WO2017110813A1 - High-hardness high-toughness powder - Google Patents

High-hardness high-toughness powder Download PDF

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Publication number
WO2017110813A1
WO2017110813A1 PCT/JP2016/087963 JP2016087963W WO2017110813A1 WO 2017110813 A1 WO2017110813 A1 WO 2017110813A1 JP 2016087963 W JP2016087963 W JP 2016087963W WO 2017110813 A1 WO2017110813 A1 WO 2017110813A1
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Prior art keywords
powder
alloy powder
hardness
sintered body
present
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PCT/JP2016/087963
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French (fr)
Japanese (ja)
Inventor
澤田　俊之
長谷川　浩之
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山陽特殊製鋼株式会社
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Application filed by 山陽特殊製鋼株式会社 filed Critical 山陽特殊製鋼株式会社
Priority to US16/064,645 priority Critical patent/US20180371584A1/en
Priority to CN201680071053.XA priority patent/CN108368567A/en
Publication of WO2017110813A1 publication Critical patent/WO2017110813A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/04—Alloys based on tungsten or molybdenum
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention is a shot material for shot peening, a raw material powder for a high hardness powder sintered body excellent in hydrochloric acid corrosion resistance, a hard friction powder, a high hardness high toughness alloy powder that can be used for sintering hard particles, and the like,
  • the present invention relates to a projection material for shot peening, a composition for powder metallurgy, and a sintered body using the same.
  • Co-Mo alloys and Co-W alloys produce various intermetallic compounds as can be seen from the respective binary phase diagrams.
  • These intermetallic compounds have high hardness and are suitable for various high hardness materials and wear resistant materials.
  • Mo and W also have an effect of improving the corrosion resistance by being dissolved in Co, and particularly have a great effect of improving the corrosion resistance against a reducing acid such as hydrochloric acid.
  • Co itself has high corrosion resistance against various acids as a base metal. Therefore, powders of these alloy compositions can be used for shot peening projection materials, raw powders for high hardness powder sintered bodies having excellent hydrochloric acid corrosion resistance, hard friction powders, hard particles for sintering, and the like.
  • a CoMoCrSi-based alloy powder [Trivalloy (registered trademark)] disclosed in WO2012 / 063512A1 (Patent Document 1) is often used.
  • Si added to increase the hardness of the alloy produces a hard but brittle silicide and lowers the bending strength of the alloy, which is problematic in applications that require a high bending strength.
  • Mo and W as much as possible in order to improve hardness and corrosion resistance, it is necessary to keep the addition amount low in consideration of toughness such as bending strength. It was real.
  • the present invention is a shot material for shot peening, a raw material powder for a high hardness powder sintered body excellent in hydrochloric acid corrosion resistance, a hard friction powder, a high hardness high toughness alloy powder that can be used for sintering hard particles, and the like,
  • An object is to provide a shot peening projection material, a powder metallurgy composition and a sintered body using the same.
  • the inventors of the present invention have studied in detail the influence of Si addition amount on an alloy containing Co as a base and containing one or two of Mo and W in a total amount of 25 mass% or more.
  • Alloy powder and powder sintered body Has found a range having high toughness (that is, the alloy powder is difficult to break and the powder sintered body has high bending strength), and the present invention has been completed.
  • the present inventors do not produce hard and brittle silicides in the composition range of the alloy of the present invention, while producing one or two intermetallic compounds of Co—Mo series and Co—W series. It has also been found that age hardenability is exhibited.
  • a powder metallurgy composition containing the alloy powder of the present invention is solidified and formed by a powder forming / firing method such as the HIP method (hot isostatic pressing method).
  • a powder forming / firing method such as the HIP method (hot isostatic pressing method).
  • the present invention includes the following alloy powder, shot peening projection material, powder metallurgy composition and sintered body.
  • An alloy powder comprising 35% or less, V containing 0% or more and 20% or less, Fe containing 0% or more and 15% or less, and the balance being made of Co and inevitable impurities.
  • It is characterized by containing one or more selected from Mn: more than 0% to 35% or less, V: more than 0% to 20% or less, and Fe: more than 0% to 15% or less.
  • a high hardness that can be used for a shot peening projection material a raw powder for a high hardness powder sintered body excellent in hydrochloric acid corrosion resistance, a hard friction powder, a hard particle for sintering, etc.
  • a high toughness powder, and a shot peening projection material, a powder metallurgy composition and a sintered body using the same can be provided.
  • the alloy powder of the present invention is, by mass%, one or two of Mo and W in total 25% to 50%, Cr 5% to 15%, Si 0% to 0.3%, Mn is 0% to 35%, V is 0% to 20%, and Fe is 0% to 15%, with the balance being Co and inevitable impurities.
  • the greatest feature of the alloy powder of the present invention is that both high hardness and high toughness are achieved by reducing the amount of Si added from the conventional CoMoCrSi alloy. In addition, age hardenability is also exhibited in the composition range of the alloy powder of the present invention. Furthermore, as an additive element that does not affect these characteristics, one or more of Mn, V, and Fe can be used.
  • the alloy powder of the present invention conventionally known methods such as gas atomization, water atomization, disk atomization, quenching foil strip or pulverization of cast material can be used.
  • Methods for obtaining spherical shapes such as gas atomization and disk atomization methods (for example, the lower limit of circularity by image analysis is 0.85 to 0.75), and methods for obtaining generally spherical shapes such as water atomization methods (for example, Alloy powder with a lower circularity of 0.80 to 0.70) can be used as a raw material powder for sintering because it can suppress surface roughness of the projection material when used as a shot peening projection material. In this case, the filling rate at the time of molding becomes high, which is advantageous for forming the near net.
  • alloy powder produced by various methods such as various pulverization methods (for example, the upper limit of circularity is 0.80 to 0.70) for obtaining irregular shapes is used for shot peening projection as a pretreatment for film formation such as spraying.
  • various pulverization methods for example, the upper limit of circularity is 0.80 to 0.70
  • the upper limit of circularity is 0.80 to 0.70
  • it has the effect of increasing the surface roughness of the projection material and improving the adhesion of the film, and when used as a raw material powder for sintering, the effect of increasing the shape retention during molding There is.
  • One or two kinds of Mo and W 25% or more and 50% or less
  • one or two kinds of Mo and W increase the hardness of the alloy, but the toughness such as bending strength is increased. Element to be reduced. If the total amount of one or two of Mo and W is less than 25%, sufficient hardness cannot be obtained. On the other hand, when the total amount of one or two of Mo and W exceeds 50%, toughness such as bending strength is lowered.
  • the total amount of one or two of Mo and W is preferably more than 30% and less than 50%, more preferably more than 35% and less than 45%.
  • Cr 5% or more and 15% or less
  • Cr is an element that increases the hardness of the alloy together with one or two of Mo and W, and also has an effect of improving corrosion resistance.
  • the amount of Cr is preferably 6 to 14%, more preferably 7 to 13%.
  • Si 0% or more and 0.3% or less
  • Si is an element that lowers the bending strength due to the formation of silicide and reduces the age hardening width, so the upper limit of the amount of Si is limited. It is necessary to specify. When the amount of Si exceeds 0.3%, the bending strength is significantly lowered and the age hardening width is also reduced.
  • the amount of Si is preferably 0.19% or less, more preferably less than 0.15%.
  • the lower limit of the amount of Si is not particularly limited as long as it is 0% or more. When Si is added, the lower limit of the amount of Si is not particularly limited as long as it exceeds 0%, and the lower limit of the amount of Si is, for example, 0.05%. Si may be additive-free (0.00%).
  • Mn 0% or more and 35% or less
  • V 0% or more and 20% or less
  • Fe 0% or more and 15% or less
  • the seeds or more are elements that do not impair the characteristics of the alloy powder of the present invention as long as they are not excessively added, and can be added as necessary.
  • Mn the amount of Mn can be appropriately adjusted within the range of more than 0% and 35% or less. Mn may not be added (0.00%).
  • V the amount of V can be appropriately adjusted within the range of more than 0% and not more than 20%.
  • V may be additive-free (0.00%).
  • the amount of Fe can be appropriately adjusted in the range of more than 0% and 15% or less. Fe may not be added (0.00%). If the amount of each element exceeds Mn: 35%, V: 20%, and Fe: 15%, the bending strength decreases.
