WO2016190037A1 - Mélange de poudres pour métallurgie des poudres à base de fer, procédé de fabrication de ce mélange de poudres, et corps fritté fabriqué à l'aide de mélange de poudres - Google Patents

Mélange de poudres pour métallurgie des poudres à base de fer, procédé de fabrication de ce mélange de poudres, et corps fritté fabriqué à l'aide de mélange de poudres Download PDF

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WO2016190037A1
WO2016190037A1 PCT/JP2016/063168 JP2016063168W WO2016190037A1 WO 2016190037 A1 WO2016190037 A1 WO 2016190037A1 JP 2016063168 W JP2016063168 W JP 2016063168W WO 2016190037 A1 WO2016190037 A1 WO 2016190037A1
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powder
iron
sintered body
type
caso
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PCT/JP2016/063168
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English (en)
Japanese (ja)
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宣明 赤城
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株式会社神戸製鋼所
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Priority to KR1020177036350A priority Critical patent/KR102113996B1/ko
Priority to US15/572,725 priority patent/US20180104739A1/en
Priority to EP16799745.1A priority patent/EP3305439B1/fr
Priority to CN201680029965.0A priority patent/CN107614159A/zh
Publication of WO2016190037A1 publication Critical patent/WO2016190037A1/fr

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    • 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
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0221—Using a mixture of prealloyed powders or a master alloy comprising S or a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/35—Iron
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/25—Oxide
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/35—Complex boride, carbide, carbonitride, nitride, oxide or oxynitride
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/45—Others, including non-metals
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/058—Particle size above 300 nm up to 1 micrometer
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • 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
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a mixed powder for iron-based powder metallurgy and a sintered body produced using the same, and more specifically, a mixed powder for iron-based powder metallurgy containing anhydrous II-type calcium sulfate in a specific ratio and the same.
  • the present invention relates to a sintered body produced using
  • Powder metallurgy is widely used as an industrial production method for various machine parts.
  • the procedure for iron-based powder metallurgy is to first prepare a mixed powder by mixing an iron-based powder, an alloy powder such as a copper (Cu) powder, a nickel (Ni) powder, a graphite powder, and a lubricant. .
  • the mixed powder is filled into a mold, press-molded, and sintered to produce a sintered body.
  • a machine part having a desired shape is prepared by subjecting the sintered body to cutting such as drilling or turning.
  • the ideal of powder metallurgy is to process the sintered body so that it can be used as a machine part without cutting the sintered body.
  • the sintering may cause non-uniform shrinkage of the raw material powder.
  • the dimensional accuracy required for mechanical parts is high, and the shape of the parts is complicated. For this reason, it is becoming essential to cut the sintered body. From such a technical background, machinability is imparted to the sintered body so that the sintered body can be processed smoothly.
  • MnS manganese sulfide
  • the addition of manganese sulfide powder is effective for relatively low speed cutting such as drilling.
  • the addition of manganese sulfide powder is not necessarily effective in recent high-speed cutting, and there are problems such as generation of dirt on the sintered body and reduction in mechanical strength.
  • Patent Document 1 Japanese Patent Publication No. 52-16684 discloses a method for imparting machinability other than the addition of manganese sulfide. Patent Document 1 discloses that 0.1 to 1.0% of calcium sulfide (CaS) and 0.1 to 2% of carbon (based on iron-based raw material powder containing iron and a required amount of carbon and copper ( C) and 0.5-5.0% copper (Cu) are disclosed.
  • CaS calcium sulfide
  • C carbon and copper
  • Cu 0.5-5.0% copper
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a mixed powder for iron-based powder metallurgy capable of producing a sintered body having stable quality and performance.
  • the mixed powder for iron-based powder metallurgy of the present invention contains powder containing anhydrous type II calcium sulfate so that the weight ratio of CaS after sintering is 0.01 wt% or more and 0.1 wt% or less. .
  • the method for producing a mixed powder for iron-based powder metallurgy according to the present invention is a step of producing a powder containing anhydrous type II calcium sulfate by heating a powder containing dihydrate gypsum or hemihydrate gypsum at 350 ° C. or more and 900 ° C. or less. And mixing the powder containing the anhydrous type II calcium sulfate and the iron-based powder.
  • FIG. 1 is an image showing an example of the appearance of chips with good chip disposal.
