiment of the heat-resistant component of the present invention is applied. The compressor blade 2 shown in FIG. 4 includes an inner rim 21 and an outer rim 22 provided concentrically with each other, and a blade portion 23 provided between them and arranged in the circumferential direction of the inner rim 21. I have. The inner rim 21 and the outer rim 22 each have an annular shape. Moreover, the wing | blade part 23 has comprised flat form containing the curved surface. The blade tip (end surface) of the blade portion 23 is coupled to the outer peripheral surface of the inner rim 21 and the inner peripheral surface of the outer rim 22. FIG. 4 shows a part of the compressor blade 2 cut out.

  Such a compressor blade 2 is one of the components constituting a jet engine or a power generation gas turbine, and rotates the turbine shaft provided further inside the inner rim 21 when the blade portion 23 receives gas. Let Thereby, a compressor can compress gas in a jet engine or a gas turbine for power generation.

  The inner rim 21, the outer rim 22 and the wing 23 may be separate members, but the compressor wing 2 shown in FIG. 4 has the inner rim 21, the outer rim 22 and the wing 23 integrated together. ing. For this reason, the relative positional accuracy of each part is high, and it is excellent in the performance as a compressor blade. And the compressor blade 2 excellent in dimensional accuracy is obtained by comprising the whole compressor blade 2 by embodiment of the sintered compact of this invention.

  In general, compressor blades are required to have a three-dimensional shape that includes a thinner and curved curved surface because of the need to improve aerodynamic performance.

  With respect to such a problem, since the entire compressor blade 2 is composed of a sintered body manufactured by a powder metallurgy method, even if the blade portion 23 has a thin and complicated three-dimensional shape, A highly accurate compressor blade 2 can be realized.

  In addition, since the sintered body according to the present embodiment has high density and excellent heat resistance, it contributes to improvement of mechanical characteristics of the compressor blade 2. That is, since the compressor blade is generally a component constituting the air flow path, sufficient fatigue strength, wear resistance, etc. are required for vibration even at high temperatures.

  With respect to such a problem, the compressor blade 2 is composed of the sintered body according to the present embodiment, and therefore has high density and excellent heat resistance and sufficient wear resistance. Therefore, the compressor blade 2 excellent in durability over a long period of time can be obtained.

  Furthermore, since the compressor blades 2 are manufactured using various molding methods, post-sintering after sintering is hardly required or the processing amount can be reduced. Further, as described above, since high density is achieved, additional processing such as HIP processing is not necessary. For this reason, the manufacturing cost can be reduced and the occurrence of defects caused by post-processing marks can be minimized.

  As mentioned above, although the metal powder for powder metallurgy, the compound, the granulated powder, the sintered compact, and the heat-resistant component of the present invention have been described based on preferred embodiments, the present invention is not limited to these.

  For example, the sintered body of the present invention can be used for automobile parts, bicycle parts, railway vehicle parts, marine parts, aircraft parts, parts for transportation equipment such as parts for space transport aircraft (for example, rockets), personal computers. Parts, parts for electronic devices such as parts for mobile phone terminals, parts for electrical equipment such as refrigerators, washing machines and air conditioners, machine parts such as machine tools and semiconductor manufacturing equipment, nuclear power plants, thermal power generation Plants, hydroelectric power plants, refineries, plant parts such as chemical complexes, clock parts, metal tableware, jewelry, ornaments such as eyeglass frames, surgical instruments, artificial bones, artificial teeth, artificial tooth roots, teeth In addition to medical devices such as orthodontic parts, they may be used for all structural parts.

  Furthermore, the heat-resistant parts of the present invention include, for example, various power generation-related parts such as nuclear parts and gas turbine parts, automobile engines, in addition to the above-described turbocharger parts, jet engine parts, and power turbine parts. Parts, various engine parts such as rocket engine parts, boiler parts, heat exchanger parts, exhaust gas treatment equipment parts, heating furnace parts, fuel cell parts, heat-resistant bolts, heat-resistant springs, heat-resistant valves, etc. It can also be applied to parts.