  • Mn and Fe are elements that contribute to a reduction in raw material costs. Therefore, it is preferable to add Mn exceeding 20% and Fe exceeding 5%. Further, V is preferably less than 15% in order to suppress a decrease in bending strength.
  • the Vickers hardness after aging treatment of the alloy powder of the present invention is preferably 500 HV or more, more preferably 700 HV or more.
  • the Vickers hardness after the aging treatment of the alloy powder is such that the coarse particles having a particle size of more than 150 ⁇ m are removed by classification using a sieve having an opening of 150 ⁇ m, and the alloy powder having a particle size of 150 ⁇ m or less is prepared in Ar.
  • the test force in the measurement of Vickers hardness is 2.94 N (300 gf).
  • Examples of the resin suitable for the production of the test sample include a thermosetting resin. Other conditions conform to JIS Z 2244: 2009.
  • the age hardening width of the alloy powder of the present invention is preferably 100 HV or more, more preferably 200 HV or more.
  • the age hardening width of the alloy powder is given by the following formula: Vickers hardness of sintered body of alloy powder-defined by Vickers hardness before aging treatment of alloy powder.
  • the Vickers hardness before aging treatment of the alloy powder is determined by removing coarse particles having a particle size exceeding 150 ⁇ m by classification using a sieve having an opening of 150 ⁇ m, filling the alloy powder having a particle size of 150 ⁇ m or less with resin, and polishing.
  • the test sample thus prepared is measured using a micro hardness tester “FM-700” manufactured by FUTURE-TECH.
  • the test force in the measurement of Vickers hardness is 2.94 N (300 gf).
  • the resin suitable for the production of the test sample include a thermosetting resin.
  • the Vickers hardness of the sintered body of the alloy powder is obtained by removing coarse particles having a particle size exceeding 150 ⁇ m by classification using a sieve having an opening of 150 ⁇ m and preparing an alloy powder having a particle size of 150 ⁇ m or less (no aging treatment).
  • the shot peening projection material of the present invention includes the alloy powder of the present invention.
  • composition for powder metallurgy of the present invention includes the alloy powder of the present invention.
  • the composition for powder metallurgy of the present invention can be produced by mixing the alloy powder of the present invention and, if necessary, other powder (for example, graphite powder).
  • a sintered body can be produced by powder metallurgy using the composition for powder metallurgy of the present invention.
  • the alloy powder of the present invention contained in the composition for powder metallurgy of the present invention is useful as a raw material powder for a high-hardness powder sintered body, a hard friction powder, a hard particle for sintering, and the like.
  • the amount of the alloy powder of the present invention contained in the composition for powder metallurgy of the present invention and other powders contained as necessary should be adjusted as appropriate according to the molding conditions, sintering conditions, etc. used in powder metallurgy. Can do.
  • Powder metallurgy using the composition for powder metallurgy of the present invention includes a step of forming a molded body by compression molding the composition for powder metallurgy of the present invention (hereinafter referred to as “molding step”), and sintering the molded body. And a method including a step of forming a sintered body (hereinafter referred to as “sintering step”).
  • the molding step can be performed, for example, by filling the mold for powder metallurgy composition of the present invention into a mold and pressurizing to form a powder compact. Prior to filling the mold with the powder metallurgy composition, a higher fatty acid-based lubricant may be applied to the inner surface of the mold.
  • the molding step can be performed using a known molding method such as a press. The molding pressure and molding temperature can be adjusted as appropriate.
  • the sintering step can be carried out, for example, by heating and sintering the powder compact obtained in the molding step.
  • the sintering temperature and the sintering time can be adjusted as appropriate.
  • the sintering atmosphere is preferably an oxidation-preventing atmosphere such as a vacuum atmosphere, an inert gas atmosphere, or a nitrogen atmosphere.
  • Examples of the powder molding / firing method include a hot press method, a hot hydraulic press method, a powder extrusion method, and a powder forging method.
  • the sintered body of the present invention is obtained by sintering a molded body of the composition for powder metallurgy of the present invention.
  • the bending strength of the sintered body of the present invention is preferably 400 MPa or more, more preferably 800 MPa or more.
  • the bending strength of the sintered body is evaluated by a three-point bending test on a test piece having a length of 4 mm, a width of 25 mm, and a thickness of 3 mm, which is determined from the sintered body with a wire.
  • the distance between the fulcrums is 10 mm
  • the surface of 4 mm in length and 25 mm in width is crushed
  • the stress (N) at that time is measured
  • the three-point bending strength is calculated based on the following equation.
  • Three-point bending strength (MPa) (3 ⁇ stress (N) ⁇ distance between support points (mm) / (2 ⁇ width of test piece (mm) ⁇ (thickness of test piece (mm) 2 )
  • the test powder was prepared by a gas atomization method, a water atomization method, a quenching ribbon pulverization method, or a casting pulverization method.
  • the melted raw material weighed to 25 kg is induction-melted to 1750 ° C. in a refractory crucible under reduced pressure Ar, discharged from a nozzle with a diameter of 7 mm at the bottom of the crucible, and atomized using nitrogen gas or water as a spraying medium. I did it.
  • the quenching ribbon pulverization method the melted raw material weighed to 30 g is induction-melted in a quartz tube under reduced pressure Ar, discharged from a 1 mm nozzle at the bottom of the quartz tube into a copper roll having a diameter of 300 mm and a rotation speed of 500 rpm, and the quenching ribbon is Obtained.
  • the melted raw material weighed to 200 g is arc-melted in a water-cooled copper mold having a diameter of 50 mm under reduced pressure Ar, and the solidified ingot is coarsely pulverized by a stamp mill, and then placed in an Ar-substituted planetary ball mill. Crushed with. This was vacuum-sealed in a quartz tube, held in a heating furnace at 1200 ° C. for 1 hour, and then subjected to a solution treatment that was air-cooled.
  • the average circularity measured by Seita Enterprise Co., Ltd. PITA-1 was 0.80 or more for gas atomized powder, 0.75 or more for water atomized powder, and less than 0.75 for pulverized powder.
  • coarse particles having a particle size exceeding 150 ⁇ m are removed by classification using a sieve having an opening of 150 ⁇ m, and the particle size is 150 ⁇ m or less.
  • the sintered body was prepared by cooling, and evaluated by measuring the Vickers hardness (same method as powder) and bending strength (three-point bending test with a fulcrum distance of 10 mm) of the sintered body. The bending strength was evaluated by a three-point bending test on a test piece having a length of 4 mm, a width of 25 mm, and a thickness of 3 mm determined from a sintered body with a wire.
  • a powder having the composition shown in Table 1 was prepared and evaluated, and the results shown in Table 1 were obtained.
  • “A” is the case where the Vickers hardness after the aging treatment of the powder is 700 HV or more
  • B is the case where the Vickers hardness is less than 700 HV and 500 HV or more
  • “C” is the case where the Vickers hardness is less than 500 HV.
  • A indicates that “Vickers hardness of sintered powder of alloy powder ⁇ Vickers hardness before aging treatment of alloy powder” is 200 HV or higher, and “B” indicates that Vickers hardness of 200 HV or higher is less than 200 HV. ", And less than 100 HV was designated as” C ".
  • the powder sintered body having a bending strength of 800 MPa or more was designated as “A”, the one having a bending strength of less than 800 MPa and 400 MPa or more was designated as “B”, and the one having less than 400 MPa was designated as “C”. .
  • No. Nos. 1 to 12 are examples of the present invention.
  • Reference numerals 13 to 23 are comparative examples.
  • Comparative Example No. 17 to 20 since the Si content in the powder composition is large (greater than 0.3% by mass), the bending strength of the powder sintered body is significantly reduced (Evaluation C), and the aging of the powder The curing width becomes small (Evaluation C). Comparative Example No. Nos. 21 to 23 have a high content of Mn, V and Fe in the powder composition (Mn: more than 35% by mass, V: more than 20% by mass, Fe: more than 15% by mass). Folding strength is inferior (Evaluation C).
  • No. which is the present invention Since all of Nos. 1 to 12 satisfy the conditions of the present invention, it can be seen that the Vickers hardness after the aging treatment of the powder, the age hardening width of the powder, and the bending strength of the powder sintered body are excellent.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention addresses the problem of providing a high-hardness high-toughness alloy powder that can be used in hard particles for sintering, a hard friction powder, a raw material powder for a high-hardness powder metallurgy material having exceptional hydrochloric acid corrosion resistance, a shot peening projection material, or the like. In order to solve this problem, the present invention provides a high-hardness high-toughness alloy powder characterized in containing, in percent by mass, a total of 25-50% of Mo and/or W, 5-15% of Cr, 0-0.3% of Si, 0-35% of Mn, 0-20% of V, and 0-15% of Fe, the balance being Co and unavoidable impurities.