  • FIG. 2 is an image showing an example of the appearance of a chip with poor chip disposal.
  • FIG. 3 is an observation image of the worn portion of the tool rake face after turning the sintered body produced in Example 26 with a cermet tip.
  • FIG. 4 is an observation image of the worn portion of the tool rake face after the sintered body produced in Example 30 was turned with a cermet tip.
  • FIG. 5 is an observation image of a worn portion of the tool rake face after the sintered body produced in Example 32 was turned with a cermet tip.
  • FIG. 6 is an observation image of a worn portion of the tool rake face after the sintered body produced in Example 33 was turned with a cermet tip.
  • FIG. 1 is an image showing an example of the appearance of chips with good chip disposal.
  • FIG. 2 is an image showing an example of the appearance of a chip with poor chip disposal.
  • FIG. 3 is an observation image of the
  • FIG. 7 is an observation image of the worn portion of the tool rake face after turning the sintered body produced in Example 34 with a cermet tip.
  • FIG. 8 is an observation image of the worn portion of the tool rake face after turning the sintered body produced in Reference Example 1 with a cermet tip.
  • the present inventor investigated why the quality and performance of the sintered body disclosed in Patent Document 1 deteriorated with time. And this inventor discovered that the quality and performance of a sintered compact fell because a sintered compact contains calcium sulfide and hemihydrate gypsum (henceforth, these 2 components are described as "CaS component"). . That is, the present inventor changed the calcium sulfate component to calcium sulfate dihydrate (CaSO 4 .2H 2 O) by absorbing moisture in the atmosphere, or the CaS component aggregated by a curing reaction to cause a coarse particle size of 63 ⁇ m or more. It was found that grains were formed.
  • CaS component calcium sulfate dihydrate
  • the CaS component is dispersed unevenly in the mixed powder or the sintered body to reduce the machinability of the sintered body, or the moisture adsorbed on the CaS component expands during the sintering and the strength of the sintered body It became clear that it lowered.
  • the present inventor has completed the present invention shown below by further diligently examining the crystal structure of calcium sulfate having low hygroscopicity based on the above findings.
  • the mixed powder for iron-based powder metallurgy of the present invention is a mixed powder obtained by mixing an iron-based powder and a powder containing anhydrous type II calcium sulfate (hereinafter also referred to as “type II CaSO 4 powder”).
  • type II CaSO 4 powder anhydrous type II calcium sulfate
  • additives such as a ternary oxide, a binary oxide, an alloy powder, a graphite powder, a lubricant, and a binder may be appropriately added to the mixed powder.
  • a small amount of inevitable impurities may be contained in the mixed powder in the process of manufacturing the mixed powder for iron-based powder metallurgy.
  • the mixed powder for iron-based powder metallurgy according to the present invention can be obtained by filling a metal mold or the like and molding it, followed by sintering.
  • the sintered body produced in this way can be used for various machine parts by cutting. The use and manufacturing method of this sintered body will be described later.
  • the iron-based powder is a main component constituting the mixed powder for iron-based powder metallurgy, and is preferably contained in a weight ratio of 60% by weight or more with respect to the entire mixed powder for iron-based powder metallurgy.
  • the weight% of iron-base powder here means the ratio for the total weight other than a lubricant among the mixed powder for iron-base powder metallurgy.
  • the definition means the weight ratio in the total weight of the iron-based powder metallurgy mixed powder excluding the lubricant.
  • the iron-based powder atomized iron powder, pure iron powder such as reduced iron powder, partially diffusion alloyed steel powder, fully alloyed steel powder, or hybrid steel powder in which alloy components are partially diffused Etc. can be used.
  • the volume average particle diameter of the iron-based powder is preferably 50 ⁇ m or more, more preferably 70 ⁇ m or more. When the volume average particle diameter of the iron-based powder is 50 ⁇ m or more, the handleability is excellent.
  • the volume average particle size of the iron-based powder is preferably 200 ⁇ m or less, and more preferably 100 ⁇ m or less. When the volume average particle diameter of the iron-based powder is 200 ⁇ m or less, it is easy to form a precise shape and sufficient strength can be obtained.
  • the mixed powder for iron-based powder metallurgy according to the present invention includes a powder containing anhydrous type II calcium sulfate (type II CaSO 4 powder).
