WO2016110929A1 - Poudre métallique pour métallurgie des poudres, composé, poudre granulée, objet fritté, et article décoratif - Google Patents

Poudre métallique pour métallurgie des poudres, composé, poudre granulée, objet fritté, et article décoratif Download PDF

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Publication number
WO2016110929A1
WO2016110929A1 PCT/JP2015/006499 JP2015006499W WO2016110929A1 WO 2016110929 A1 WO2016110929 A1 WO 2016110929A1 JP 2015006499 W JP2015006499 W JP 2015006499W WO 2016110929 A1 WO2016110929 A1 WO 2016110929A1
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Prior art keywords
sintered body
mass
powder
metal powder
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English (en)
Japanese (ja)
Inventor
貴之 田村
中村　英文
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Seiko Epson Corp
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Seiko Epson Corp
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Priority claimed from JP2015255353A external-priority patent/JP6358246B2/ja
Application filed by Seiko Epson Corp filed Critical Seiko Epson Corp
Priority to EP15876807.7A priority Critical patent/EP3243581A4/fr
Priority to US15/542,294 priority patent/US11498123B2/en
Publication of WO2016110929A1 publication Critical patent/WO2016110929A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26B—HAND-HELD CUTTING TOOLS NOT OTHERWISE PROVIDED FOR
    • B26B3/00—Hand knives with fixed blades
    • B26B3/02—Table-knives
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases

Definitions

  • the present invention relates to a metal powder for powder metallurgy, a compound, a granulated powder, a sintered body, and a decorative article.
  • a composition containing a metal powder and a binder is formed into a desired shape to obtain a formed body, and then the formed body is degreased and sintered to produce 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.
  • Patent Document 1 proposes a metal powder for powder metallurgy composed of at least one element selected from the group consisting of Fe, Co, and Ni and unavoidable elements including Zr and Si. According to such metal powder for powder metallurgy, the sinterability is improved by the action of Zr, and a high-density sintered body can be easily manufactured.
  • Patent Document 2 discloses that C is 0.03% by weight or less, Ni is 8 to 32% by weight, Cr is 12 to 32% by weight, Mo is 1 to 7% by weight, and the balance is 100 parts by weight of stainless steel powder composed of Fe and inevitable impurities. And a metal injection molding composition characterized by comprising 0.1 to 5.5 parts by weight of one or more powders of Ti or / and Nb having an average particle size of 10 to 60 ⁇ m . By using such a composition in which two kinds of powders are mixed, a sintered body having a high sintered density and excellent corrosion resistance can be obtained.
  • Patent Document 3 C: 0.95 to 1.4 mass%, Si: 1.0 mass% or less, Mn: 1.0 mass% or less, Cr: 16 to 18 mass%, Nb: The composition is comprised of 0.02 to 3% by mass, the balance being Fe and inevitable impurities, the density after sintering is 7.65 to 7.75 g / cm 3 , and is molded by a metal injection molding method. A needle seal for a needle valve is disclosed. Thereby, a high-density needle seal is obtained.
  • the sintered body thus obtained has been widely used for various machine parts and structural parts.
  • An object of the present invention is to provide a metal powder for powder metallurgy capable of producing a high-density sintered body, a compound and a granulated powder, and a high-density sintered body and a decorative article produced using the metal powder for powder metallurgy. Is to provide.
  • the metal powder for powder metallurgy of the present invention is mainly composed of Co, Cr is contained in a proportion of 16% by mass to 35% by mass, Si is contained in a proportion of 0.3% by mass or more and 2.0% by mass or less,
  • One element selected from the group consisting of Ti, V, Y, Zr, Nb, Hf and Ta is the first element, and one element selected from the group, the group in the periodic table of elements is When the element larger than the first element or the group in the periodic table of the elements is the same as the first element and the element in the periodic table of the elements 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 alloy composition can be optimized and the densification during the sintering of the metal powder for powder metallurgy can be promoted.
  • a metal powder for powder metallurgy capable of producing a high-density sintered body without additional processing is obtained.
  • Mo is further contained in a proportion of 3% by mass or more and 12% by mass or less. Thereby, the corrosion resistance of a sintered compact can be improved more.
  • N is further contained in a ratio of 0.09 mass% to 0.5 mass%. Thereby, the toughness and impact resistance of a sintered compact can be improved more.
  • a value obtained by dividing the content ratio E2 of the second element by the mass number of the second element is X2, and the content ratio E1 of the first element is the mass number of the first element.
  • X1 / X2 is preferably 0.3 or more and 3 or less.
  • the metal powder for powder metallurgy 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. 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.
  • 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. As a result, the density of the sintered body to be manufactured becomes necessary and sufficient.
  • the average particle size is preferably 0.5 ⁇ m or more and 30 ⁇ m or less.
  • the compound of the present invention comprises the metal powder for powder metallurgy of the present invention and a binder for binding particles of the metal powder for powder metallurgy. 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 16% by mass to 35% by mass, Si is contained in a proportion of 0.3% by mass or more and 2.0% by mass or less,
  • One element selected from the group consisting of Ti, V, Y, Zr, Nb, Hf and Ta is the first element, and one element selected from the group, the group in the periodic table of elements is When the element larger than the first element or the group in the periodic table of the elements is the same as the first element and the element in the periodic table of the elements 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 decorative article of the present invention is characterized in that it includes a portion made of the sintered body of the present invention. Thereby, a high-density ornament is obtained, without performing an additional process.
  • the decorative article of the present invention is preferably a watch exterior part. As a result, a high-density watch exterior part can be obtained without additional processing.
  • the decorative article of the present invention is preferably a jewelry. As a result, a high-density accessory can be obtained without additional processing.
  • the decorative article of the present invention is preferably a tableware. Thereby, a high-density tableware is obtained, without performing an additional process.
  • FIG. 3 is a side view showing a turbocharger nozzle vane (when the wing 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.
  • a composition containing 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.
  • 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.
  • the obtained sintered body may be further densified by performing additional processing such as hot isostatic pressing (HIP processing).
  • additional processing involves a lot of labor and cost, and is an obstacle when expanding the use of the sintered body.
  • 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.
  • the metal powder for powder metallurgy according to the present invention includes Cr in a proportion of 16% by mass to 35% by mass and Si in a proportion of 0.3% by mass to 2.0% by mass.
  • the first element described later is contained in a proportion of 0.01% by mass or more and 0.5% by mass or less
  • the second element described later is contained in a proportion of 0.01% by mass or more and 0.5% by mass or less
  • the balance Is a metal powder composed of Co and other elements.