Next, examples of the present invention will be described.
1. Production of sintered body (Zr-Nb system) (Sample No. 1)
[1] First, a metal powder having the composition shown in Table 1 manufactured by the water atomization method was prepared. The average particle size of the prepared metal powder is shown in Table 4.
The powder composition shown in Table 1 was identified and quantified by inductively coupled plasma emission spectrometry (ICP analysis). For ICP analysis, an ICP device (CIROS120 type) manufactured by Rigaku Corporation was used. For carbon identification and quantification, a carbon / sulfur analyzer (CS-200) manufactured by LECO was used. Further, an oxygen / nitrogen analyzer (TC-300 / EF-300) manufactured by LECO was used for identification and quantification of O.

  [2] Next, the metal powder and a mixture of polypropylene and wax (organic binder) were weighed and mixed so that the mass ratio was 9: 1 to obtain a mixed raw material.

[3] Next, the mixed raw material was kneaded with a kneader to obtain a compound.
[4] Next, this compound was molded by an injection molding machine under the molding conditions shown below to produce a molded body.

<Molding conditions>
-Material temperature: 150 ° C
Injection pressure: 11 MPa (110 kgf / cm ² )

  [5] Next, the obtained molded body was subjected to heat treatment (degreasing treatment) under the following degreasing conditions to obtain a degreased body.

<Degreasing conditions>
・ Degreasing temperature: 500 ° C
・ Degreasing time: 1 hour (holding time at degreasing temperature)
・ Degreasing atmosphere: Nitrogen atmosphere

  [6] Next, the obtained degreased body was fired under the firing conditions shown below. This obtained the sintered compact. The shape of the sintered body was a cylindrical shape having a diameter of 10 mm and a thickness of 5 mm.

<Baking conditions>
・ Baking temperature: 1250 ° C
-Firing time: 3 hours (holding time at the firing temperature)
・ Baking atmosphere: Argon atmosphere

(Sample Nos. 2 to 30)
Except for changing the composition and the like of the metal powder for powder metallurgy as shown in Table 1, each sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1. Sample No. About 30 sintered compacts, the HIP process was performed on the following conditions after baking. Sample No. The sintered bodies 16 and 17 were obtained using metal powders produced by the gas atomization method. In Table 1, “gas” is written in the remarks column.

<HIP processing conditions>
・ Heating temperature: 1100 ° C
・ Heating time: 2 hours ・ Pressure: 100 MPa

In Table 1, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a trace amount of impurities, but the description in Table 1 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 1 was 0.5 mass% or less.

(Sample No. 31)
[1] First, a metal powder having the composition shown in Table 2 was sampled. As in the case of 1, it was produced by the water atomization method. The average particle size of the prepared metal powder is shown in Table 5.

  [2] Next, the metal powder was granulated by spray drying. The binder used at this time was polyvinyl alcohol, and the amount used was 1 part by mass with respect to 100 parts by mass of the metal powder. Moreover, 50 mass parts solvent (ion-exchange water) was used with respect to 1 mass part of polyvinyl alcohol. This obtained the granulated powder with an average particle diameter of 50 micrometers.

  [3] Next, this granulated powder was compacted under the molding conditions shown below. A press molding machine was used for this molding. Moreover, the shape of the molded body to be produced was a 20 mm square cube shape.

<Molding conditions>
・ Material temperature: 90 ℃
Molding pressure: 600 MPa (6 t / cm ² )

  [4] Next, the obtained molded body was subjected to heat treatment (degreasing treatment) under the following degreasing conditions to obtain a degreased body.

<Degreasing conditions>
・ Degreasing temperature: 450 ° C
・ Degreasing time: 2 hours (holding time at the degreasing temperature)
・ Degreasing atmosphere: Nitrogen atmosphere

  [5] Next, the obtained degreased body was fired under the firing conditions shown below. This obtained the sintered compact.

<Baking conditions>
・ Baking temperature: 1250 ° C
-Firing time: 3 hours (holding time at the firing temperature)
・ Baking atmosphere: Argon atmosphere

(Sample No. 32-45)
Except for changing the composition of the metal powder for powder metallurgy as shown in Table 2, each sample No. In the same manner as in the case of 31, a sintered body was obtained. Sample No. About 45 sintered compacts, after baking, the HIP process was performed on condition of the following. Sample No. The sintered bodies 38 and 39 were obtained using metal powders produced by the gas atomization method. In Table 2, “gas” is written in the remarks column.

<HIP processing conditions>
・ Heating temperature: 1100 ° C
・ Heating time: 2 hours ・ Pressure: 100 MPa

In Table 2, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a small amount of impurities, but the description in Table 2 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 2 was 0.5 mass% or less.