  • the present invention overturns the conventional technical common sense (for example, Patent Document 1), which has been considered that the machinability of a sintered body can be improved only by adding a component that becomes calcium sulfide (CaS) after sintering. is there. That is, dihydrate gypsum (CaSO 4 .2H 2 O), anhydrous type III calcium sulfate (III type CaSO 4 ), hemihydrate gypsum (CaSO 4 .1 / 2H 2 O), etc. absorb water over time.
  • anhydrous type II calcium sulfate has low hygroscopicity and does not absorb moisture in the atmosphere, so the mass may increase even if it is stored for a certain period in a state of being contained in the iron-based powder metallurgy mixed powder. Absent.
  • anhydrous type II calcium sulfate can be changed to CaS after sintering to enhance the machinability of the sintered body.
  • mixed powder for iron-based powder metallurgy containing type II CaSO 4 powder is dihydrate gypsum (CaSO 4 .2H 2 O), anhydrous type III calcium sulfate (type III CaSO 4 ), hemihydrate gypsum (CaSO 4).
  • dihydrate gypsum CaSO 4 .2H 2 O
  • anhydrous type III calcium sulfate type III CaSO 4
  • hemihydrate gypsum CaSO 4
  • Type II CaSO 4 powder contains anhydrous type II calcium sulfate as a main component, but dihydrate gypsum (CaSO 4 .2H 2 O), anhydrous type III calcium sulfate (type III CaSO 4 ), hemihydrate gypsum ( CaSO 4 ⁇ 1 / 2H 2 O) or the like may be contained.
  • the type II CaSO 4 powder is preferably as the weight ratio of anhydrous type II calcium sulfate is larger, more preferably the weight ratio of anhydrous type II calcium sulfate is 70% by weight or more, more preferably 80% by weight or more. Particularly preferably, it consists only of anhydrous type II calcium sulfate. Further, the surface of the type II CaSO 4 powder may be coated with a lubricant or a binder described later.
  • the type II CaSO 4 powder is preferably contained in the iron-based powder metallurgy mixed powder so that the weight ratio of CaS after sintering is 0.01 wt% or more and 0.1 wt% or less.
  • the weight ratio of CaS after sintering is more preferably 0.02% by weight or more, and the weight ratio of CaS after sintering is more preferably 0.03% by weight or more.
  • a sintered body containing CaS at such a weight ratio is particularly excellent in machinability.
  • Type II CaSO 4 powder is contained so that the weight ratio of CaS after sintering is 0.09 wt% or less, more preferably 0.08 wt% or less. By including CaS at such a weight ratio, the strength of the sintered body can be increased.
  • weight ratio of CaS after sintering means the weight ratio of CaS in the sintered body obtained by sintering the mixed powder for iron-based powder metallurgy.
  • the weight ratio of CaS contained in the sintered body after sintering can be adjusted by the weight ratio of type II CaSO 4 powder contained before sintering.
  • the weight ratio of CaS contained in the sintered body is the weight of Ca obtained by taking a sample piece by processing the sintered body with a drill or the like and quantitatively analyzing the weight of Ca contained in the sample piece. , By calculating the weight of CaS. This conversion is performed by integrating the molecular weight of CaS (72.143) by dividing by the atomic weight of Ca (40.078). Since Ca hardly reacts and disappears during sintering, the weight of Ca does not change before and after sintering, and Ca and S are combined at 1: 1.
  • the volume average particle diameter of the type II CaSO 4 powder is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
  • the volume average particle size of the type II CaSO 4 powder is preferably 60 ⁇ m or less, more preferably 30 ⁇ m or less, and still more preferably 20 ⁇ m or less.
  • Such a type II CaSO 4 powder having a volume average particle diameter can be obtained, for example, by heating hemihydrate gypsum to 350 ° C. or more and 900 ° C. or less and pulverizing and classifying what is held for 1 hour or more and 10 hours or less. it can.
  • the volume average particle size of type II CaSO 4 powder is small, even if a small amount the amount of type II CaSO 4 powder can improve the machinability of the sintered body.
  • the volume average particle size is a value of the particle size D 50 of 50% of the integrated value in the particle size distribution obtained using a laser diffraction particle size distribution measuring apparatus (Nikkiso Microtrack “MODEL 9320-X100”).
  • the lower limit of R 1/3 / W is 15 It is preferable that it is above, More preferably, it is 20 or more, More preferably, it is 25 or more.