  • 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.
  • a sintered body having excellent mechanical properties can be obtained.
  • 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 the group consisting of the seven elements. Selected from the group consisting of the seven elements and the first element selected from the group consisting of the seven elements.
  • the element in the periodic table of the elements is the same element, and the period in the periodic table of the elements is larger than the first element.
  • the alloy composition of the metal powder for powder metallurgy according to the present invention will be described in more detail.
  • the metal powder for powder metallurgy may be simply referred to as “metal powder”.
  • Cr Cr (chromium) Cr is an element that imparts corrosion resistance to the sintered body to be produced.
  • a metal powder containing Cr By using a metal powder containing Cr, a sintered body that can maintain high mechanical properties over a long period of time can be obtained. For this reason, for example, even when the obtained sintered body comes into contact with the skin, the metal ions are more difficult to elute, so that the compatibility with the living body can be further improved.
  • the Cr content in the metal powder is 16% by mass or more and 35% by mass or less, preferably 27% by mass or more and 34% by mass or less, and more preferably 28% by mass or more and 33% by mass or less.
  • the Cr content is less than the lower limit, depending on the overall composition, the corrosion resistance of the manufactured sintered body becomes insufficient.
  • 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.
  • the metal powder for powder metallurgy of the present invention may contain Mo (molybdenum) as necessary.
  • Mo is an element that acts to further increase the corrosion resistance of the sintered body to be produced. That is, the corrosion resistance due to the addition of Cr can be further enhanced by the addition of Mo. This is considered to be due to the fact that the passive film mainly composed of an oxide of Cr is densified by adding Mo. Therefore, in the sintered body manufactured using the metal powder to which Mo is added, the metal ions are more difficult to elute, and the compatibility with the living body can be further improved.
  • the Mo content in the metal powder is preferably 3% by mass or more and 12% by mass or less, more preferably 4% by mass or more and 11% by mass or less, and further preferably 5% by mass or more and 9% by mass or less. . If the Mo content is below the lower limit, depending on the Cr or Si content, the amount of Mo relative to the Cr or Si will be relatively large, and the balance of the contained elements will be lost. There is a risk that the physical characteristics will deteriorate.
  • Si Si silicon
  • Si silicon
  • Si oxide in which a part of Si is oxidized is generated in the alloy.
  • 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 mechanical properties of the sintered body can be further enhanced.
  • 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 can be obtained.
  • the Si content in the metal powder is 0.3% by mass or more and 2.0% by mass or less, preferably 0.5% by mass or more and 1.0% by mass or less, and 0.6% by mass or more. It is more preferable that it is 0.9 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.
  • the sintered body has the effect of improving the mechanical properties as described above, while a certain amount of silicon oxide is present. By being present, the oxide amount of transition metal elements such as Co, Cr, and Mo contained in the sintered body can be sufficiently suppressed.
  • an appropriate hardness can be given to the sintered body. That is, it is considered that when a certain amount of Si that is not silicon oxide is present, at least one of Co, Cr, and Mo and Si form a hard intermetallic compound, which increases the hardness of the sintered body. Durability and abrasion resistance can be improved by increasing the hardness of the sintered body.
  • the intermetallic compound is not particularly limited, and an example, CoSi 2, Cr 3 Si, MoSi 2, Mo 5 Si 3 and the like.
  • the ratio of Si content to the Mo content is preferably 0.05 or more and 0.2 or less in terms of mass ratio. More preferably, it is 0.15 or less. Thereby, higher mechanical properties (for example, a good balance between hardness and toughness) can be imparted to the sintered body.
  • the silicon oxide may be distributed at any position, but is preferably distributed so as to segregate at the grain boundary (interface between the metal crystals).
  • the silicon oxide is segregated at such a position, the enlargement of the metal crystal is more reliably suppressed, and a sintered body having more excellent mechanical characteristics can be obtained.
  • the silicon oxide precipitates segregated at the grain boundaries naturally maintain an appropriate distance, the silicon oxide precipitates can be more uniformly dispersed in the sintered body. As a result, the probability that the silicon oxide is spatially continuously distributed is lowered, and the deterioration of the mechanical characteristics based on the silicon oxide can be avoided.
  • the segregated silicon oxide precipitates can be identified in size, distribution, etc. by qualitative analysis surface analysis.
  • the average diameter of the region where Si is segregated is preferably 0.1 ⁇ m or more and 10 ⁇ m or less, and is 0.3 ⁇ m or more and 8 ⁇ m or less. Is more preferable. If the average diameter of the region where Si is segregated is within the above range, the size of the silicon oxide precipitates is optimal for achieving the effects as described above. That is, when the average diameter of the region where Si is segregated is less than the lower limit value, the silicon oxide precipitates are not segregated to a sufficient size, and the above effects may not be sufficiently obtained. On the other hand, if the average diameter of the region where Si is segregated exceeds the upper limit, the mechanical properties of the sintered body may be deteriorated.
  • the average diameter of the region where Si is segregated is obtained as the average value of the diameters of circles having the same area as that of the region where Si is segregated (projected area circle equivalent diameter) in the Si composition image. Can do.
  • the sintered compact manufactured using the metal powder for powder metallurgy of the present invention includes a first phase mainly composed of Co and a second phase mainly composed of Co 3 Mo. Yes.
  • a first phase mainly composed of Co
  • a second phase mainly composed of Co 3 Mo.
  • the first phase and the second phase are included in an appropriate ratio from the above viewpoint.
  • the sintered body was subjected to a crystal structure analysis by an X-ray diffraction method using CuK ⁇ rays, and when the highest peak height among peaks caused by Co was set to 1, it was attributed to Co 3 Mo.
  • the highest peak height is preferably from 0.01 to 0.5, more preferably from 0.02 to 0.4.
  • identifying a peak due to Co it is identified based on a Co database of an ICDD (The International Center for Diffraction Data) card.
  • ICDD The International Center for Diffraction Data
  • the peak is identified based on the Co 3 Mo database of the ICDD card.
  • the proportion of Co 3 Mo is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less.
  • the dendrite phase is a crystal structure grown in a dendritic shape, but if such a dendrite phase is contained in a large amount, the mechanical properties of the sintered body deteriorate. Therefore, reducing the dendrite phase content is effective in enhancing the mechanical properties of the sintered body.
  • the cross section of the sintered body is observed with a scanning electron microscope, and the area ratio occupied by the dendrite phase in the obtained observation image is preferably 20% or less, and more preferably 10% or less. .
  • a sintered body satisfying such conditions is particularly excellent in mechanical properties.