(Sample No. 46)
[1] First, a premix powder having the composition shown in Table 3 manufactured by the water atomization method was prepared. Here, the “premix powder” refers to a mixed powder of powder obtained by subtracting the C (carbon) component from the composition ratio shown in Table 3 and C powder. In addition, Table 6 shows the average particle diameter of the prepared metal powder (powder obtained by reducing the C component).

  [2] Next, the premix powder and a mixture of polypropylene and wax (organic binder) were weighed and mixed so as to have a mass ratio of 9: 1 to obtain a mixed raw material.

[3] Next, the mixed raw material was kneaded with a kneader to obtain a compound.
[4] Next, this compound was molded by an injection molding machine under the molding conditions shown below to produce a molded body.

<Molding conditions>
-Material temperature: 150 ° C
Injection pressure: 11 MPa (110 kgf / cm ² )

  [5] Next, the obtained molded body was subjected to heat treatment (degreasing treatment) under the following degreasing conditions to obtain a degreased body.

<Degreasing conditions>
・ Degreasing temperature: 500 ° C
・ Degreasing time: 1 hour (holding time at degreasing temperature)
・ Degreasing atmosphere: Nitrogen atmosphere

  [6] Next, the obtained degreased body was fired under the firing conditions shown below. This obtained the sintered compact. The shape of the sintered body was a cylindrical shape having a diameter of 10 mm and a thickness of 5 mm.

<Baking conditions>
・ Baking temperature: 1250 ° C
-Firing time: 3 hours (holding time at the firing temperature)
・ Baking atmosphere: Argon atmosphere

(Sample No. 47-60)
Except for changing the composition and the like of the metal powder for powder metallurgy as shown in Table 3, each sample No. In the same manner as in the case of No. 46, a sintered body was obtained. Sample No. About 60 sintered compacts, the HIP process was performed on the following conditions after baking.

<HIP processing conditions>
・ Heating temperature: 1100 ° C
・ Heating time: 2 hours ・ Pressure: 100 MPa

In Table 3, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a small amount of impurities, but the description in Table 3 was omitted. In addition, the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 3 was all 0.5 mass% or less.

2. Evaluation of Sintered Body (Zr-Nb System) 2.1 Evaluation of Relative Density With respect to the sintered bodies manufactured using the above metal powder, the sintered density was measured according to the method for measuring the density of the sintered metal material specified in JIS Z 2501 (2000), and each sintered body was measured. The relative density of each sintered body was calculated with reference to the true density of the metal powder for powder metallurgy used to manufacture the powder.
The calculation results are shown in Tables 4-6.

2.2 Evaluation of hardness Each sample No. shown in Tables 1-3. Vickers hardness was measured according to the test method of the Vickers hardness test prescribed | regulated to JISZ2244 (2009) about the sintered compact manufactured using this metal powder.

  The measured hardness was evaluated according to the following evaluation criteria. In the evaluation, the hardness of the sample described as “* 1” in the remarks column of each table was set to 100 for the hardness of the sample described as “* 1 standard” in each table. The relative value was evaluated by observing the following evaluation criteria. Similarly, the hardness of the sample described as “* 2” in the remarks column of Table 1 is relative to the hardness of the sample described as “Standard of * 2” in Table 1 as 100. Regarding the hardness of the sample whose value is described as “* 3”, the relative value when the hardness of the sample described as “standard of * 3” in Table 1 is taken as 100 is expressed as “* 4”. The hardness of the sample described as “* 4” is determined by observing the relative value when the hardness of the sample described as “* 4 standard” in Table 1 is 100, according to the following evaluation criteria. evaluated.

<Vickers hardness evaluation criteria>
A: Relative value of Vickers hardness is 110 or more B: Relative value of Vickers hardness is 105 or more and less than 110 C: Relative value of Vickers hardness is 100 or more and less than 105 D: Relative of Vickers hardness The evaluation result whose value is less than 100 is shown in Tables 4-6.

2.3 Evaluation of tensile strength, 0.2% proof stress and elongation The sintered body produced using the metal powder was measured for tensile strength, 0.2% proof stress, and elongation according to a metal material tensile test method defined in JIS Z 2241 (2011).