  • the upper limit of R 1/3 / W is preferably 400 or less, more preferably 340 or less, and even more preferably 270 or less. Such a definition is based on the inventor's experience that the relationship between the volume average particle diameter proportional to the cube root of the volume ratio and the weight ratio correlates with various properties of the sintered body. By satisfying such a numerical range, a sintered body having good crushing strength, machinability and chip treatability can be obtained.
  • the ternary oxide may be added to improve machinability when the sintered body is used for cutting for a long time.
  • the ternary oxide can remarkably enhance the machinability of the sintered body in combination with the addition of the type II CaSO 4 powder.
  • the ternary oxide means a composite oxide of three elements, specifically selected from the group consisting of Ca, Mg, Al, Si, Co, Ni, Ti, Mn, Fe and Zn. Of these, a complex oxide of the three elements is preferable, and a Ca—Al—Si oxide, a Ca—Mg—Si oxide, and the like are more preferable.
  • the Ca-Al-Si-based oxides 2CaO ⁇ Al 2 O 3 ⁇ SiO 2 or the like.
  • Examples of the Ca—Mg—Si oxide include 2CaO ⁇ MgO ⁇ 2SiO 2 .
  • the 2CaO ⁇ Al 2 O 3 ⁇ SiO 2 reacts with TiO 2 contained in the coating applied in the cutting tool or cutting tool, because it forms a protective film on the surface of the cutting tool, wear of the cutting tool Property can be remarkably improved.
  • the shape of the ternary oxide is not particularly limited, but a spherical shape or a shape in which it is crushed, that is, a shape having a round shape as a whole is preferable.
  • the lower limit of the volume average particle diameter of the ternary oxide is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more. As the volume average particle size is smaller, there is a tendency that the machinability of the sintered body can be improved by adding a small amount. Further, the upper limit of the volume average particle diameter of the ternary oxide is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 9 ⁇ m or less. When the volume average particle diameter is too large, it becomes difficult to improve the machinability of the sintered body.
  • the volume average particle diameter of the ternary oxide is a value measured by the same measurement method as that for the type II CaSO 4 powder.
  • the lower limit of the content of the ternary oxide is preferably 0.01% by weight or more, more preferably 0.03% by weight or more, and still more preferably 0.05% by weight or more.
  • the upper limit of the content of the ternary oxide is preferably 0.25% by weight or less, more preferably 0.2% by weight or less, and further preferably 0.15% by weight or less.
  • the weight ratio of the ternary oxide to the sintered CaS is preferably included in a ratio of 1: 9 to 9: 1, more preferably 3: 7 to 9: 1, and still more preferably 4: 6 to 7: 3.
  • the machinability of the sintered body can be significantly improved.
  • the binary oxide may be added to improve the machinability at the initial cutting when the sintered body is used for cutting.
  • the binary oxide means a composite oxide of two elements, specifically selected from the group consisting of Ca, Mg, Al, Si, Co, Ni, Ti, Mn, Fe and Zn. It is preferable to be a complex oxide of two kinds of elements, more preferably a Ca—Al-based oxide, a Ca—Si-based oxide, and the like.
  • the Ca—Al-based oxide include CaO ⁇ Al 2 O 3 and 12CaO ⁇ 7Al 2 O 3 .
  • the Ca—Si-based oxide include 2CaO ⁇ SiO 2 .
  • the shape, volume average particle diameter, measuring method and weight ratio of the binary oxide are the same as those of the ternary oxide.
  • the mixed powder for iron-based powder metallurgy of the present invention preferably contains 0.02 wt% or more and 0.3 wt% or less of both binary oxide and ternary oxide in terms of the total weight.
  • the total weight of the oxides is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more. From the viewpoint of cost, the smaller the weight ratio of the binary oxide and the ternary oxide, the better.
  • the total weight of the oxides is preferably 0.25% by weight or less, more preferably 0.2% by weight or less. When the total weight of the oxides is 0.25% by weight or less, the crushing strength of the sintered body can be sufficiently ensured.
  • the weight ratio of the binary oxide to CaS after sintering is preferably included in a ratio of 1: 9 to 9: 1, more preferably 3: 6 to 9: 1, and still more preferably 4: 6 to 7 : 3.
  • a sintered body excellent in machinability at the initial stage of cutting can be produced.