Description

高硬度高靭性粉末High hardness and tough powder 関連出願の相互参照Cross-reference of related applications
　本出願は、２０１５年１２月２２日に出願された日本出願である特願２０１５－２４９１９９に基づく優先権を主張するものであり、それらの開示内容全体は、参照により本明細書に組み込まれる。 This application claims priority based on Japanese Patent Application No. 2015-249199, filed on December 22, 2015, the entire disclosure of which is incorporated herein by reference.
　本発明は、ショットピーニング用投射材、塩酸耐食性に優れる高硬度粉末焼結体用の原料粉末、硬質摩擦粉末、焼結用硬質粒子などに使用することができる高硬度高靭性合金粉末、ならびに、それを使用したショットピーニング用投射材、粉末冶金用組成物および焼結体に関する。 The present invention is a shot material for shot peening, a raw material powder for a high hardness powder sintered body excellent in hydrochloric acid corrosion resistance, a hard friction powder, a high hardness high toughness alloy powder that can be used for sintering hard particles, and the like, The present invention relates to a projection material for shot peening, a composition for powder metallurgy, and a sintered body using the same.
　従来、Ｃｏ－Ｍｏ系およびＣｏ－Ｗ系の合金は、それぞれの２元状態図からわかるとおり、様々な金属間化合物を生成する。これらの金属間化合物は高硬度を有しており、各種の高硬度材料および耐摩耗材料に適している。また、ＭｏおよびＷは、Ｃｏに固溶することにより、耐食性を改善する効果もあり、特に塩酸のような還元性酸に対する耐食性を改善する効果が大きい。また、Ｃｏ自体もベース金属として各種酸に対して高い耐食性を有する。したがって、これらの合金組成の粉末は、ショットピーニング用投射材、塩酸耐食性に優れる高硬度粉末焼結体用の原料粉末、硬質摩擦粉末、焼結用硬質粒子などに利用することができる。 Conventionally, Co-Mo alloys and Co-W alloys produce various intermetallic compounds as can be seen from the respective binary phase diagrams. These intermetallic compounds have high hardness and are suitable for various high hardness materials and wear resistant materials. Mo and W also have an effect of improving the corrosion resistance by being dissolved in Co, and particularly have a great effect of improving the corrosion resistance against a reducing acid such as hydrochloric acid. Further, Co itself has high corrosion resistance against various acids as a base metal. Therefore, powders of these alloy compositions can be used for shot peening projection materials, raw powders for high hardness powder sintered bodies having excellent hydrochloric acid corrosion resistance, hard friction powders, hard particles for sintering, and the like.
　例えば、ＷＯ２０１２／０６３５１２Ａ１号公報（特許文献１）に開示されている、ＣｏＭｏＣｒＳｉ系合金粉末〔トリバロイ（登録商標）〕が多く使用されている。一方、合金の高硬度化のために添加されるＳｉは、硬質ではあるが脆性な珪化物を生成し、合金の抗折強度を低下させるため、特に高い抗折強度が必要な用途においては問題となる場合もあった。これらのことから、ＭｏおよびＷを、硬さおよび耐食性改善のために、可能な限り多量に添加したい場合でも、抗折強度等の靭性を考慮し、添加量を低く留めざるを得ない状況が実状であった。 For example, a CoMoCrSi-based alloy powder [Trivalloy (registered trademark)] disclosed in WO2012 / 063512A1 (Patent Document 1) is often used. On the other hand, Si added to increase the hardness of the alloy produces a hard but brittle silicide and lowers the bending strength of the alloy, which is problematic in applications that require a high bending strength. There was also a case. From these, even when it is desired to add Mo and W as much as possible in order to improve hardness and corrosion resistance, it is necessary to keep the addition amount low in consideration of toughness such as bending strength. It was real.
ＷＯ２０１２／０６３５１２Ａ１公報WO2012 / 063512A1 Publication
　本発明は、ショットピーニング用投射材、塩酸耐食性に優れる高硬度粉末焼結体用の原料粉末、硬質摩擦粉末、焼結用硬質粒子などに使用することができる高硬度高靭性合金粉末、ならびに、それを使用したショットピーニング用投射材、粉末冶金用組成物および焼結体を提供することを目的とする。 The present invention is a shot material for shot peening, a raw material powder for a high hardness powder sintered body excellent in hydrochloric acid corrosion resistance, a hard friction powder, a high hardness high toughness alloy powder that can be used for sintering hard particles, and the like, An object is to provide a shot peening projection material, a powder metallurgy composition and a sintered body using the same.
　本発明者らは、Ｃｏをベースとし、ＭｏおよびＷの１種または２種を合計で２５質量％以上含む合金に関して、Ｓｉ添加量が与える影響を詳細に検討し、合金粉末及び粉末焼結体が高い靭性を有する（すなわち、合金粉末が割れにくく、粉末焼結体が高い抗折強度を有する）範囲を見出し、本発明を完成させるに至った。なお、本発明者らは、本発明の合金の組成範囲において、硬質かつ脆性な珪化物が生成されない一方、Ｃｏ－Ｍｏ系およびＣｏ－Ｗ系の１種または２種の金属間化合物の生成により、時効硬化性が発揮されることも見出しており、例えば、本発明の合金粉末を含む粉末冶金用組成物をＨＩＰ法（熱間静水圧プレス法）などの粉末成形・焼成方法により固化成形した後、熱処理により粉末焼結体の硬さを変化させることが可能であることから、粉末焼結体を低硬度の状態で機械加工し、その後、時効処理により粉末焼結体の硬度を上げることもできる。したがって、本発明の合金粉末は、機械加工が容易な低硬度の状態で加工し、耐摩耗性に優れる高硬度の状態にして使用できる粉末焼結体を提供することを可能とした。 The inventors of the present invention have studied in detail the influence of Si addition amount on an alloy containing Co as a base and containing one or two of Mo and W in a total amount of 25 mass% or more. Alloy powder and powder sintered body Has found a range having high toughness (that is, the alloy powder is difficult to break and the powder sintered body has high bending strength), and the present invention has been completed. Note that the present inventors do not produce hard and brittle silicides in the composition range of the alloy of the present invention, while producing one or two intermetallic compounds of Co—Mo series and Co—W series. It has also been found that age hardenability is exhibited. For example, a powder metallurgy composition containing the alloy powder of the present invention is solidified and formed by a powder forming / firing method such as the HIP method (hot isostatic pressing method). After that, it is possible to change the hardness of the powder sintered body by heat treatment, so machine the powder sintered body in a low hardness state, and then increase the hardness of the powder sintered body by aging treatment You can also. Therefore, the alloy powder of the present invention can be processed in a low hardness state that can be easily machined, and can provide a powder sintered body that can be used in a high hardness state excellent in wear resistance.
　したがって、本発明は、以下の合金粉末、ショットピーニング用投射材、粉末冶金用組成物および焼結体を包含する。
［１］質量％で、ＭｏおよびＷの１種または２種を合計で２５％以上５０％以下、Ｃｒを５％以上１５％以下、Ｓｉを０％以上０．３％以下、Ｍｎを０％以上３５％以下、Ｖを０％以上２０％以下、ならびに、Ｆｅを０％以上１５％以下含有し、残部がＣｏおよび不可避的不純物からなることを特徴とする、合金粉末。
［２］質量％で、Ｍｎ：０％超３５％以下、Ｖ：０％超２０％以下およびＦｅ：０％超１５％以下から選ばれた１種または２種以上を含有することを特徴とする、［１］に記載の合金粉末。
［３］時効処理後のビッカース硬さが５００ＨＶ以上である、［１］または［２］に記載の合金粉末。
［４］次式：
　合金粉末の焼結体のビッカース硬さ－合金粉末の時効処理前のビッカース硬さ
により定義される合金粉末の時効硬化幅が１００ＨＶ以上である、［１］～［３］のいずれかにに記載の合金粉末。
［５］［１］～［４］のいずれかに記載の合金粉末を含む、ショットピーニング用投射材。
［６］［１］～［４］のいずれかに記載の合金粉末を含む、粉末冶金用組成物。
［７］［６］に記載の粉末冶金用組成物の成形体を焼結して得られる焼結体。
［８］抗折強度が４００ＭＰａ以上である、［７］に記載の焼結体。 Accordingly, the present invention includes the following alloy powder, shot peening projection material, powder metallurgy composition and sintered body.