  And about these measured physical-property values, it evaluated in accordance with the following evaluation criteria. In the evaluation, regarding the physical property values of the samples described as “* 1” in the remarks column of each table, the physical property values of the samples described as “* 1 standard” in each table are set to 100. The relative value was evaluated by observing the following evaluation criteria. Similarly, the physical property value of the sample described as “* 2” in the remarks column of Table 1 is relative to the physical property value of the sample described as “Standard of * 2” in Table 1 as 100. As for the physical property value of the sample whose value is described as “* 3”, the relative value when the physical property value of the sample described as “* 3 standard” in Table 1 is set to 100 is “* 4”. The physical property values of the samples described as “* 4” are as follows. The relative values when the physical property values of the samples described as “* 4 criteria” in Table 1 are set to 100 are as follows. evaluated.

<Evaluation criteria for tensile strength>
A: The relative value of the tensile strength of the sintered body is 109 or more B: The relative value of the tensile strength of the sintered body is 106 or more and less than 109 C: The relative value of the tensile strength of the sintered body is 103 D: The relative value of the tensile strength of the sintered body is 100 or more and less than 103 E: The relative value of the tensile strength of the sintered body is 97 or more and less than 100 F: Tensile strength of the sintered body Relative strength value is less than 97

<Evaluation criteria for 0.2% proof stress>
A: The relative value of 0.2% yield strength of the sintered body is 109 or more B: The relative value of 0.2% yield strength of the sintered body is 106 or more and less than 109 C: 0.2% of the sintered body The relative value of the yield strength is 103 or more and less than 106 D: The relative value of the 0.2% yield strength of the sintered body is 100 or more and less than 103 E: The relative value of the 0.2% yield strength of the sintered body is 97 or more and 100 F: Relative value of 0.2% proof stress of the sintered body is less than 97

<Evaluation criteria for elongation>
A: Relative value of elongation of sintered body is 115 or more B: Relative value of elongation of sintered body is 110 or more and less than 115 C: Relative value of elongation of sintered body is 105 or more and less than 110 D : The relative value of the elongation of the sintered body is 100 or more and less than 105 E: The relative value of the elongation of the sintered body is 95 or more and less than 100 F: The relative value of the elongation of the sintered body is less than 95 The evaluation results are shown in Tables 4-6.

  As is apparent from Tables 4 to 6, the sintered body corresponding to the example has a higher relative density than the sintered body corresponding to the comparative example (excluding the sintered body subjected to HIP treatment). Was recognized. It was also recognized that there were significant differences in properties such as tensile strength, 0.2% proof stress and elongation.

  On the other hand, when the respective physical property values were compared between the sintered body corresponding to the example and the sintered body subjected to the HIP treatment, it was recognized that both were comparable.

3. Production of sintered body (Hf-Nb series) (Sample Nos. 61-74)
Except for changing the composition and the like of the metal powder for powder metallurgy as shown in Table 7, each sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1.

In Table 7, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a small amount of impurities, but the description in Table 7 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 7 was 0.5 mass% or less.

(Sample No. 75-81)
Except for changing the composition and the like of the metal powder for powder metallurgy as shown in Table 8, each sample No. In the same manner as in the case of No. 46, a sintered body was obtained.

In Table 8, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a small amount of impurities, but the description in Table 8 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 8 was 0.5 mass% or less.

4). 4. Evaluation of Sintered Body (Hf—Nb System) 4.1 Evaluation of Relative Density Each sample No. shown in Tables 7 and 8 With respect to the sintered bodies manufactured using the above metal powder, the sintered density was measured according to the method for measuring the density of the sintered metal material specified in JIS Z 2501 (2000), and each sintered body was measured. The relative density of each sintered body was calculated with reference to the true density of the metal powder for powder metallurgy used to manufacture the powder.
The calculation results are shown in Tables 9 and 10.

4.2 Evaluation of hardness Each sample No. shown in Tables 7 and 8 was used. The Vickers hardness was measured according to the method of the Vickers hardness test prescribed | regulated to JISZ2244 (2009) about the sintered compact manufactured using this metal powder.

The measured hardness was evaluated according to the evaluation criteria described in 2.2.
The evaluation results are shown in Tables 9 and 10.

4.3 Evaluation of tensile strength, 0.2% proof stress and elongation Each sample No. shown in Tables 7 and 8 The sintered body produced using the metal powder was measured for tensile strength, 0.2% proof stress, and elongation according to a metal material tensile test method defined in JIS Z 2241 (2011).