  • the metal powder since the volume of each particle is very small, the metal powder has a high cooling rate and high cooling uniformity when manufactured from a molten state. For this reason, in the sintered compact manufactured from such a metal powder, the production
  • the volume to be cooled increases, so the cooling rate decreases and the cooling uniformity also decreases. As a result, it is considered that a relatively large amount of dendrite phase is generated in the sintered body produced by such a method.
  • the area ratio described above is calculated as the ratio of the area occupied by the dendrite phase to the area of the observation image, and one side of the observation image is set to about 50 ⁇ m or more and 1000 ⁇ m or less.
  • the metal powder for powder metallurgy of the present invention may contain N (nitrogen) as necessary.
  • N is an element that acts to enhance the mechanical properties of the sintered body to be produced. Since N is an austenitizing element, it acts to promote austenitization of the crystal structure of the sintered body and increase toughness.
  • the inclusion of N suppresses the formation of a dendrite phase in the sintered body, and the content of the dendrite phase becomes very small. From such a viewpoint, toughness can be increased.
  • the obtained sintered body has moderate hardness, high toughness, and low dendrite phase content. For this reason, such a sintered body is rich in impact resistance and the like.
  • the N content in the metal powder is preferably 0.09% by mass or more and 0.5% by mass or less, more preferably 0.12% by mass or more and 0.4% by mass or less, and 0.14% by mass. % To 0.25% by mass, more preferably 0.15% to 0.22% by mass.
  • the N content is less than the lower limit, depending on the composition of the alloy, the crystal structure of the sintered body may become insufficiently austenitized, and the toughness of the sintered body may be easily lowered. This is considered to be because an excessive hcp structure ( ⁇ phase) is precipitated in the sintered body.
  • the N content exceeds the upper limit, depending on the composition of the alloy, a large amount of various nitrides may be generated and the composition may be difficult to sinter. For this reason, there is a possibility that the sintered density of the sintered body is lowered and the corrosion resistance and mechanical properties are lowered.
  • the generated nitride include Cr 2 N.
  • the austenite phase becomes particularly dominant, and a remarkable improvement in toughness is observed as the hardness decreases.
  • a sintered body manufactured using a metal powder containing N at such a content rate is subjected to crystal structure analysis by an X-ray diffraction method using CrK ⁇ rays, the main peak due to the austenite phase is very strong.
  • the peak due to the hcp structure and other peaks are all 5% or less of the height of the main peak. This shows that the austenite phase is dominant.
  • the ratio of N content (N / Si) to Si content is preferably 0.1 or more and 0.8 or less, and more preferably 0.2 or more and 0.6 or less in terms of mass ratio. preferable.
  • N when N is added in the above-described proportion, N penetrates into the crystal structure and dissolves therein, so that distortion of the crystal structure is suppressed. As a result, hysteresis in the behavior of thermal expansion and contraction is suppressed, and the thermal characteristics of the sintered body can be stabilized.
  • the ratio of the N content to the Si content is below the lower limit, depending on the composition of the alloy, the distortion of the crystal structure cannot be sufficiently suppressed, and the toughness and the like may be reduced.
  • the upper limit depending on the composition of the alloy, the composition becomes difficult to sinter, the sintered density of the sintered body is lowered, and the mechanical properties may be lowered.
  • the metal powder for powder metallurgy of the present invention may contain C (carbon) as necessary.
  • C is an element that acts to enhance the mechanical properties of the sintered body to be produced.
  • the addition of C increases the hardness and tensile strength of the sintered body.
  • the mechanical properties of the sintered body can be improved by combining the C with the first element and the second element to generate carbides.
  • the C content in the metal powder is preferably 1.5% by mass or less, and more preferably 0.7% by mass or less. If the C content exceeds the upper limit, depending on the composition of the alloy, the brittleness of the sintered body increases and the mechanical properties may deteriorate.
  • the lower limit value of the addition amount is not particularly set, but it is preferable that the lower limit value is set to about 0.05% by mass in order to sufficiently exhibit the above-described effect.
  • the C content is preferably about 0.02 to 0.5 times the Si content, more preferably about 0.05 to 0.3 times.
  • the N content is preferably about 0.3 to 10 times the C content, more preferably about 2 to 8 times.
  • first element and second element The first element and the second element are combined with oxygen or the like contained in the binder or metal powder in the molded body, and precipitate carbides and oxides (hereinafter collectively referred to as “carbides and the like”) in the alloy. . 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.
  • 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. .
  • the first element and the second element are two elements selected from the group consisting of seven elements of Ti, V, Y, Zr, Nb, Hf, and Ta. It is preferable that an element belonging to Group 4A or Group 4A (Ti, Y, Zr, Hf) is included.
  • an element belonging to Group 3A or 4A is included as at least one of the first element and the second element, oxygen contained as an oxide in the metal powder is removed, and the sinterability of the metal powder is particularly enhanced. Can do.
  • the first element may be one element selected from the group consisting of seven elements of Ti, V, Y, Zr, Nb, Hf and Ta, but preferably the seven elements
  • the element belongs to Group 3A or Group 4A of the long-period element periodic table.
  • Elements belonging to Group 3A or Group 4A can remove oxygen contained in the metal powder as an oxide 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.
  • 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.
  • the second element is one element selected from the group consisting of seven elements of Ti, V, Y, Zr, Nb, Hf, and Ta
  • the first element is Any element may be used as long as it is different, but it is preferably an element belonging to Group 5A of the periodic table of the long-period element in the group consisting of the seven elements.
  • the elements belonging to Group 5A can efficiently precipitate the above-described carbides and the like, so that significant growth of crystal grains during sintering can be efficiently inhibited. 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.
  • the first element is an element belonging to Group 4A and the second element is Nb is employed.
  • 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.
  • 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.
  • 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. .
  • the first element and the second element each precipitate carbide or the like.
  • the element belonging to the 3A group or the 4A group is selected as the first element, and the second element is described above.
  • 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 metal powder only needs to contain two kinds of elements selected from the group consisting of the seven elements, but the elements are selected from this group and are different from the two kinds of elements. May further be included. That is, the metal powder may contain three or more elements selected from the group consisting of the seven elements. As a result, the effect described above can be further enhanced, although it differs somewhat depending on the combination.
  • the ratio of the content ratio of the first element and the content ratio of the second element is set in consideration of the mass number of the element selected as the first element and the mass number of the element selected as the second element. Is preferred.
  • the value obtained by dividing the content E1 (mass%) of the first element by the mass number of the first element is taken as an index X1
  • the content E2 (mass%) of the second element is the mass number of the second element.