  • the alloy powder is added to promote bonding between the iron-based powders and to increase the strength of the sintered body after sintering.
  • Such an alloy powder is preferably contained in an amount of 0.1 wt% or more and 10 wt% or less with respect to the entire mixed powder for iron-based powder metallurgy.
  • the content is 0.1% by weight or more, the strength of the sintered body can be increased, and when the content is 10% by weight or less, dimensional accuracy during sintering of the sintered body can be ensured.
  • alloy powder examples include non-ferrous metal powders such as copper (Cu) powder, nickel (Ni) powder, Mo powder, Cr powder, V powder, Si powder, and Mn powder, and cuprous oxide powder. You may use individually by 1 type and may use 2 or more types together.
  • the lubricant is added to the iron-based powder metallurgy mixed powder so that a compact obtained by compressing the iron-based powder metallurgy mixed powder in the mold can be easily taken out from the mold.
  • a lubricant is added to the iron-based powder metallurgy mixed powder, it is possible to reduce the extraction pressure when the molded body is taken out from the mold, and thus it is possible to prevent cracking of the molded body and damage to the mold.
  • the lubricant may be added to the iron-based powder metallurgy mixed powder, or may be applied to the surface of the mold.
  • the lubricant When the lubricant is added to the iron-based powder metallurgy mixed powder, the lubricant is preferably contained in an amount of 0.01% by mass to 1.5% by mass with respect to the weight of the iron-based powder metallurgy mixed powder. More preferably, it is contained in an amount of from 1% by mass to 1.2% by mass, and more preferably from 0.2% by mass to 1.0% by mass.
  • the content of the lubricant is 0.01% by mass or more, it is easy to obtain an effect of reducing the punching pressure of the molded body.
  • the content of the lubricant When the content of the lubricant is 1.5% by mass or less, a high-density sintered body can be easily obtained and a high-strength sintered body can be obtained.
  • the lubricant is selected from the group consisting of metal soap (lithium stearate, calcium stearate, zinc stearate, etc.), stearic acid monoamide, fatty acid amide, amide wax, hydrocarbon wax and cross-linked (meth) acrylic acid alkyl ester resin.
  • metal soap lithium stearate, calcium stearate, zinc stearate, etc.
  • stearic acid monoamide fatty acid amide
  • amide wax hydrocarbon wax
  • hydrocarbon wax hydrocarbon wax
  • the binder is added to adhere the alloy powder, the graphite powder and the like to the iron-based powder surface.
  • a butene polymer, a methacrylic acid polymer, or the like is used.
  • the butene polymer it is preferable to use a 1-butene homopolymer composed of butene alone or a copolymer of butene and alkene.
  • the alkene is preferably a lower alkene, preferably ethylene or propylene.
  • the methacrylic acid polymer is selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, ethyl hexyl methacrylate, lauryl methacrylate, methyl acrylate and ethyl acrylate 1 More than seeds can be used.
  • the binder is preferably contained in an amount of 0.01% by mass or more and 0.5% by mass or less, and more preferably 0.05% by mass or more and 0.4% by mass or less, based on the weight of the mixed powder for iron-based powder metallurgy. More preferably, it is 0.1 to 0.3% by mass.
  • a type II CaSO 4 powder contained in the mixed powder for iron-based powder metallurgy is prepared.
  • the type II CaSO 4 powder is preferably obtained by heating hemihydrate gypsum or dihydrate gypsum having a volume average particle size of 0.1 ⁇ m or more and 60 ⁇ m or less at 300 ° C. or more and 900 ° C. or less.
  • the volume average particle diameter of hemihydrate gypsum or dihydrate gypsum is preferably the same or slightly smaller than the volume average particle diameter of type II CaSO 4 powder in consideration of aggregation during heating.
  • the lower limit of the heating temperature is preferably 350 ° C. or higher, more preferably 400 ° C. or higher.
  • the upper limit of heating temperature is 800 degrees C or less, More preferably, it is 700 degrees C or less, More preferably, it is 500 degrees C or less.
  • the heating temperature is 900 ° C. or less, a type II CaSO 4 powder having a particle diameter of 100 ⁇ m or less, which is a typical powder to be mixed with the iron-based powder, can be obtained.