[1] In mass%, one or two of Mo and W in total 25% to 50%, Cr 5% to 15%, Si 0% to 0.3%, Mn 0% An alloy powder comprising 35% or less, V containing 0% or more and 20% or less, Fe containing 0% or more and 15% or less, and the balance being made of Co and inevitable impurities.
[2] It is characterized by containing one or more selected from Mn: more than 0% to 35% or less, V: more than 0% to 20% or less, and Fe: more than 0% to 15% or less. The alloy powder according to [1].
[3] The alloy powder according to [1] or [2], wherein the Vickers hardness after aging treatment is 500 HV or more.
[4] The following formula:
The Vickers hardness of the sintered body of the alloy powder-the age hardening width of the alloy powder defined by the Vickers hardness before the aging treatment of the alloy powder is 100 HV or more, according to any one of [1] to [3] Alloy powder.
[5] A shot peening projection material comprising the alloy powder according to any one of [1] to [4].
[6] A composition for powder metallurgy comprising the alloy powder according to any one of [1] to [4].
[7] A sintered body obtained by sintering a molded body of the composition for powder metallurgy according to [6].
[8] The sintered body according to [7], wherein the bending strength is 400 MPa or more.
　以上に述べたように、本発明により、ショットピーニング用投射材、塩酸耐食性に優れる高硬度粉末焼結体用の原料粉末、硬質摩擦粉末、焼結用硬質粒子などに使用することができる高硬度高靭性粉末、ならびに、それを使用したショットピーニング用投射材、粉末冶金用組成物および焼結体を提供することができる。 As described above, according to the present invention, a high hardness that can be used for a shot peening projection material, a raw powder for a high hardness powder sintered body excellent in hydrochloric acid corrosion resistance, a hard friction powder, a hard particle for sintering, etc. A high toughness powder, and a shot peening projection material, a powder metallurgy composition and a sintered body using the same can be provided.
　以下、本発明について詳細に説明する。なお、本発明において、「％」は、別段規定される場合を除き、質量％を意味する。 Hereinafter, the present invention will be described in detail. In the present invention, “%” means mass% unless otherwise specified.
〔合金粉末〕
　本発明の合金粉末は、質量％で、ＭｏおよびＷの１種または２種を合計で２５％以上５０％以下、Ｃｒを５％以上１５％以下、Ｓｉを０％以上０．３％以下、Ｍｎを０％以上３５％以下、Ｖを０％以上２０％以下、ならびに、Ｆｅを０％以上１５％以下含有し、残部がＣｏおよび不可避的不純物からなることを特徴とする。 [Alloy powder]
The alloy powder of the present invention is, by mass%, one or two of Mo and W in total 25% to 50%, Cr 5% to 15%, Si 0% to 0.3%, Mn is 0% to 35%, V is 0% to 20%, and Fe is 0% to 15%, with the balance being Co and inevitable impurities.
　本発明の合金粉末における最大の特徴は、Ｓｉの添加量を、従来のＣｏＭｏＣｒＳｉ合金より低減することにより、高硬度と高靭性を両立させたことである。また、本発明の合金粉末の組成範囲において、時効硬化性も発揮される。さらに、これらの特徴に影響しない添加元素として、Ｍｎ、Ｖ、Ｆｅの１種または２種以上の使用も可能である。 The greatest feature of the alloy powder of the present invention is that both high hardness and high toughness are achieved by reducing the amount of Si added from the conventional CoMoCrSi alloy. In addition, age hardenability is also exhibited in the composition range of the alloy powder of the present invention. Furthermore, as an additive element that does not affect these characteristics, one or more of Mn, V, and Fe can be used.
　なお、本発明の合金粉末の製法としては、従来から知られている、ガスアトマイズ、水アトマイズ、ディスクアトマイズ、急冷箔帯または鋳造材の粉砕などが利用することができる。ガスアトマイズ、ディスクアトマイズ法などの球形状が得られる工法（例えば、画像解析による円形度の下限値が０．８５～０．７５）や、水アトマイズ法などの概ね球形状が得られる工法（例えば、円形度の下限値が０．８０～０．７０）による合金粉末は、ショットピーニング投射材として使用する場合には、被投射材の表面荒れを抑制することができ、焼結用原料粉末として使用する場合には、成形時の充填率が高くなり、ニアネットの成形に有利となる。 In addition, as a manufacturing method of the alloy powder of the present invention, conventionally known methods such as gas atomization, water atomization, disk atomization, quenching foil strip or pulverization of cast material can be used. Methods for obtaining spherical shapes such as gas atomization and disk atomization methods (for example, the lower limit of circularity by image analysis is 0.85 to 0.75), and methods for obtaining generally spherical shapes such as water atomization methods (for example, Alloy powder with a lower circularity of 0.80 to 0.70) can be used as a raw material powder for sintering because it can suppress surface roughness of the projection material when used as a shot peening projection material. In this case, the filling rate at the time of molding becomes high, which is advantageous for forming the near net.
　一方、各種粉砕法などの、不定形状が得られる工法（例えば、円形度の上限値が０．８０～０．７０）による合金粉末は、溶射など成膜処理の前処理としてのショットピーニング用投射材として使用する場合には、被投射材の表面粗度を上げ、皮膜の密着性を改善する効果があり、焼結用原料粉末に使用する場合には、成形時の保形性を高める効果がある。 On the other hand, alloy powder produced by various methods such as various pulverization methods (for example, the upper limit of circularity is 0.80 to 0.70) for obtaining irregular shapes is used for shot peening projection as a pretreatment for film formation such as spraying. When used as a material, it has the effect of increasing the surface roughness of the projection material and improving the adhesion of the film, and when used as a raw material powder for sintering, the effect of increasing the shape retention during molding There is.
　以下、本発明の合金粉末の成分組成を規制した理由について説明する。
　ＭｏおよびＷの１種または２種：２５％以上５０％以下
　本発明の合金粉末において、ＭｏおよびＷの１種または２種は、合金の硬さを増加させるが、抗折強度等の靭性を低下させる元素である。ＭｏおよびＷの１種または２種の合計量が２５％未満では、十分な硬さが得られない。一方、ＭｏおよびＷの１種または２種の合計量が５０％を超えると、抗折強度等の靱性が低下する。ＭｏおよびＷの１種または２種の合計量は、好ましくは３０％を超え５０％未満、より好ましくは３５％を超え４５％未満である。 The reason why the composition of the alloy powder of the present invention is regulated will be described below.
One or two kinds of Mo and W: 25% or more and 50% or less In the alloy powder of the present invention, one or two kinds of Mo and W increase the hardness of the alloy, but the toughness such as bending strength is increased. Element to be reduced. If the total amount of one or two of Mo and W is less than 25%, sufficient hardness cannot be obtained. On the other hand, when the total amount of one or two of Mo and W exceeds 50%, toughness such as bending strength is lowered. The total amount of one or two of Mo and W is preferably more than 30% and less than 50%, more preferably more than 35% and less than 45%.
　Ｃｒ：５％以上１５％以下
　本発明の合金粉末において、Ｃｒは、ＭｏおよびＷの１種または２種とともに、合金の硬さを上昇させる元素であり、耐食性改善の効果も有する。Ｃｒの量が５％未満では、硬さおよび耐食性が不十分であり、Ｃｒの量が１５％を超えると、時効前硬さが高くなり、時効硬化幅が小さくなってしまう。Ｃｒの量は、好ましくは６～１４％、より好ましくは７～１３％である。 Cr: 5% or more and 15% or less In the alloy powder of the present invention, Cr is an element that increases the hardness of the alloy together with one or two of Mo and W, and also has an effect of improving corrosion resistance. When the amount of Cr is less than 5%, the hardness and corrosion resistance are insufficient, and when the amount of Cr exceeds 15%, the pre-aging hardness increases and the age hardening width decreases. The amount of Cr is preferably 6 to 14%, more preferably 7 to 13%.