  • the ratio X1 / X2 of the index X1 with respect to the index X2 is preferably 0.3 or more and 3 or less, more preferably 0.5 or more and 2 or less. More preferably, it is 75 or more and 1.3 or less.
  • hole remaining in a molded object can be discharged
  • hole produced in a sintered compact can be suppressed to the minimum. Therefore, by setting X1 / X2 within the above range, a metal powder capable of producing 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.
  • the mass number of Zr is 91.2 and the mass number 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.
  • the mass number of Hf is 178.5 and the mass number 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.
  • the mass number of Ti is 47.9 and the mass number 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.
  • E1 / E2 is 0.15. It is preferably 1.54 or more and more preferably 0.26 or more and 1.03 or less.
  • E1 / E2 is 0.29. It is preferably 2.87 or less and more preferably 0.48 or more and 1.91 or less.
  • the mass number of V is 50.9 and the mass number of Nb is 92.9, so 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.
  • E1 / E2 is 0.16. It is preferably 1.58 or more and more preferably 0.26 or more and 1.05 or less.
  • the mass number of Zr is 91.2 and the mass number 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.
  • the mass number of Zr is 91.2 and the mass number of V is 50.9, so E1 / E2 is 0.54. It is preferably 5.38 or less and more preferably 0.90 or more and 3.58 or less.
  • E1 / E2 can be calculated in the same manner as described above for combinations other than those described above.
  • the total (E1 + E2) of the content ratio E1 of the first element and the content ratio E2 of the second element is preferably 0.05% by mass or more and 0.6% by mass or less, and more preferably 0.10% by mass or more and 0.0. It is more preferably 48% by mass or less, and further preferably 0.12% by mass or more and 0.24% by mass or less.
  • (E1 + E2) / Si when the ratio of the total content of the first element and the content of the second element to the content of Si is (E1 + E2) / Si, (E1 + E2) / Si is 0.1 or more and 0.7 or less. Is more preferably 0.15 or more and 0.6 or less, and further preferably 0.2 or more and 0.5 or less.
  • (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, it is possible to obtain a metal powder capable of producing a sintered body having excellent mechanical properties such as toughness and excellent corrosion resistance derived from Si, despite its high density.
  • 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.
  • a sintered body having finer crystals can be obtained.
  • Such a sintered body has particularly high mechanical properties.
  • the sintered body has such a granular shape, the first region having a relatively high silicon oxide content, and the second region having a relatively low silicon oxide content than the first region, Is easily formed.
  • the presence of the first region makes it possible to reduce the oxide concentration inside the crystal and suppress the remarkable growth of crystal grains as described above.
  • O oxygen
  • Co cobalt
  • the first region exists mainly in the crystal grain boundary
  • the second region exists mainly in the crystal grain. Therefore, in the first region, when the sum of the content ratios of the two elements of O and Si is compared with the content ratio of Co, the sum of the content ratios of the two elements is greater than the content ratio of Co.
  • the second region the sum of the contents of the two elements O and Si is much smaller than the content of Co. From these facts, it is understood that Si and O are integrated in the first region.
  • the sum of the Si content and the O content is preferably 1.5 times to 10,000 times the Co content.
  • the Si content in the first region is preferably 3 to 10,000 times the Si content in the second region.
  • At least one of the content ratio of the first element and the content ratio of the second element has a relationship that the content ratio in the first region is larger than the content rate in the second region. Satisfied.
  • the first element carbide, the second element carbide, and the like described above serve as nuclei when silicon oxide accumulates in the first region.
  • the content rate of the first element in the first region is not less than 3 times and not more than 10,000 times the content rate of the first element in the second region.
  • the content of the second element in the first region is preferably 3 to 10,000 times the content of the second element in the second region.
  • silicon oxide as described above is considered to be one of the causes of densification of the sintered body. Therefore, even if the sintered body has been densified by the present invention, it is considered that silicon oxide may not be accumulated depending on the composition ratio. That is, depending on the composition ratio, the first region and the second region may not be included.
  • the diameter of the granular first region varies depending on the Si content in the entire sintered body, but is about 0.5 ⁇ m to 15 ⁇ m, and preferably about 1 ⁇ m to 10 ⁇ m.
  • the diameter of the first region is obtained as an average value of the diameters of circles having the same area as the area of the first region specified from light and shade (circle equivalent diameter) in the electron micrograph of the cross section of the sintered body. it can. When the average value is obtained, 10 or more measured values are used.
  • (E1 + E2) / C is preferably 1 or more and 16 or less. It is more preferably 2 or more and 13 or less, and further preferably 3 or more and 10 or less.
  • the metal powder for powder metallurgy of the present invention may contain at least one of Fe, Ni, Mn, W, and S as necessary, in addition to the elements described above. In addition, these elements may be inevitably included.
  • Fe is an element that imparts high mechanical properties to the sintered body to be produced.
  • the content rate of Fe in a metal powder is not specifically limited, It is preferable that it is 0.01 to 25 mass%, and it is more preferable that it is 0.03 to 5 mass%.
  • Ni is an element that imparts high toughness to the manufactured sintered body.
  • the content rate of Ni in a metal powder is not specifically limited, It is preferable that it is 0.01 to 40 mass%, and it is more preferable that it is 0.02 to 37 mass%. By setting the Ni content within the above range, a sintered body having high density and excellent toughness can be obtained.
  • Mn like Si, is an element that imparts corrosion resistance and high mechanical properties to the sintered body to be produced.
  • the content of Mn in the metal powder is not particularly limited, but is preferably 0.05% by mass or more and 1.5% by mass or less, and more preferably 0.1% by mass or more and 1% by mass or less.
  • 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.
  • W is an element that enhances the heat resistance of the sintered body to be produced.
  • the content rate of W in a metal powder is not specifically limited, It is preferable that they are 1 mass% or more and 20 mass% or less, and it is more preferable that they are 2 mass% or more and 16 mass% or less.
  • S is an element that enhances the machinability of the sintered body to be produced.
  • 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.
  • B, Se, Te, Pd, etc. may be added to the metal powder for powder metallurgy of the present invention.
  • the content of these elements is not particularly limited, but is preferably less than 0.1% by mass, and preferably less than 0.2% by mass in total. In addition, these elements may be inevitably included.
  • the metal powder for powder metallurgy according to the present invention may contain impurities.
  • the impurities include all elements other than the elements described above. Specifically, for example, Li, Be, Na, Mg, P, 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 set so that each element is less than the contents of Co, Cr, Si, the first element and the second element.
  • 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.
  • these elements may be intentionally added because the effects as described above are not inhibited.