  • the heating temperature when the heating temperature is 700 ° C. or less, it is difficult for agglomeration of hemihydrate gypsum or dihydrate gypsum, and it is possible to obtain type II CaSO 4 powder while maintaining the volume average particle diameter of hemihydrate gypsum or dihydrate gypsum. it can.
  • the heating temperature is high, strong agglomeration occurs, so that the pulverization step is preferably performed.
  • the heating temperature is 300 ° C. or higher, the water content of the hemihydrate gypsum or dihydrate gypsum can be dehydrated to obtain a type II CaSO 4 powder.
  • anhydrous III-type CaSO 4 may be formed instead of anhydrous II-type CaSO 4 , which is not preferable.
  • the heating time is preferably a time period during which hemihydrate gypsum or dihydrate gypsum can be dehydrated into type II calcium sulfate, and preferably 1 hour or more and 8 hours or less.
  • part of the hemihydrate gypsum may remain as hemihydrate gypsum without changing to type II calcium sulfate, or may change to anhydrous type III calcium sulfate. For this reason, it is preferable that heating time is 2 hours or more, More preferably, it is 3 hours or more.
  • the mixed powder for iron-based powder metallurgy according to the present invention can be produced by mixing the iron-based powder and the type II CaSO 4 powder produced above using, for example, a mechanical stirring mixer.
  • various additives such as ternary oxides, alloy powders, graphite powders, lubricants, binary oxides, and binders may be added as appropriate.
  • the mechanical stirring mixer include a high speed mixer, a nauter mixer, a V-type mixer, and a double cone blender.
  • the order of mixing the powders is not particularly limited.
  • the mixing temperature is not particularly limited, but is preferably 150 ° C. or lower from the viewpoint of suppressing oxidation of the iron-based powder in the mixing step.
  • a compacted body is manufactured by applying a pressure of 300 MPa to 1200 MPa.
  • the molding temperature at this time is preferably 25 ° C. or higher and 150 ° C. or lower.
  • a sintered compact can be obtained by sintering the green compact produced above by a normal sintering method.
  • the sintering condition may be a non-oxidizing atmosphere or a reducing atmosphere.
  • the green compact is preferably sintered for 5 minutes to 60 minutes at a temperature of 1000 ° C. to 1300 ° C. in an atmosphere such as a nitrogen atmosphere, a mixed atmosphere of nitrogen and hydrogen, and a hydrocarbon.
  • the sintered body produced as described above can be used as machine parts such as automobiles, agricultural equipment, electric tools, and home appliances by processing with various tools such as cutting tools as necessary.
  • the cutting tool for processing the sintered body include a drill, an end mill, a milling cutting tool, a turning cutting tool, a reamer, and a tap.
  • the mixed powder for iron-based powder metallurgy of the above embodiment a sintered body with stable quality and performance can be produced.
  • the anhydrous type II calcium sulfate contained in the iron-based powder metallurgy mixed powder of the above embodiment has low hygroscopicity and does not absorb moisture in the atmosphere. Therefore, the powder containing anhydrous type II calcium sulfate is in the atmosphere. Even if stored for a certain period of time, the mass will not increase. For this reason, by using powder containing anhydrous type II calcium sulfate (type II CaSO 4 powder) instead of calcium sulfide and hemihydrate gypsum as a component to be sintered into CaS, various performances of the sintered body can be achieved. It can be increased stably.
  • the type II CaSO 4 powder has a volume average particle diameter of 0.1 ⁇ m or more and 60 ⁇ m or less, the machinability of the sintered body can be improved.
  • the mixed powder for iron-based powder metallurgy according to the above embodiment further includes one or more ternary oxides selected from the group consisting of Ca—Al—Si oxides and Ca—Mg—Si oxides.
  • the machinability in long-time cutting can be improved.
  • the mixed powder for iron-based powder metallurgy according to the above embodiment has a weight ratio of ternary oxide to CaS after sintering of 3: 7 to 9: 1, which improves machinability in long-term cutting. Can be made.
  • Example 1 First, commercially available hemihydrate gypsum powder was classified with a sieve to obtain ⁇ 63 / + 45 ⁇ m (volume average particle diameter of 54 ⁇ m). The classified hemihydrate gypsum was heated at 350 ° C. for 5 hours in an atmospheric heating furnace to obtain anhydrous type II calcium sulfate powder (type II CaSO 4 powder). This type II CaSO 4 powder was classified with a sieve to obtain ⁇ 63 / + 45 ⁇ m (volume average particle diameter 54 ⁇ m). The yield of the obtained type II CaSO 4 powder was 100%. This yield is a value obtained by calculating the percentage of the weight of the type II CaSO 4 powder after heating minus the weight of the type II CaSO 4 powder removed by classification from the weight.