　Ｓｉ：０％以上０．３％以下
　本発明の合金粉末において、Ｓｉは、珪化物生成により抗折強度を低下させ、また、時効硬化幅を小さくする元素であるため、Ｓｉの量の上限を規定する必要がある。Ｓｉの量が０．３％を超えると、抗折強度の低下が顕著となり、時効硬化幅も小さくなる。Ｓｉの量は、好ましくは０．１９％以下、より好ましくは０．１５％未満である。Ｓｉの量の下限値は０％以上である限り特に限定されない。Ｓｉが添加される場合、Ｓｉの量の下限値は０％超である限り特に限定されず、Ｓｉの量の下限値は、例えば、０．０５％である。Ｓｉは、無添加（０．００％）であってもよい。 Si: 0% or more and 0.3% or less In the alloy powder of the present invention, Si is an element that lowers the bending strength due to the formation of silicide and reduces the age hardening width, so the upper limit of the amount of Si is limited. It is necessary to specify. When the amount of Si exceeds 0.3%, the bending strength is significantly lowered and the age hardening width is also reduced. The amount of Si is preferably 0.19% or less, more preferably less than 0.15%. The lower limit of the amount of Si is not particularly limited as long as it is 0% or more. When Si is added, the lower limit of the amount of Si is not particularly limited as long as it exceeds 0%, and the lower limit of the amount of Si is, for example, 0.05%. Si may be additive-free (0.00%).
　Ｍｎ：０％以上３５％以下、Ｖ：０％以上２０％以下、Ｆｅ：０％以上１５％以下の１種または２種以上
　本発明の合金粉末において、Ｍｎ、Ｖ、Ｆｅの１種または２種以上は、過度に添加しない範囲において本発明の合金粉末の特徴を損なうことのない元素であり、必要に応じて添加することができる。Ｍｎが添加される場合、Ｍｎの量は０％超３５％以下の範囲で適宜調整可能である。Ｍｎは無添加（０．００％）であってもよい。Ｖが添加される場合、Ｖの量は０％超２０％以下の範囲で適宜調整可能である。Ｖは無添加（０．００％）であってもよい。Ｆｅが添加される場合、Ｆｅの量は０％超１５％以下の範囲で適宜調整可能である。Ｆｅは無添加（０．００％）であってもよい。それぞれの元素の添加量が、Ｍｎ：３５％、Ｖ：２０％、Ｆｅ：１５％を超えると、抗折強度が低下する。一方、Ｍｎ、Ｆｅは原料費の低減に寄与する元素である。したがって、Ｍｎは２０％を超えて、Ｆｅは５％を超えて添加することが好ましい。また、Ｖは抗折強度の低下を抑制するため、好ましくは１５％未満である。 Mn: 0% or more and 35% or less, V: 0% or more and 20% or less, Fe: 0% or more and 15% or less, one or more of Mn, V, and Fe in the alloy powder of the present invention The seeds or more are elements that do not impair the characteristics of the alloy powder of the present invention as long as they are not excessively added, and can be added as necessary. When Mn is added, the amount of Mn can be appropriately adjusted within the range of more than 0% and 35% or less. Mn may not be added (0.00%). When V is added, the amount of V can be appropriately adjusted within the range of more than 0% and not more than 20%. V may be additive-free (0.00%). When Fe is added, the amount of Fe can be appropriately adjusted in the range of more than 0% and 15% or less. Fe may not be added (0.00%). If the amount of each element exceeds Mn: 35%, V: 20%, and Fe: 15%, the bending strength decreases. On the other hand, Mn and Fe are elements that contribute to a reduction in raw material costs. Therefore, it is preferable to add Mn exceeding 20% and Fe exceeding 5%. Further, V is preferably less than 15% in order to suppress a decrease in bending strength.
　本発明の合金粉末の時効処理後のビッカース硬さは、好ましくは５００ＨＶ以上、さらに好ましくは７００ＨＶ以上である。合金粉末の時効処理後のビッカース硬さは、目開き１５０μｍの篩を使用した分級により粒径が１５０μｍを超える粗粒子を除去し、粒径を１５０μｍ以下に揃えた合金粉末を、Ａｒ中において、８００℃で３時間、時効処理した後、時効処理された合金粉末を樹脂埋めし、研磨して作製した試験サンプルに対し、ＦＵＴＵＲＥ－ＴＥＣＨ社の微小硬度計「ＦＭ－７００」を使用して測定する。ビッカース硬さの測定における試験力は２．９４Ｎ（３００ｇｆ）とする。試験サンプルの作製に適した樹脂としては、熱硬化性樹脂が挙げられる。その他の条件は、ＪＩＳ　Ｚ　２２４４：２００９に準じる。 The Vickers hardness after aging treatment of the alloy powder of the present invention is preferably 500 HV or more, more preferably 700 HV or more. The Vickers hardness after the aging treatment of the alloy powder is such that the coarse particles having a particle size of more than 150 μm are removed by classification using a sieve having an opening of 150 μm, and the alloy powder having a particle size of 150 μm or less is prepared in Ar. Measured using a FUTURE-TECH micro hardness tester “FM-700” for a test sample prepared by aging treatment at 800 ° C. for 3 hours and then filling and polishing the aged alloy powder. To do. The test force in the measurement of Vickers hardness is 2.94 N (300 gf). Examples of the resin suitable for the production of the test sample include a thermosetting resin. Other conditions conform to JIS Z 2244: 2009.
　本発明の合金粉末の時効硬化幅は、好ましくは１００ＨＶ以上、さらに好ましくは２００ＨＶ以上である。合金粉末の時効硬化幅は、次式：
　合金粉末の焼結体のビッカース硬さ－合金粉末の時効処理前のビッカース硬さ
により定義される。合金粉末の時効処理前のビッカース硬さは、目開き１５０μｍの篩を使用した分級により粒径が１５０μｍを超える粗粒子を除去し、粒径を１５０μｍ以下に揃えた合金粉末を樹脂埋めし、研磨して作製した試験サンプルに対し、ＦＵＴＵＲＥ－ＴＥＣＨ社の微小硬度計「ＦＭ－７００」を使用して測定する。ビッカース硬さの測定における試験力は２．９４Ｎ（３００ｇｆ）とする。試験サンプルの作製に適した樹脂としては、熱硬化性樹脂が挙げられる。その他の条件は、ＪＩＳ　Ｚ　２２４４：２００９に準じる。合金粉末の焼結体のビッカース硬さは、目開き１５０μｍの篩を使用した分級により粒径が１５０μｍを超える粗粒子を除去し、粒径を１５０μｍ以下に揃えた合金粉末（時効処理なし）を、内径３０ｍｍ、高さ３０ｍｍのステンレス製カプセルに充填、脱気、封入し、保持温度１１５０℃、保持時間３ｈ、成形圧力１４７ＭＰａでＨＩＰ成形し、その後、徐冷して焼結体を作製し、合金粉末のビッカース硬さと同様に測定する。 The age hardening width of the alloy powder of the present invention is preferably 100 HV or more, more preferably 200 HV or more. The age hardening width of the alloy powder is given by the following formula:
Vickers hardness of sintered body of alloy powder-defined by Vickers hardness before aging treatment of alloy powder. The Vickers hardness before aging treatment of the alloy powder is determined by removing coarse particles having a particle size exceeding 150 μm by classification using a sieve having an opening of 150 μm, filling the alloy powder having a particle size of 150 μm or less with resin, and polishing. The test sample thus prepared is measured using a micro hardness tester “FM-700” manufactured by FUTURE-TECH. The test force in the measurement of Vickers hardness is 2.94 N (300 gf). Examples of the resin suitable for the production of the test sample include a thermosetting resin. Other conditions conform to JIS Z 2244: 2009. The Vickers hardness of the sintered body of the alloy powder is obtained by removing coarse particles having a particle size exceeding 150 μm by classification using a sieve having an opening of 150 μm and preparing an alloy powder having a particle size of 150 μm or less (no aging treatment). Filled, degassed and sealed in a stainless capsule with an inner diameter of 30 mm and a height of 30 mm, HIP molded at a holding temperature of 1150 ° C., a holding time of 3 h, a molding pressure of 147 MPa, and then gradually cooled to produce a sintered body, It is measured in the same manner as the Vickers hardness of the alloy powder.
〔ショットピーニング用投射材〕
　本発明のショットピーニング投射材は、本発明の合金粉末を含む。 [Projection material for shot peening]
The shot peening projection material of the present invention includes the alloy powder of the present invention.