  • O oxygen
  • 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 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 content of Co is not particularly limited, but is preferably 50% by mass or more, and more preferably 55% by mass or more and 67.5% by mass or less.
  • 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).
  • Analysis method, iron and steel specified in JIS G 1253 (2002)-spark discharge emission spectrometry, iron and steel specified in JIS G 1256 (1997), X-ray fluorescence analysis, JIS G 1211 to G 1237 Can be specified by the weight, titration, absorptiometry, etc. defined in the above.
  • SPECTRO spark discharge optical spectroscopic analyzer, model: SPECTROLAB, type: LAVMB08A
  • ICP apparatus IROS120 type manufactured by Rigaku Corporation
  • 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 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) Determination method of aluminum in iron and steel JIS G 1225 (2006) Iron and steel-arsenic determination method JIS G 12
  • N nitrogen
  • O oxygen
  • JIS G 1228 (2006) the nitrogen determination method for iron and steel specified in JIS G 1228 (2006)
  • the oxygen of metallic materials 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 ⁇ m or more and 30 ⁇ m or less, more preferably 1 ⁇ m or more and 20 ⁇ m or less, and further preferably 2 ⁇ m or more and 10 ⁇ m or less.
  • 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 the mass basis obtained by the laser diffraction method.
  • 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.
  • the maximum particle size is preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less.
  • 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 the mass basis obtained by the laser diffraction method.
  • 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
  • the minor axis is the maximum length that can be taken in the direction perpendicular to the major axis.
  • the average value of aspect ratio is calculated
  • 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.
  • 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.
  • surface activity surface energy
  • the metal powder for powder metallurgy according to the present invention preferably contains a chemical component of a cobalt chromium alloy specified in JIS T 6115 (2013), for example.
  • the above “chemical component” refers to a chemical component defined in JIS T 6115 (2013). Specifically, for example, it refers to a combination of elements contained in the content (unit: mass%) defined in 4.3 of JIS T 6115 (2013).
  • 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.
  • the metal powder for powder metallurgy is uniformly dispersed.
  • 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. .
  • an atomizing method for example, a water atomizing method, a gas atomizing method, a high-speed rotating water atomizing method, etc.
  • a reduction method for example, a carbonyl method, and a pulverizing method.
  • the metal powder for powder metallurgy of the present invention is preferably produced by an atomizing method, more preferably produced 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.
  • the pressure of water sprayed toward the molten metal 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.
  • 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.
  • the apex angle of the cone formed by the atomized water is preferably about 10 ° to 40 °, and more preferably about 15 ° to 35 °.
  • the molten metal can be cooled particularly quickly. For this reason, a high quality powder is obtained in a wide alloy composition.
  • 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.
  • classification methods include sieving classification, inertia classification, dry classification such as centrifugal classification, and wet classification such as sedimentation classification.
  • examples of the binder 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, polyvinyl chloride, and polyvinylidene chloride.
  • polyesters such as polyamide, polyethylene terephthalate, polybutylene terephthalate, polyether, polyvinyl alcohol, polyvinylpyrrolidone or copolymers thereof, various waxes, paraffins, higher fatty acids (eg stearic acid), higher alcohols,
  • organic binders such as higher fatty acid esters and higher fatty acid amides.
  • one kind or a mixture of two or more kinds can be used.
  • 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.
  • 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.
  • a plasticizer may be added to the kneaded material as necessary.
  • 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.
  • 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.
  • kneading temperature 50 ° C. or more and 200 ° C. Or less
  • kneading time about 15 minutes or more and 210 minutes or less.
  • 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.
  • 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.
  • the metal powder for powder metallurgy of the present invention is subjected to a granulation treatment to bind a plurality of metal particles with a binder.
  • binder used in the production of the granulated powder examples 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.
  • polyolefins such as polyethylene, polypropylene and ethylene-vinyl acetate copolymer
  • the binder preferably contains polyvinyl alcohol or polyvinyl pyrrolidone. 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.
  • 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.
  • the content of the binder is within the above range, the granulated powder is efficiently formed while suppressing remarkably large particles from being granulated or from leaving a large amount of non-granulated metal particles. be able to.
  • the shape stability of the molded body can be made particularly excellent.
  • 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.
  • additives such as a plasticizer, a lubricant, an antioxidant, a degreasing accelerator, and a surfactant may be added to the granulated powder as necessary.
  • 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.
  • a solvent that dissolves the binder is used as necessary.
  • 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 ⁇ m to 200 ⁇ m, more preferably about 20 ⁇ m to 100 ⁇ m, and further preferably about 25 ⁇ m to 60 ⁇ m.
  • 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 the mass basis obtained by the laser diffraction method.
  • molding method of the molded body.
  • various molding methods such as a powder molding (compression molding) method, a metal powder injection molding (MIM) method, and an extrusion molding method are used.
  • MIM metal powder injection molding
  • extrusion molding method can be used.
  • 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).
  • 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.
  • the material temperature is about 80 ° C. to 210 ° C.
  • 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.
  • the shape and size of the molded body to be produced is determined in consideration of the shrinkage of the molded body in the subsequent degreasing and firing steps.
  • the molded body is heated to decompose the binder, thereby removing the binder from the molded body and performing a degreasing treatment.
  • 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.
  • 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.
  • 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.
  • a reducing gas atmosphere such as hydrogen
  • an inert gas atmosphere such as nitrogen or argon
  • an oxidizing gas atmosphere such as air
  • the reduced pressure atmosphere etc. which reduced pressure is mentioned.
  • examples of the gas that decomposes the binder include ozone gas.
  • 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.
  • machining such as cutting, grinding
  • This sintering causes the metal powder for powder metallurgy to diffuse at the interface between the particles, resulting in sintering.
  • 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 and particle size of the metal powder for powder metallurgy used in the production of the molded body and the degreased body, but it 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, preferably 1 hour or more and 6 hours or less.
  • the firing temperature or the firing atmosphere described later may be changed during the firing process.
  • the entire degreased body can be sufficiently sintered while preventing oversintering and oversintering and the crystal structure becoming enlarged.
  • a sintered body having a high density and particularly excellent mechanical properties can be obtained.
  • the firing temperature is relatively low, the heating temperature in the firing furnace can be easily controlled, and therefore the temperature of the degreased body is also likely to be constant. As a result, a more uniform sintered body can be produced.
  • 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 the 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.
  • 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
  • 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.
  • the sintered body thus obtained has high density and excellent mechanical properties. 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.
  • 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.