  • sintered bodies Two types were produced using the above mixed powder for iron-based powder metallurgy.
  • the mixed powder for iron-based powder metallurgy immediately after production was filled in a mold, and the ring shape was an outer diameter of 64 mm, an inner diameter of 24 mm, and a thickness of 20 mm, and the molding density was 7.00 g / cm 3.
  • a test piece was molded so that Next, this ring-shaped test piece was sintered at 1130 ° C. for 30 minutes in a 10 volume% H 2 —N 2 atmosphere to produce a sintered body.
  • the sintered body after 10 days was prepared in the same manner as the sintered body immediately after that, except that the mixed powder for iron-based powder metallurgy was left in the atmosphere for 10 days and the mold was filled. .
  • Example 2 to 8 sintered bodies were produced in the same manner as in Example 1 except that the heating temperature of the hemihydrate gypsum powder was changed as shown in the column of “Heat treatment temperature” in Table 1. .
  • Comparative Examples 1 to 3 sintered bodies were produced in the same manner as in Example 1, except that anhydrous type II calcium sulfate was changed to the material shown in the column “CaS component” in Table 1. In Comparative Example 1, a sintered body was produced in the same manner as in Example 1, except that anhydrous type II calcium sulfate was not added.
  • JPMA M 01 Japan Powder Metallurgy Industry Association Standard
  • JPMA M 01 Japan Powder Metallurgy Industry Association Standard
  • Example 8 the sintered body after 10 days of Example 8 has various performances deteriorated compared with those of Examples 1 to 7 as compared with the sintered body immediately after. This is because the heating temperature for the hemihydrate gypsum of Example 8 was lower than that of Examples 1 to 7, so that part of the hemihydrate gypsum did not change to type II calcium sulfate, and type III sulfuric acid This may be due to the change to calcium or remaining as hemihydrate gypsum and the hygroscopic nature of these components.
  • the stability of various performances of the sintered body obtained in Example 8 is remarkably superior to that of Comparative Examples 1 to 3. For this reason, as in Example 8, it was revealed that the effect of improving the stability of the sintered body can be obtained even if the entire hemihydrate gypsum is not made of type II calcium sulfate.
  • the yield tends to decrease as the heating temperature of hemihydrate gypsum increases.
  • the cause of this is considered to be that the higher the heating temperature, the more the II-type calcium sulfate agglomerates into large particles, and the large particles were removed by classification. Therefore, in order to efficiently obtain a powder composed of II-type calcium sulfate, it has become clear that the heating temperature of the hemihydrate gypsum is preferably 350 ° C. or higher and 600 ° C. or lower.
  • Example 9 to 29 (Examples 9 to 29) Implementation was performed except that the volume average particle diameter of type II CaSO 4 powder and the weight ratio of CaS after sintering were changed as shown in the columns of “volume average particle diameter” and “CaS weight ratio” in Table 2.
  • a sintered body was produced in the same manner as in Example 1, and each item was evaluated by the same method as in Example 1. The results are shown in Table 2. Adjustment of the volume average particle diameter of the type II CaSO 4 powder used in each example was performed by variously crushing and classifying the heat-treated type II CaSO 4 powder.
  • Example 9 to 29 As in Example 1 above, two types of sintered body immediately after and sintered body after 10 days were prepared and the respective characteristics were evaluated. Both measured values were obtained for all evaluation items. Since it was the same or negligible difference, only one measured value is shown in Table 2. From the results shown in Table 2, it is clear that the sintered bodies produced using the mixed powders for iron-based powder metallurgy of Examples 9 to 29 have stable quality and performance, and the effects of the present invention are shown. It was.
  • Chip treatability in Table 2 is a result of evaluating the appearance of chips generated by turning using a cermet tip based on the following evaluation criteria. (Evaluation criteria for chip disposal) A: The number of spring-like turns (the number of curls) is 1 or less (for example, FIG. 1). ⁇ : The curl number is within 1 to 3 turns. X: The curl number exceeds 3 windings (for example, FIG. 2).