The measured physical property values were evaluated according to the evaluation criteria described in 2.3.
The evaluation results are shown in Tables 9 and 10.

  As can be seen from Tables 9 and 10, the sintered body corresponding to the example was found to have a higher relative density than the sintered body corresponding to the comparative example. It was also recognized that there were significant differences in properties such as tensile strength, 0.2% proof stress and elongation.

5. Production of sintered body (Ti-Nb system) (Sample Nos. 82-91)
Except for changing the composition of the metal powder for powder metallurgy as shown in Table 11, each sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1.

In Table 11, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples” and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a trace amount of impurities, but the description in Table 11 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 11 was 0.5 mass% or less.

6). Evaluation of Sintered Body (Ti-Nb System) 6.1 Evaluation of Relative Density With respect to the sintered bodies manufactured using the above metal powder, the sintered density was measured according to the method for measuring the density of the sintered metal material specified in JIS Z 2501 (2000), and each sintered body was measured. The relative density of each sintered body was calculated with reference to the true density of the metal powder for powder metallurgy used to manufacture the powder.
Table 12 shows the calculation results.

6.2 Evaluation of Hardness Each sample No. shown in Table 11 The Vickers hardness was measured according to the method of the Vickers hardness test prescribed | regulated to JISZ2244 (2009) about the sintered compact manufactured using this metal powder.

The measured hardness was evaluated according to the evaluation criteria described in 2.2.
The evaluation results are shown in Table 12.

6.3 Evaluation of tensile strength, 0.2% proof stress and elongation Each sample No. shown in Table 11 The sintered body produced using the metal powder was measured for tensile strength, 0.2% proof stress, and elongation according to a metal material tensile test method defined in JIS Z 2241 (2011).

The measured physical property values were evaluated according to the evaluation criteria described in 2.3.
The evaluation results are shown in Table 12.

  As apparent from Table 12, the sintered body corresponding to the example was found to have a higher relative density than the sintered body corresponding to the comparative example. It was also recognized that there were significant differences in properties such as tensile strength, 0.2% proof stress and elongation.

7). Production of sintered body (Nb-Ta series) (Sample Nos. 92 to 101)
Except for changing the composition and the like of the metal powder for powder metallurgy as shown in Table 13, Sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1.

In Table 13, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a small amount of impurities, but the description in Table 13 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 13 was 0.5 mass% or less.

8). Evaluation of Sintered Body (Nb-Ta System) 8.1 Evaluation of Relative Density Each sample No. shown in Table 13 With respect to the sintered bodies manufactured using the above metal powder, the sintered density was measured according to the method for measuring the density of the sintered metal material specified in JIS Z 2501 (2000), and each sintered body was measured. The relative density of each sintered body was calculated with reference to the true density of the metal powder for powder metallurgy used to manufacture the powder.
Table 14 shows the calculation results.

8.2 Evaluation of Hardness Each sample No. shown in Table 13 The Vickers hardness was measured according to the method of the Vickers hardness test prescribed | regulated to JISZ2244 (2009) about the sintered compact manufactured using this metal powder.

The measured hardness was evaluated according to the evaluation criteria described in 2.2.
The evaluation results are shown in Table 14.

8.3 Evaluation of Tensile Strength, 0.2% Yield Strength and Elongation Each sample No. shown in Table 13 The sintered body produced using the metal powder was measured for tensile strength, 0.2% proof stress, and elongation according to a metal material tensile test method defined in JIS Z 2241 (2011).

The measured physical property values were evaluated according to the evaluation criteria described in 2.3.
The evaluation results are shown in Table 14.

  As is clear from Table 14, the sintered body corresponding to the example was found to have a higher relative density than the sintered body corresponding to the comparative example. It was also recognized that there were significant differences in properties such as tensile strength, 0.2% proof stress and elongation.

9. Production of sintered body (Y-Nb system) (Sample Nos. 102 to 112)
Except for changing the composition of the metal powder for powder metallurgy as shown in Table 15, each sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1.

In Table 15, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a trace amount of impurities, but the description in Table 15 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 15 was 0.5 mass% or less.

10. Evaluation of Sintered Body (Y-Nb System) 10.1 Evaluation of Relative Density With respect to the sintered bodies manufactured using the above metal powder, the sintered density was measured according to the method for measuring the density of the sintered metal material specified in JIS Z 2501 (2000), and each sintered body was measured. The relative density of each sintered body was calculated with reference to the true density of the metal powder for powder metallurgy used to manufacture the powder.
Table 16 shows the calculation results.