  • the sintered body produced by molding, degreasing and sintering the composition containing the metal powder for powder metallurgy of the present invention and the binder has the conventional tensile strength and 0.2% proof stress. It becomes larger than the tensile strength and 0.2% proof stress of the sintered body similarly sintered using metal powder. This is presumably because the alloy composition was optimized to enhance the sinterability of the metal powder and the mechanical properties of the sintered body produced thereby were improved.
  • the sintered body manufactured as described above has a high hardness surface. Specifically, although it varies slightly depending on the composition of the metal powder for powder metallurgy, as an example, it is expected that the surface Vickers hardness is 300 or more and 780 or less. Further, it is expected to be preferably 340 or more and 600 or less. Since the sintered body having such hardness has both wear resistance and impact resistance, the sintered body has particularly high durability.
  • the sintered body has a sufficiently high density and mechanical properties without any additional treatment.
  • various additional treatments are performed. You may make it give.
  • an additional process for increasing the density such as the HIP process described above, may be used.
  • the light element in the metal powder volatilizes, and the composition of the finally obtained sintered body slightly changes from the composition in the metal powder. Sometimes it is.
  • 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%).
  • 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%).
  • the manufactured sintered body may be subjected to the HIP process as part of an additional process performed as necessary.
  • the HIP process even if the HIP process is performed, a sufficient effect may not be exhibited.
  • the sintered body can be further densified, but 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.
  • 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.
  • the sintered body produced according to the present invention requires little additional treatment for the purpose of improving mechanical properties, the composition and the 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.
  • the porosity in the vicinity of the surface is often relatively smaller than the internal porosity. The reason for this is not clear, but it can be mentioned that the addition of the first element and the second element makes it easier for the sintering reaction to proceed in the vicinity of the surface than in the molded body. .
  • A2-A1 is preferably 0.1% or more and 3% or less. More preferably, it is 0.2% or more and 2% or less.
  • a sintered body having A2-A1 in such a range has the necessary and sufficient mechanical strength, while allowing the surface to be easily flattened. That is, a surface having high specularity can be obtained by polishing the surface of the sintered body.
  • Such a highly specular sintered body has not only high mechanical strength but also excellent aesthetics. For this reason, this sintered compact is used suitably also for the use as which the outstanding aesthetic appearance is requested
  • the porosity A1 in the vicinity of the surface of the sintered body refers to a porosity within a range of a radius of 25 ⁇ m centering on a position at a depth of 50 ⁇ m from the surface in the cross section of the sintered body.
  • the porosity A2 inside the sintered body refers to a porosity within a range of a radius of 25 ⁇ m around a position of a depth of 300 ⁇ m from the surface in the cross section of the sintered body.
  • the sintered body of the present invention can be applied to, for example, a decorative article. At least a part of the embodiment of the decorative article of the present invention is composed of the above-described sintered body (embodiment of the sintered body of the present invention).
  • Embodiments of the decorative article of the present invention include, for example, a watch case (a trunk, a back cover, a one-piece case in which the trunk and the back cover are integrated), a watch band (a band middle ring, a band / bangle attachment / detachment mechanism, etc.) .), Bezels (for example, rotating bezels), crowns (for example, screw lock type crowns), buttons, glass rims, dial rings, parting plates, packing parts such as clocks, glasses (for example, glasses frames) , Tie pins, cufflinks, rings, necklaces, bracelets, anklets, brooches, pendants, earrings, earrings and other accessories, spoons, forks, chopsticks, knives, butter knives, bottle openers, lighters or their cases, golf clubs Sports equipment, nameplates, panels, prize cups, and other housings (eg mobile phones, smartphones, Brett terminal, mobile computers, music players, cameras, can be applied various equipment parts of the housing) of the shaver or the
  • All of these items may be used in contact with the human skin and must have an excellent aesthetic appearance, as well as body fluids such as sweat and saliva, foods, detergents, and other Resistance to chemicals is also required. Therefore, by applying the decorative article of the present invention to these articles, it is possible to maintain a decorative article having excellent corrosion resistance resulting from high densification, that is, an excellent aesthetic appearance over a long period of time, and altering the body fluid etc. It is possible to realize a decorative product that does not easily cause In addition, these decorative products have excellent mechanical properties due to the high-density sintered body, so that they are particularly resistant to corrosion and hardness, and are not easily scratched. From this point of view as well, an excellent aesthetic appearance is maintained over a long period of time. can do.
  • FIG. 1 is a perspective view showing a watch case to which an embodiment of the decorative article of the present invention is applied
  • FIG. 2 is a partial sectional perspective view showing a bezel to which the embodiment of the decorative article of the present invention is applied.
  • the watch case 11 shown in FIG. 1 includes a case main body 112 and a band attaching portion 114 that is provided so as to protrude from the case main body 112 and attaches the watch band.
  • a watch case 11 can construct a container together with a glass plate and a back cover (not shown). A movement, dial, etc. (not shown) are accommodated in this container. Therefore, this container protects the movement and the like from the external environment and has a great influence on the aesthetic appearance of the watch.
  • the bezel 12 shown in FIG. 2 has an annular shape, is attached to the watch case, and is rotatable with respect to the watch case as necessary. When the bezel 12 is attached to the watch case, the bezel 12 is positioned outside the watch case, so that the bezel 12 affects the aesthetic appearance of the watch.
  • FIG. 3 is a perspective view showing a ring to which an embodiment of the decorative article of the present invention is applied.
  • the ring 21 shown in FIG. 3 includes a ring main body 212, a pedestal 214 provided on the ring main body 212, and a jewel 216 attached to the pedestal 214.
  • the ring body 212 and the base 214 are integrally formed of the above-described sintered body.
  • the jewel 216 is fixed by a caulking claw 218 included in the pedestal 214.
  • the ring main body 212 and the pedestal 214 are used in contact with a human finger or the like, the ring main body 212 and the pedestal 214 are also exposed to sweat for a long period of time. For this reason, when the corrosion resistance of the ring main body 212 or the pedestal 214 is low, rust is generated by perspiration, which may cause deterioration in aesthetic appearance and mechanical characteristics. Therefore, by using the above-described sintered body as a constituent material of the ring body 212 and the base 214, an accessory having excellent corrosion resistance can be obtained. In addition, since such ring body 212 and pedestal 214 have excellent mechanical properties due to the high-density sintered body, they have particularly high corrosion resistance and hardness and are hardly scratched. A beautiful aesthetic appearance can be maintained.
  • FIG. 4 is a plan view showing a knife to which an embodiment of the decorative article of the present invention is applied.