〔粉末冶金用組成物〕
　本発明の粉末冶金用組成物は、本発明の合金粉末を含む。
　本発明の粉末冶金用組成物は、本発明の合金粉末と、必要によりその他の粉末（例えば、黒鉛粉末）とを混合することにより製造することができる。 [Composition for powder metallurgy]
The composition for powder metallurgy of the present invention includes the alloy powder of the present invention.
The composition for powder metallurgy of the present invention can be produced by mixing the alloy powder of the present invention and, if necessary, other powder (for example, graphite powder).
　本発明の粉末冶金用組成物を使用した粉末冶金により焼結体（焼結合金）を製造することができる。本発明の粉末冶金用組成物に含まれる本発明の合金粉末は、高硬度粉末焼結体用の原料粉末、硬質摩擦粉末、焼結用硬質粒子などとして有用である。 A sintered body (sintered alloy) can be produced by powder metallurgy using the composition for powder metallurgy of the present invention. The alloy powder of the present invention contained in the composition for powder metallurgy of the present invention is useful as a raw material powder for a high-hardness powder sintered body, a hard friction powder, a hard particle for sintering, and the like.
　本発明の粉末冶金用組成物に含まれる本発明の合金粉末および必要に応じて含まれるその他の粉末の量は、粉末冶金に使用される成形条件、焼結条件等に応じて適宜調整することができる。 The amount of the alloy powder of the present invention contained in the composition for powder metallurgy of the present invention and other powders contained as necessary should be adjusted as appropriate according to the molding conditions, sintering conditions, etc. used in powder metallurgy. Can do.
　本発明の粉末冶金用組成物を使用した粉末冶金は、本発明の粉末冶金用組成物を圧縮成形して成形体を形成する工程（以下「成形工程」という）と、該成形体を焼結して焼結体を形成する工程（以下「焼結工程」という）とを含む方法により実施することができる。 Powder metallurgy using the composition for powder metallurgy of the present invention includes a step of forming a molded body by compression molding the composition for powder metallurgy of the present invention (hereinafter referred to as “molding step”), and sintering the molded body. And a method including a step of forming a sintered body (hereinafter referred to as “sintering step”).
　成形工程は、例えば、本発明の粉末冶金用組成物を金型へ充填し、加圧して粉末成形体を形成することにより実施することができる。粉末冶金用組成物を金型へ充填する前に、金型の内面に高級脂肪酸系潤滑剤を塗布してもよい。成形工程は、プレス等の公知の成形方法を使用して実施することができる。成形圧力及び成形温度は、適宜調整可能である。 The molding step can be performed, for example, by filling the mold for powder metallurgy composition of the present invention into a mold and pressurizing to form a powder compact. Prior to filling the mold with the powder metallurgy composition, a higher fatty acid-based lubricant may be applied to the inner surface of the mold. The molding step can be performed using a known molding method such as a press. The molding pressure and molding temperature can be adjusted as appropriate.
　焼結工程は、例えば、成形工程で得られた粉末成形体を加熱して焼結することにより実施することができる。焼結温度及び焼結時間は、適宜調整可能である。焼結雰囲気は、真空雰囲気、不活性ガス雰囲気、窒素雰囲気等の酸化防止雰囲気であることが好ましい。 The sintering step can be carried out, for example, by heating and sintering the powder compact obtained in the molding step. The sintering temperature and the sintering time can be adjusted as appropriate. The sintering atmosphere is preferably an oxidation-preventing atmosphere such as a vacuum atmosphere, an inert gas atmosphere, or a nitrogen atmosphere.
　粉末成形・焼成方法としては、例えば、ホットプレス法、熱間水圧プレス法、粉末押し出し法、粉末鍛造法等が挙げられる。 Examples of the powder molding / firing method include a hot press method, a hot hydraulic press method, a powder extrusion method, and a powder forging method.
〔焼結体〕
　本発明の焼結体は、本発明の粉末冶金用組成物の成形体を焼結して得られる。
　本発明の焼結体の抗折強度は、好ましくは４００ＭＰａ以上、さらに好ましくは８００ＭＰａ以上である。 (Sintered body)
The sintered body of the present invention is obtained by sintering a molded body of the composition for powder metallurgy of the present invention.
The bending strength of the sintered body of the present invention is preferably 400 MPa or more, more preferably 800 MPa or more.
　焼結体の抗折強度は、焼結体からワイヤーで割り出した、縦４ｍｍ、幅２５ｍｍ、厚さ３ｍｍの試験片を、三点曲げ試験によって評価する。三点曲げ試験は、支点間距離１０ｍｍで、縦４ｍｍ、幅２５ｍｍの面を圧下し、その時の応力（Ｎ）を測定し、次式に基づき、三点曲げ強度を算出する。
三点曲げ強度（ＭＰａ）＝（３×応力（Ｎ）×支点間距離（ｍｍ）／（２×試験片の幅（ｍｍ）×（試験片の厚さ（ｍｍ）2） The bending strength of the sintered body is evaluated by a three-point bending test on a test piece having a length of 4 mm, a width of 25 mm, and a thickness of 3 mm, which is determined from the sintered body with a wire. In the three-point bending test, the distance between the fulcrums is 10 mm, the surface of 4 mm in length and 25 mm in width is crushed, the stress (N) at that time is measured, and the three-point bending strength is calculated based on the following equation.
Three-point bending strength (MPa) = (3 × stress (N) × distance between support points (mm) / (2 × width of test piece (mm) × (thickness of test piece (mm) 2 )
　以下、本発明について、実施例に基づいて具体的に説明する。
　先ず、合金粉末の作製について説明する。供試粉末は、ガスアトマイズ法、水アトマイズ法、急冷リボン粉砕法または鋳造粉砕法で作製した。 Hereinafter, the present invention will be specifically described based on examples.
First, preparation of alloy powder will be described. The test powder was prepared by a gas atomization method, a water atomization method, a quenching ribbon pulverization method, or a casting pulverization method.
　アトマイズ法では、２５ｋｇに秤量した溶解原料を、減圧Ａｒ下の耐火物製坩堝内で１７５０℃まで誘導溶解し、坩堝下部の直径７ｍｍのノズルから出湯し、窒素ガスまたは水を噴霧媒体としてアトマイズを行なった。 In the atomizing method, the melted raw material weighed to 25 kg is induction-melted to 1750 ° C. in a refractory crucible under reduced pressure Ar, discharged from a nozzle with a diameter of 7 mm at the bottom of the crucible, and atomized using nitrogen gas or water as a spraying medium. I did it.
　急冷リボン粉砕法では、３０ｇに秤量した溶解原料を、減圧Ａｒ下の石英管内で誘導溶解し、石英管底の１ｍｍのノズルから、直径３００ｍｍ、回転数５００ｒｐｍの銅ロールに出湯し、急冷リボンを得た。これを、Ａｒ置換した遊星ボールミル内で粉砕した。これを、石英管中に真空封入し、加熱炉内に、１２００℃で１時間保持した後、空冷する溶体化処理を行った。 In the quenching ribbon pulverization method, the melted raw material weighed to 30 g is induction-melted in a quartz tube under reduced pressure Ar, discharged from a 1 mm nozzle at the bottom of the quartz tube into a copper roll having a diameter of 300 mm and a rotation speed of 500 rpm, and the quenching ribbon is Obtained. This was pulverized in an Ar-substituted planetary ball mill. This was vacuum-sealed in a quartz tube, held in a heating furnace at 1200 ° C. for 1 hour, and then subjected to a solution treatment that was air-cooled.
　鋳造粉砕法では、２００ｇに秤量した溶解原料を、直径５０ｍｍの水冷銅鋳型内で、減圧Ａｒ下でアーク溶解し、凝固させたインゴットを、スタンプミルで粗粉砕した後、Ａｒ置換した遊星ボールミル内で粉砕した。これを、石英管中に真空封入し、加熱炉内に、１２００℃で１時間保持した後、空冷する溶体化処理を行った。 In the casting pulverization method, the melted raw material weighed to 200 g is arc-melted in a water-cooled copper mold having a diameter of 50 mm under reduced pressure Ar, and the solidified ingot is coarsely pulverized by a stamp mill, and then placed in an Ar-substituted planetary ball mill. Crushed with. This was vacuum-sealed in a quartz tube, held in a heating furnace at 1200 ° C. for 1 hour, and then subjected to a solution treatment that was air-cooled.