10.2 Evaluation of Hardness Each sample No. shown in Table 15 The Vickers hardness was measured according to the method of the Vickers hardness test prescribed | regulated to JISZ2244 (2009) about the sintered compact manufactured using this metal powder.

The measured hardness was evaluated according to the evaluation criteria described in 2.2.
The evaluation results are shown in Table 16.

10.3 Evaluation of tensile strength, 0.2% proof stress and elongation Each sample No. shown in Table 15 The sintered body produced using the metal powder was measured for tensile strength, 0.2% proof stress, and elongation according to a metal material tensile test method defined in JIS Z 2241 (2011).

The measured physical property values were evaluated according to the evaluation criteria described in 2.3.
The evaluation results are shown in Table 16.

  As is clear from Table 16, the sintered body corresponding to the example was found to have a higher relative density than the sintered body corresponding to the comparative example. It was also recognized that there were significant differences in properties such as tensile strength, 0.2% proof stress and elongation.

11. Production of sintered body (V-Nb system) (Sample Nos. 113 to 122)
Except for changing the composition and the like of the metal powder for powder metallurgy as shown in Table 17, each sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1.

In Table 17, each sample No. Among the metal powders for powder metallurgy, those corresponding to the present invention are referred to as “Examples”, and those not corresponding to the present invention are referred to as “Comparative Examples”.
Each metal powder for powder metallurgy contained a small amount of impurities, but the description in Table 17 was omitted. In addition, all the content rate of O (oxygen) of the metal powder which concerns on the Example described in Table 17 was 0.5 mass% or less.

12 Evaluation of Sintered Body (V-Nb System) 12.1 Evaluation of Relative Density With respect to the sintered bodies manufactured using the above metal powder, the sintered density was measured according to the method for measuring the density of the sintered metal material specified in JIS Z 2501 (2000), and each sintered body was measured. The relative density of each sintered body was calculated with reference to the true density of the metal powder for powder metallurgy used to manufacture the powder.
Table 18 shows the calculation results.

12.2 Evaluation of Hardness Each sample No. shown in Table 17 The Vickers hardness was measured according to the method of the Vickers hardness test prescribed | regulated to JISZ2244 (2009) about the sintered compact manufactured using this metal powder.

The measured hardness was evaluated according to the evaluation criteria described in 2.2.
The evaluation results are shown in Table 18.

12.3 Evaluation of tensile strength, 0.2% proof stress and elongation Each sample No. shown in Table 17 The sintered body produced using the metal powder was measured for tensile strength, 0.2% proof stress, and elongation according to a metal material tensile test method defined in JIS Z 2241 (2011).

The measured physical property values were evaluated according to the evaluation criteria described in 2.3.
The evaluation results are shown in Table 18.

  As is clear from Table 18, the sintered body corresponding to the example was found to have a higher relative density than the sintered body corresponding to the comparative example. It was also recognized that there were significant differences in properties such as tensile strength, 0.2% proof stress and elongation.

  In addition to the examples described in Tables 1 to 18, as examples of combinations of the first element and the second element, the same applies to Ti-Zr-based, Zr-Ta-based, and Zr-V-based metal powders. Sintered bodies were manufactured as described above, and showed the same tendency as described above with respect to relative density, hardness, tensile strength, proof stress and elongation.

DESCRIPTION OF SYMBOLS 1 ... Nozzle vane, 2 ... Compressor blade, 11 ... Shaft part, 12 ... Blade part, 13 ... Axis, 14 ... Center hole, 15 ... Flat part, 16 ... Flange part, 17 ... Chamfering, 18 ... Chamfering, 21 ... Inside Rim, 22 ... outer rim, 23 ... wing, θ ... angle

Claims (17)