  • the knife 31 shown in FIG. 4 includes a grip portion 312 and a blade portion 314 extending from the grip portion 312.
  • the grip portion 312 and the blade portion 314 are integrally formed of the sintered body described above.
  • the grip portion 312 since the grip portion 312 is used in a state of touching a human hand or the like, the grip portion 312 also touches sweat for a long period of time.
  • the blade portion 314 is used in contact with food or the like, it comes into contact with acid or the like.
  • each shape of the exterior parts for clocks, accessories, and tableware as described above is only an example, and the embodiment of the decorative article of the present invention is not limited to the illustrated shape.
  • the exterior part for a watch is not limited to the exterior part for a wristwatch, but can also be applied to an exterior part for a pocket watch.
  • the sintered body of the present invention can be applied to, for example, a supercharger part. At least a part of a supercharger component described later is composed of the above-described sintered body (embodiment of the sintered body of the present invention).
  • turbocharger parts include, for example, turbocharger nozzle vanes, turbocharger turbine wheels, wastegate valves, turbine housings, and the like. All of these articles are exposed to high temperatures over a long period of time and slide between other parts, so that wear resistance is required.
  • the sintered body of the present invention since the sintered body of the present invention has a high density, it has excellent mechanical properties and high weather resistance and hardness. For this reason, the supercharger component excellent in durability over a long period of time can be obtained.
  • nozzle vane for a turbocharger (hereinafter, also referred to as “nozzle vane”) will be described as an example of a turbocharger part.
  • FIG. 5 is a side view showing a turbocharger nozzle vane (when the wing is viewed in plan)
  • FIG. 6 is a plan view of the nozzle vane shown in FIG. 5
  • FIG. 7 is a nozzle vane shown in FIG. FIG.
  • a nozzle vane 41 illustrated in FIG. 5 includes a shaft portion 411 and a blade portion 412.
  • the shaft portion 411 has a circular cross section with a central axis of the axis 413 in the cross-sectional shape of the main portion.
  • the shaft portion 411 is rotatably supported by a nozzle mount (not shown) on the blade portion 412 side (left side in FIG. 5), and a portion on the opposite side (right side in FIG. 5) from the blade portion 412. It is fixed to a nozzle plate (not shown).
  • a center hole 414 is formed on one end surface of the shaft portion 411 (the right end surface in FIG. 5).
  • the center hole 414 is formed so that its cross-sectional shape is circular and its center coincides with the axis 413.
  • a pair of flat portions 415 (two-surface cut portions) facing each other via an axis 413 are provided on the outer peripheral surface on one end side (right side in FIG. 5) of the shaft portion 411 (see FIG. 7).
  • Each flat portion 415 is used in a state of being applied to an abutting surface formed on a lever plate (not shown).
  • the rotation angle around the axis 413 of the shaft portion 411 is restricted, and the rotation angle around the shaft portion 411 of the nozzle vane 41 can be adjusted with high accuracy.
  • Each flat portion 415 is formed so as to be inclined at an angle ⁇ with respect to the protruding direction (blade surface) of the wing portion 412 (see FIG. 7).
  • a wing portion 412 is provided at the other end portion (left end portion in FIG. 5) of the shaft portion 411. That is, the wing part 412 is provided so as to protrude from one end part of the shaft part 411. Further, a flange portion 416 that protrudes outside the shaft portion 411 is formed at the other end portion of the shaft portion 411.
  • the wing portion 412 has a strip shape extending in a direction perpendicular to the axis 413 of the shaft portion 411 in a plan view, as shown in FIG. Further, the protruding length of the wing part 412 from the shaft part 411 is longer at one end side (lower side in FIG. 5) than the other end side (upper side in FIG. 5).
  • chamfers 417 and 418 are applied to edges at both end portions in the width direction (left and right direction in FIG. 5) of the wing portion 412 in a plan view. As shown in FIGS. 6 and 7, the wing part 412 is slightly curved in the thickness direction. Further, the thickness of the wing portion 412 gradually decreases toward each end in the extending direction (projecting direction).
  • the nozzle vane 41 as described above is composed of the sintered body of the present invention. Since the sintered body of the present invention has a high density, the nozzle vane 41 has excellent mechanical properties and excellent wear resistance. As a result, it is possible to realize a supercharger that is excellent in durability over a long period of time.
  • the present invention is not limited to these.
  • the sintered body of the present invention includes, for example, parts for transportation equipment such as parts for automobiles, parts for bicycles, parts for railway vehicles, parts for ships, parts for aircraft, parts for space transport aircraft (for example, rockets).
  • parts for electronic devices such as parts for personal computers, parts for mobile phones, parts for electrical equipment such as refrigerators, washing machines, air conditioners, machine parts such as machine tools and semiconductor manufacturing equipment, nuclear power plants, Plant parts such as thermal power plants, hydroelectric power plants, refineries, chemical complexes, watch parts, metal tableware, jewelry, ornaments such as eyeglass frames, surgical instruments, artificial bones, artificial teeth, artificial roots
  • medical devices such as orthodontic parts, it is used for all structural parts.
  • the mixed raw material was kneaded with a kneader to obtain a compound.
  • this compound was molded by an injection molding machine under the molding conditions shown below to produce a molded body.
  • the obtained defatted 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.
  • 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. The sintered body of 29 was subjected to HIP treatment under the following conditions after firing.
  • Sample No. The sintered bodies 14 to 16 were obtained using metal powders produced by the gas atomizing method. In Table 1, “gas” is written in the remarks column.
  • Examples 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”.
  • Examples those corresponding to the present invention are referred to as “Examples”
  • Comparative Examples those not corresponding to the present invention are referred to as “Comparative Examples”.
  • Each sintered body contained a small amount of impurities, but the description in Table 1 was omitted.
  • 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.
  • 50 mass parts solvent ion-exchange water
  • this granulated powder was compacted under the molding conditions shown below.
  • a press molding machine was used for this molding.
  • the shape of the molded body to be produced was a 20 mm square cube shape.
  • sample Nos. 31-40 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 30, a sintered body was obtained. Sample No. About 40 sintered bodies, after firing, HIP treatment was performed under the following conditions.