　なお、セイシン企業社製のＰＩＴＡ－１で測定した平均円形度は、ガスアトマイズ粉末が０．８０以上、水アトマイズ粉末が０．７５以上、粉砕粉末は０．７５未満であった。 In addition, the average circularity measured by Seita Enterprise Co., Ltd. PITA-1 was 0.80 or more for gas atomized powder, 0.75 or more for water atomized powder, and less than 0.75 for pulverized powder.
　合金粉末の硬さについては、目開き１５０μｍの篩を使用した分級により粒径が１５０μｍを超える粗粒子を除去し、粒径を１５０μｍ以下に揃えた粉末を樹脂に埋め、研磨して試験サンプルを作製し、試験サンプルのビッカース硬さを測定することにより評価した。ビッカース硬さの測定は、ＦＵＴＵＲＥ－ＴＥＣＨ社の微小硬度計「ＦＭ－７００」を使用し、試験荷重２．９４Ｎ（３００ｇｆ）にて実施した。試験サンプルの作製には、熱硬化性樹脂を使用した。試験サンプルのビッカース硬さは、ｎ＝５の平均値で評価した。また、Ａｒ中において、８００℃で３時間、時効処理した粉末についても同様にビッカース硬さを測定した。 Regarding the hardness of the alloy powder, coarse particles having a particle size exceeding 150 μm are removed by classification using a sieve having an opening of 150 μm, and a powder having a particle size of 150 μm or less is embedded in a resin and polished to prepare a test sample. It produced and evaluated by measuring the Vickers hardness of a test sample. The Vickers hardness was measured using a microhardness meter “FM-700” manufactured by FUTURE-TECH with a test load of 2.94 N (300 gf). A thermosetting resin was used for preparing the test sample. The Vickers hardness of the test sample was evaluated by an average value of n = 5. The Vickers hardness was also measured in the same manner for the powder that was aged at 800 ° C. for 3 hours in Ar.
　合金粉末を使用した粉末冶金により作製した焼結体の硬さおよび抗折強度については、目開き１５０μｍの篩を使用した分級により粒径が１５０μｍを超える粗粒子を除去し、粒径を１５０μｍ以下に揃えた粉末（時効処理なし）を、内径３０ｍｍ、高さ３０ｍｍのステンレス製カプセルに充填、脱気、封入し、保持温度１１５０℃、保持時間３ｈ、成形圧力１４７ＭＰａでＨＩＰ成形し、その後、徐冷して焼結体を作製し、焼結体のビッカース硬さ（粉末と同様の方法）と抗折強度（支点間距離１０ｍｍの三点曲げ試験）を測定することにより評価した。抗折強度は、焼結体からワイヤーで割り出した縦４ｍｍ、幅２５ｍｍ、厚さ３ｍｍの試験片を、三点曲げ試験によって評価した。三点曲げ試験の条件は、支点間距離１０ｍｍで実施し、縦４ｍｍ、幅２５ｍｍの面を厚さ方向に圧下し、その時の応力（Ｎ）を測定し、次の式に基づき、三点曲げ強度を算出した。算出した三点曲げ強度を抗折強度（ＭＰａ）とした。
三点曲げ強度（ＭＰａ）＝（３×応力（Ｎ）×支点間距離（ｍｍ））／（２×試験片の幅（ｍｍ）×（試験片の厚さ（ｍｍ）2） Regarding the hardness and bending strength of the sintered body produced by powder metallurgy using alloy powder, coarse particles having a particle size exceeding 150 μm are removed by classification using a sieve having an opening of 150 μm, and the particle size is 150 μm or less. Filled with stainless steel capsules with an inner diameter of 30 mm and a height of 30 mm, deaerated and sealed, and HIP-molded at a holding temperature of 1150 ° C., a holding time of 3 h and a molding pressure of 147 MPa, and then gradually The sintered body was prepared by cooling, and evaluated by measuring the Vickers hardness (same method as powder) and bending strength (three-point bending test with a fulcrum distance of 10 mm) of the sintered body. The bending strength was evaluated by a three-point bending test on a test piece having a length of 4 mm, a width of 25 mm, and a thickness of 3 mm determined from a sintered body with a wire. The three-point bending test was performed at a fulcrum distance of 10 mm, a 4 mm long and 25 mm wide surface was squeezed in the thickness direction, and the stress (N) at that time was measured. Intensity was calculated. The calculated three-point bending strength was defined as the bending strength (MPa).
Three-point bending strength (MPa) = (3 × stress (N) × distance between supporting points (mm)) / (2 × width of test piece (mm) × (thickness of test piece (mm) 2 )
　各評価項目について、表１に示す組成の粉末を作製し、評価を行ない、表１に示す結果を得た。粉末の硬さについては、粉末の時効処理後のビッカース硬さが７００ＨＶ以上のものを「Ａ」、７００ＨＶ未満５００ＨＶ以上のものを「Ｂ」、５００ＨＶ未満のものを「Ｃ」とした。 For each evaluation item, a powder having the composition shown in Table 1 was prepared and evaluated, and the results shown in Table 1 were obtained. Regarding the hardness of the powder, “A” is the case where the Vickers hardness after the aging treatment of the powder is 700 HV or more, “B” is the case where the Vickers hardness is less than 700 HV and 500 HV or more, and “C” is the case where the Vickers hardness is less than 500 HV.
　粉末の時効硬化幅については、「合金粉末の焼結体のビッカース硬さ－合金粉末の時効処理前のビッカース硬さ」が２００ＨＶ以上のものを「Ａ」、２００ＨＶ未満１００ＨＶ以上のものを「Ｂ」、１００ＨＶ未満のものを「Ｃ」とした。 Regarding the age hardening width of the powder, “A” indicates that “Vickers hardness of sintered powder of alloy powder−Vickers hardness before aging treatment of alloy powder” is 200 HV or higher, and “B” indicates that Vickers hardness of 200 HV or higher is less than 200 HV. ", And less than 100 HV was designated as" C ".
　粉末焼結体の抗折強度については、粉末焼結体の抗折強度が８００ＭＰａ以上のものを「Ａ」、８００ＭＰａ未満４００ＭＰａ以上のものを「Ｂ」、４００ＭＰａ未満のものを「Ｃ」とした。 With respect to the bending strength of the powder sintered body, the powder sintered body having a bending strength of 800 MPa or more was designated as “A”, the one having a bending strength of less than 800 MPa and 400 MPa or more was designated as “B”, and the one having less than 400 MPa was designated as “C”. .
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、Ｎｏ．１～１２は本発明例であり、Ｎｏ．１３～２３は比較例である。 As shown in Table 1, No. Nos. 1 to 12 are examples of the present invention. Reference numerals 13 to 23 are comparative examples.
　表１に示す比較例Ｎｏ．１３は、粉末組成におけるＭｏ元素とＷ元素の合計量が少ない（２５質量％未満）ため、粉末の時効処理後のビッカース硬さが劣る（評価Ｃ）。比較例Ｎｏ．１４は、粉末組成におけるＭｏ元素とＷ元素の合計量が多い（５０質量％超）ため、粉末焼結体の抗折強度が劣る（評価Ｃ）。比較例Ｎｏ．１５は、粉末組成においてＣｒを含有しないために、粉末の時効処理後のビッカース硬さおよび耐食性が劣る（評価Ｃ）。比較例Ｎｏ．１６は、粉末組成におけるＣｒの含有量が多い（１５質量％超）ため、粉末の時効処理前の硬さが高くなり、粉末の時効硬化幅が小さくなる（評価Ｃ）。 Comparative example No. shown in Table 1. In No. 13, since the total amount of Mo element and W element in the powder composition is small (less than 25% by mass), the Vickers hardness after aging treatment of the powder is inferior (Evaluation C). Comparative Example No. No. 14 has a large total amount of Mo element and W element in the powder composition (greater than 50% by mass), so that the bending strength of the powder sintered body is inferior (Evaluation C). Comparative Example No. Since No. 15 does not contain Cr in the powder composition, Vickers hardness and corrosion resistance after aging treatment of the powder are inferior (Evaluation C). Comparative Example No. No. 16 has a high Cr content in the powder composition (greater than 15% by mass), so that the hardness of the powder before the aging treatment increases and the age hardening width of the powder decreases (Evaluation C).