Co is the main component,
Cr is contained in a proportion of 10% by mass to 25% by mass,
Ni is contained in a proportion of 5% by mass or more and 40% by mass or less,
At least one of Mo and W is included in a ratio of 2% by mass to 20% by mass in total,
Si is contained in a proportion of 0.3% by mass or more and 1.5% by mass or less,
C is included in a proportion of 0.05% by mass or more and 0.8% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a proportion of 0.01% by mass to 0.5% by mass,
The metal powder for powder metallurgy, characterized in that the second element is contained in a proportion of 0.01% by mass or more and 0.5% by mass or less. Co is the main component,
Cr is contained at a ratio of 15% by mass or more and 24% by mass or less,
Ni is contained in a ratio of 7% by mass to 32% by mass,
At least one of Mo and W is included in a ratio of 5% by mass to 18% by mass in total,
Si is contained at a ratio of 0.4% by mass or more and 1.2% by mass or less,
C is contained in a proportion of 0.2% by mass or more and 0.6% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a ratio of 0.03% by mass to 0.2% by mass,
The metal powder for powder metallurgy, characterized in that the second element is contained in a proportion of 0.03% by mass or more and 0.2% by mass or less. Co is the main component,
Cr is contained in a proportion of 18% by mass to 23% by mass,
Ni is contained in a proportion of 9% by mass to 36% by mass,
At least one of Mo and W is included in a ratio of 7% by mass to 16% by mass in total,
Si is contained in a proportion of 0.5% by mass or more and 1% by mass or less,
C is contained in a proportion of 0.3% by mass or more and 0.5% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a proportion of 0.05% by mass or more and 0.1% by mass or less,
The metal powder for powder metallurgy, wherein the second element is contained in a proportion of 0.05% by mass or more and 0.1% by mass or less.   The metal powder for powder metallurgy according to any one of claims 1 to 3, further comprising Fe in a proportion of 0.5 mass% to 5 mass%.   The metal powder for powder metallurgy according to any one of claims 1 to 3, further comprising Fe in a proportion of 0.8 mass% to 3 mass%.   The metal powder for powder metallurgy according to any one of claims 1 to 3, further comprising Fe in a proportion of 1% by mass to 2.5% by mass. When the value obtained by dividing the content of the first element by the atomic weight of the first element is X1, and the value obtained by dividing the content of the second element by the atomic weight of the second element is X2, X1 / X2 is The metal powder for powder metallurgy according to any one of claims 1 to 6, which is 0.3 or more and 3 or less. When the value obtained by dividing the content of the first element by the atomic weight of the first element is X1, and the value obtained by dividing the content of the second element by the atomic weight of the second element is X2, X1 / X2 is The metal powder for powder metallurgy according to any one of claims 1 to 6, which is 0.5 or more and 2 or less. When the value obtained by dividing the content of the first element by the atomic weight of the first element is X1, and the value obtained by dividing the content of the second element by the atomic weight of the second element is X2, X1 / X2 is The metal powder for powder metallurgy according to any one of claims 1 to 6, wherein the metal powder is 0.75 to 1.3.   The metal powder for powder metallurgy according to any one of claims 1 to 9, wherein the total content of the first element and the content of the second element is 0.05% by mass or more and 0.6% by mass or less. .   The metal powder for powder metallurgy according to any one of claims 1 to 9, wherein the total content of the first element and the content of the second element is 0.10 mass% or more and 0.48 mass% or less. .   The metal powder for powder metallurgy according to any one of claims 1 to 9, wherein the total content of the first element and the content of the second element is 0.12% by mass or more and 0.24% by mass or less. .   The metal powder for powder metallurgy according to any one of claims 1 to 12, wherein the average particle size is 0.5 µm or more and 30 µm or less.   A compound comprising the metal powder for powder metallurgy according to any one of claims 1 to 13.   A granulated powder comprising the metal powder for powder metallurgy according to any one of claims 1 to 13. Co is the main component,
Cr is contained in a proportion of 10% by mass to 25% by mass,
Ni is contained in a proportion of 5% by mass or more and 40% by mass or less,
At least one of Mo and W is included in a ratio of 2% by mass to 20% by mass in total,
Si is contained in a proportion of 0.3% by mass or more and 1.5% by mass or less,
C is included in a proportion of 0.05% by mass or more and 0.8% by mass or less,
Ti, V, Y, Zr, and one element selected from the group consisting of Nb and Hf as a first element, V, Z r, Nb, with one kind of element selected from the group consisting of Hf and Ta When the element in the periodic table of elements is larger than the first element or the element in the periodic table of elements is the same as the first element and the element in the periodic table of elements is larger than the first element is the second element. ,
The first element is included in a proportion of 0.01% by mass to 0.5% by mass,
A sintered body characterized in that the second element is contained in a proportion of 0.01% by mass or more and 0.5% by mass or less.   A heat-resistant component comprising the sintered body according to claim 16.

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