  • ⁇ Evaluation criteria for tensile strength> A: Tensile strength of the sintered body is 695 MPa or more B: Tensile strength of the sintered body is 685 MPa or more and less than 695 MPa C: Tensile strength of the sintered body is 675 MPa or more and less than 685 MPa D: Sintering The tensile strength of the body is 665 MPa or more and less than 675 MPa E: The tensile strength of the sintered body is 655 MPa or more and less than 665 MPa F: The tensile strength of the sintered body is less than 655 MPa
  • ⁇ Evaluation criteria for 0.2% proof stress> A: 0.2% yield strength of the sintered body is 490 MPa or more B: 0.2% yield strength of the sintered body is 480 MPa or more and less than 490 MPa C: 0.2% yield strength of the sintered body is 470 MPa or more and less than 480 MPa D: The 0.2% yield strength of the sintered body is 460 MPa or more and less than 470 MPa E: The 0.2% yield strength of the sintered body is 450 MPa or more and less than 460 MPa F: The 0.2% yield strength of the sintered body is Less than 450 MPa
  • the fatigue strength was measured according to a test method defined in JIS Z 2273 (1978).
  • the applied waveform of the load corresponding to the repetitive stress was a double sine wave, and the minimum maximum stress ratio (minimum stress / maximum stress) was 0.1.
  • the repetition frequency was 30 Hz, and the number of repetitions was 1 ⁇ 10 7 times.
  • the measured fatigue strength was evaluated according to the following evaluation criteria.
  • 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).
  • the sintered body corresponding to the comparative example excluding the sintered body subjected to HIP treatment.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • the evaluation results are shown in Table 6.
  • Example No. 80 Metal powder, Ti powder having an average particle diameter of 40 ⁇ m, and Nb powder having an average particle diameter of 25 ⁇ m were mixed to prepare a mixed powder. In addition, in preparation of mixed powder, each mixing amount of metal powder, Ti powder, and Nb powder was adjusted so that the composition of mixed powder might become a composition shown in Table 7.
  • sample No. A sintered body was obtained in the same manner as in the method for producing a sintered body of No. 1.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • the evaluation results are shown in Table 8.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • Table 10 shows the evaluation results.
  • 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.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • the evaluation results are shown in 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.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • the evaluation results are shown in 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.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • the evaluation results are shown in 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.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2.
  • the evaluation results are shown in Table 18.
  • the measured hardness was evaluated according to the evaluation criteria described in 2.2. Table 20 shows the evaluation results.
  • 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.
  • the specular gloss of the sintered body was measured in accordance with the specular gloss measurement method specified in JIS Z 8741 (1997).
  • the incident angle of light with respect to the surface of the sintered body was 60 °, and glass having a specular gloss of 90 and a refractive index of 1.500 was used as a reference surface for calculating the specular gloss.
  • the measured specular gloss was evaluated according to the following evaluation criteria.
  • the sintered body corresponding to the example had a higher specular gloss than the sintered body corresponding to the comparative example. This is considered to be due to the fact that the ratio of regular reflection is increased while light scattering is suppressed due to the particularly small porosity in the vicinity of the surface of the sintered body.

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Abstract

Cette invention concerne : une poudre métallique pour métallurgie des poudres, un composé et une poudre granulée qui sont appropriés pour produire un objet fritté de haute densité ; et un objet fritté de haute densité et un article décoratif, tous deux obtenus au moyen de la poudre métallique pour métallurgie des poudres. Ladite poudre métallique pour métallurgie des poudres est caractérisée en ce que le Co est le composant principal, en ce qu'elle contient du Cr dans une proportion de 16 à 35 % en masse et du Si dans une proportion de 0,3 à 2,0 % en masse, et lorsqu'un élément choisi dans le groupe constitué par Ti, V, Y, Zr, Nb, Hf et Ta est pris en tant que premier élément et lorsqu'un élément qui est un élément choisi dans ledit groupe et qui appartient à un groupe ultérieur du tableau périodique par rapport au premier élément ou appartient au même groupe du tableau périodique que le premier élément et à une période ultérieure de celui-ci par rapport au premier élément est pris en tant que second élément, alors le premier élément est contenu dans une proportion de 0,01 à 0,5 % en masse et le second élément est contenu dans une proportion de 0,01 à 0,5 % en masse.
PCT/JP2015/006499 2015-01-08 2015-12-28 Poudre métallique pour métallurgie des poudres, composé, poudre granulée, objet fritté, et article décoratif Ceased WO2016110929A1 (fr)

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EP15876807.7A EP3243581A4 (fr) 2015-01-08 2015-12-28 Poudre métallique pour métallurgie des poudres, composé, poudre granulée, objet fritté, et article décoratif
US15/542,294 US11498123B2 (en) 2015-01-08 2015-12-28 Metal powder for powder metallurgy, compound, granulated powder, sintered body, and ornament

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5285905A (en) * 1976-01-12 1977-07-16 Mitsubishi Metal Corp Co base sintered alloy of excellent cuttability used for parts of deco rations
JPH03146631A (ja) * 1985-08-13 1991-06-21 Pfizer Hospital Prod Group Inc ガス霧化により製造される分散強化コバルト―クロム―モリブデン合金から製造される人工補装具
JP2008001942A (ja) * 2006-06-22 2008-01-10 Iwate Univ 多孔質Ｃｏ基合金焼結被覆材およびその製造方法
JP2009138259A (ja) * 2007-11-13 2009-06-25 Seiko Epson Corp 粉末冶金用金属粉末、焼結体および焼結体の製造方法
JP2010150587A (ja) * 2008-12-24 2010-07-08 Seiko Epson Corp 粉末冶金用金属粉末の製造方法および粉末冶金用金属粉末
JP2015183277A (ja) * 2014-03-26 2015-10-22 セイコーエプソン株式会社 装飾品、皮膚接触材料、粉末冶金用金属粉末および装飾品の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5285905A (en) * 1976-01-12 1977-07-16 Mitsubishi Metal Corp Co base sintered alloy of excellent cuttability used for parts of deco rations
JPH03146631A (ja) * 1985-08-13 1991-06-21 Pfizer Hospital Prod Group Inc ガス霧化により製造される分散強化コバルト―クロム―モリブデン合金から製造される人工補装具
JP2008001942A (ja) * 2006-06-22 2008-01-10 Iwate Univ 多孔質Ｃｏ基合金焼結被覆材およびその製造方法
JP2009138259A (ja) * 2007-11-13 2009-06-25 Seiko Epson Corp 粉末冶金用金属粉末、焼結体および焼結体の製造方法
JP2010150587A (ja) * 2008-12-24 2010-07-08 Seiko Epson Corp 粉末冶金用金属粉末の製造方法および粉末冶金用金属粉末
JP2015183277A (ja) * 2014-03-26 2015-10-22 セイコーエプソン株式会社 装飾品、皮膚接触材料、粉末冶金用金属粉末および装飾品の製造方法

Non-Patent Citations (1)

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Title
See also references of EP3243581A4 *

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