  • Example 30 to 34 In Examples 30 to 34, as shown in Table 3, except that a part of the type II CaSO 4 powder was replaced with 2CaO ⁇ Al 2 O 3 ⁇ SiO 2 or 2CaO ⁇ MgO ⁇ 2SiO 2 , Example 26 was used. A sintered body was produced in the same manner as described above. Reference Examples 1 and 2 were sintered in the same manner as in Example 26 except that all of the type II CaSO 4 powder was replaced with 2CaO ⁇ Al 2 O 3 ⁇ SiO 2 or 2CaO ⁇ MgO ⁇ 2SiO 2 , respectively. The body was made.
  • 2CaO ⁇ Al 2 O 3 ⁇ SiO 2 and 2CaO ⁇ MgO ⁇ 2SiO 2 having a volume average particle diameter of 2 ⁇ m were used.
  • the type II CaSO 4 powder used had a volume average particle diameter of 18.4 ⁇ m.
  • Example 30 to 34 Each item was evaluated by the same method as in Example 26 with respect to the sintered bodies of Examples and Comparative Examples thus produced. The results are shown in Table 3.
  • Example 30 to 34 two kinds of sintered bodies were produced immediately after and sintered bodies after 10 days, and the characteristics of each were evaluated. However, both measured values were the same or negligible in all evaluation items. Because of the difference, only one measurement value is shown in Table 3. Therefore, it was revealed that the sintered bodies produced using the mixed powders for iron-based powder metallurgy of Examples 30 to 34 were stable in quality and performance, and the effects of the present invention were shown.
  • the reason why the amount of tool wear can be reduced in this way is considered to be due to the interaction between the two types of CaSO 4 powder and the ternary oxide.

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

Le mélange de poudres pour métallurgie des poudres à base de fer de l'invention contient une poudre contenant un sulfate de calcium type II anhydre, de sorte que le rapport massique de CaS après frittage est supérieur ou égal à 0,01% en masse et inférieur ou égal à 0,1% en masse. De préférence, ladite poudre contenant un sulfate de calcium type II anhydre présente un diamètre de particule moyen en volume supérieur ou égal à 0,1μｍ et inférieur ou égal à 60μｍ, et contient également une sorte ou plus d'oxyde ternaire choisie dans un groupe constitué d'un oxyde à base de Ca-Al-Si et d'un oxyde à base de Ca-Mg-Si. Enfin, de préférence le rapport massique dudit oxyde ternaire et dudit CaS après frittage, est compris entre 3:7 et 9:1.
PCT/JP2016/063168 2015-05-27 2016-04-27 Mélange de poudres pour métallurgie des poudres à base de fer, procédé de fabrication de ce mélange de poudres, et corps fritté fabriqué à l'aide de mélange de poudres WO2016190037A1 (fr)

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KR1020177036350A KR102113996B1 (ko) 2015-05-27 2016-04-27 철기 분말 야금용 혼합 분말 및 그의 제조 방법, 및 그것을 이용하여 제작한 소결체
US15/572,725 US20180104739A1 (en) 2015-05-27 2016-04-27 Mixed powder for iron-based powder metallurgy, method for producing same, and sintered body produced using same
EP16799745.1A EP3305439B1 (fr) 2015-05-27 2016-04-27 Mélange de poudres pour métallurgie des poudres à base de fer, procédé de fabrication de ce mélange de poudres, et corps fritté fabriqué à l'aide de mélange de poudres
CN201680029965.0A CN107614159A (zh) 2015-05-27 2016-04-27 铁基粉末冶金用混合粉和其制造方法、以及使用其制作的烧结体

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SE545171C2 (en) * 2016-12-02 2023-05-02 Kobe Steel Ltd Powder mixture for iron-based powder metallurgy, and method for manufacturing sintered compact using same

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SE545171C2 (en) * 2016-12-02 2023-05-02 Kobe Steel Ltd Powder mixture for iron-based powder metallurgy, and method for manufacturing sintered compact using same

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US20180104739A1 (en) 2018-04-19
JP6480266B2 (ja) 2019-03-06
EP3305439A1 (fr) 2018-04-11
EP3305439A4 (fr) 2018-05-30
KR20180008730A (ko) 2018-01-24
CN107614159A (zh) 2018-01-19

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