　比較例Ｎｏ．１７～２０は、いずれも粉末組成におけるＳｉの含有量が多い（０．３質量％超）ために、粉末焼結体の抗折強度の低下が顕著となるとともに（評価Ｃ）、粉末の時効硬化幅が小さくなる（評価Ｃ）。比較例Ｎｏ．２１～２３は、粉末組成におけるＭｎ，Ｖ、Ｆｅの含有量がいずれも多い（Ｍｎ：３５質量％超、Ｖ：２０質量％超、Ｆｅ：１５質量％超）ため、粉末焼結体の抗折強度が劣る（評価Ｃ）。 Comparative Example No. In Nos. 17 to 20, since the Si content in the powder composition is large (greater than 0.3% by mass), the bending strength of the powder sintered body is significantly reduced (Evaluation C), and the aging of the powder The curing width becomes small (Evaluation C). Comparative Example No. Nos. 21 to 23 have a high content of Mn, V and Fe in the powder composition (Mn: more than 35% by mass, V: more than 20% by mass, Fe: more than 15% by mass). Folding strength is inferior (Evaluation C).
　これに対して、本発明であるＮｏ．１～１２は、いずれも本発明の条件を満たしていることから粉末の時効処理後のビッカース硬さ、粉末の時効硬化幅、粉末焼結体の抗折強度が優れていることが分かる。 On the other hand, No. which is the present invention. Since all of Nos. 1 to 12 satisfy the conditions of the present invention, it can be seen that the Vickers hardness after the aging treatment of the powder, the age hardening width of the powder, and the bending strength of the powder sintered body are excellent.
　以上のように、ＭｏおよびＷの１種または２種を合計で２５～５０％含有することにより、十分な硬度を得ると同時に、Ｃｒを５～１５％含有することにより、耐食性を高め、Ｓｉの含有量の上限を０．３％に規制することにより、抗折強度と大きな時効硬化幅の両立を図り、時効硬化性、抗折強度に優れたショットピーニング用投射材、塩酸耐食性に優れる高硬度粉末焼結体用の原料粉末、硬質摩擦粉末、焼結用硬質粒子などに使用することができる高硬度高靱性粉末を提供することができる。 As described above, by containing one or two of Mo and W in a total of 25 to 50%, sufficient hardness is obtained, and at the same time, by containing 5 to 15% of Cr, the corrosion resistance is improved, and Si By limiting the upper limit of the content to 0.3%, both the bending strength and the large age hardening width are achieved, and the shot peening projection material with excellent age hardening and bending strength, and high hydrochloric acid corrosion resistance. It is possible to provide a high hardness and high toughness powder that can be used as a raw material powder for a hard powder sintered body, a hard friction powder, a hard particle for sintering, and the like.

Claims (8)

  1. 　質量％で、ＭｏおよびＷの１種または２種を合計で２５％以上５０％以下、Ｃｒを５％以上１５％以下、Ｓｉを０％以上０．３％以下、Ｍｎを０％以上３５％以下、Ｖを０％以上２０％以下、ならびに、Ｆｅを０％以上１５％以下含有し、残部がＣｏおよび不可避的不純物からなることを特徴とする、合金粉末。 1% or 2 types of Mo and W in total 25% to 50%, Cr 5% to 15%, Si 0% to 0.3%, Mn 0% to 35% by mass% Hereinafter, an alloy powder comprising V in a range of 0% to 20%, Fe in a range of 0% to 15%, and the balance consisting of Co and inevitable impurities.
  2. 　質量％で、Ｍｎ：０％超３５％以下、Ｖ：０％超２０％以下およびＦｅ：０％超１５％以下から選ばれた１種または２種以上を含有することを特徴とする、請求項１に記載の合金粉末。 It contains one or more selected from Mn: more than 0% and not more than 35%, V: more than 0% and not more than 20% and Fe: more than 0% and not more than 15%. Item 4. The alloy powder according to Item 1.
  3. 　時効処理後のビッカース硬さが５００ＨＶ以上である、請求項１に記載の合金粉末。 The alloy powder according to claim 1, wherein the Vickers hardness after the aging treatment is 500 HV or more.
  4. 　次式：
    　合金粉末の焼結体のビッカース硬さ－合金粉末の時効処理前のビッカース硬さ
    により定義される合金粉末の時効硬化幅が１００ＨＶ以上である、請求項１に記載の合金粉末。     The following formula:
    The alloy powder according to claim 1, wherein the age-hardening width of the alloy powder defined by the Vickers hardness of the sintered body of the alloy powder-the Vickers hardness before the aging treatment of the alloy powder is 100 HV or more.
  5. 　請求項１に記載の合金粉末を含む、ショットピーニング用投射材。 A shot peening projection material comprising the alloy powder according to claim 1.
  6. 　請求項１に記載の合金粉末を含む、粉末冶金用組成物。 A composition for powder metallurgy comprising the alloy powder according to claim 1.
  7. 　請求項６に記載の粉末冶金用組成物の成形体を焼結して得られる焼結体。 A sintered body obtained by sintering a molded body of the composition for powder metallurgy according to claim 6.
  8. 　抗折強度が４００ＭＰａ以上である、請求項７に記載の焼結体。 The sintered body according to claim 7, wherein the bending strength is 400 MPa or more.
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JP7377113B2 (en) 2020-01-27 2023-11-09 山陽特殊製鋼株式会社 Powder for shot peening
CN115354241B (en) * 2022-09-01 2023-05-12 西北工业大学 Low-temperature wear-resistant alloy with strong plasticity synergistic improvement and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3410732A (en) * 1965-04-30 1968-11-12 Du Pont Cobalt-base alloys
JPS59211546A (en) * 1983-05-17 1984-11-30 Sumitomo Metal Ind Ltd Cobalt alloy for thermal spraying
JPS62207847A (en) * 1986-03-10 1987-09-12 Toyota Motor Corp Ferrous sintered alloy for valve seat
JPH09150257A (en) * 1995-11-28 1997-06-10 Toshiba Mach Co Ltd Highly wear resistant composite material and manufacture thereof
US20050142026A1 (en) * 2003-12-29 2005-06-30 Wu James B.C. Ductile cobalt-based Laves phase alloys
JP2006316745A (en) * 2005-05-13 2006-11-24 Mitsubishi Materials Pmg Corp Manufacturing method for iron-based sintered alloy valve seat exhibiting excellent wear resistance in high temperature/dry condition and the valve seat
JP2007023383A (en) * 2005-06-13 2007-02-01 Hitachi Powdered Metals Co Ltd Sintered valve seat and production method therefor

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325994A (en) * 1979-12-29 1982-04-20 Ebara Corporation Coating metal for preventing the crevice corrosion of austenitic stainless steel and method of preventing crevice corrosion using such metal
JPH04107235A (en) * 1990-08-27 1992-04-08 Nippon Steel Corp Conductor roll for electroplating
KR100431597B1 (en) * 2001-12-21 2004-05-17 재단법인 포항산업과학연구원 Cobalt alloys with improved wear resistance used in the bushes and the sleeves of molten-zinc bath
US6852176B2 (en) * 2002-07-17 2005-02-08 Deloro Stellite Holdings Corporation Wear-resistant, corrosion-resistant cobalt-based alloys
KR100796117B1 (en) * 2005-06-13 2008-01-21 히다치 훈마츠 야킨 가부시키가이샤 Sintered valve seat and method of manufacturing the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3410732A (en) * 1965-04-30 1968-11-12 Du Pont Cobalt-base alloys
JPS59211546A (en) * 1983-05-17 1984-11-30 Sumitomo Metal Ind Ltd Cobalt alloy for thermal spraying
JPS62207847A (en) * 1986-03-10 1987-09-12 Toyota Motor Corp Ferrous sintered alloy for valve seat
JPH09150257A (en) * 1995-11-28 1997-06-10 Toshiba Mach Co Ltd Highly wear resistant composite material and manufacture thereof
US20050142026A1 (en) * 2003-12-29 2005-06-30 Wu James B.C. Ductile cobalt-based Laves phase alloys
JP2006316745A (en) * 2005-05-13 2006-11-24 Mitsubishi Materials Pmg Corp Manufacturing method for iron-based sintered alloy valve seat exhibiting excellent wear resistance in high temperature/dry condition and the valve seat
JP2007023383A (en) * 2005-06-13 2007-02-01 Hitachi Powdered Metals Co Ltd Sintered valve seat and production method therefor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUJITA ET AL: "Effect of addiction of Co system hard particle on CU-10% Sn-10% and lead bronze sintered alloy", MEETING OF JAPAN SOCIETY OF POWDER AND POWDER METALLURGY, 18 November 1998 (1998-11-18) *

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