WO2020013227A1 - Sintered alloy and method for producing same - Google Patents

Sintered alloy and method for producing same Download PDF

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Publication number
WO2020013227A1
WO2020013227A1 PCT/JP2019/027344 JP2019027344W WO2020013227A1 WO 2020013227 A1 WO2020013227 A1 WO 2020013227A1 JP 2019027344 W JP2019027344 W JP 2019027344W WO 2020013227 A1 WO2020013227 A1 WO 2020013227A1
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Prior art keywords
mass
phosphorus
powder
copper
alloy
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PCT/JP2019/027344
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French (fr)
Japanese (ja)
Inventor
大輔 深江
英昭 河田
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日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to JP2020530226A priority Critical patent/JP7248027B2/en
Priority to EP19834991.2A priority patent/EP3822379B1/en
Priority to CN201980045440.XA priority patent/CN112368409B/en
Publication of WO2020013227A1 publication Critical patent/WO2020013227A1/en

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1103Making porous workpieces or articles with particular physical characteristics
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a sintered alloy suitable for a turbocharger turbo component or the like and a method for producing the same, and more particularly, to a sintered alloy suitable for a nozzle body or the like which requires heat resistance, corrosion resistance and wear resistance, and a method for producing the same. .
  • a turbine is rotatably supported by a turbine housing connected to an exhaust manifold of the internal combustion engine, and a plurality of nozzle vanes are rotatably supported so as to surround an outer peripheral side of the turbine.
  • Exhaust gas flowing into the turbine housing flows into the turbine from the outer peripheral side and is discharged in the axial direction, and at that time, rotates the turbine.
  • the air supplied to the internal combustion engine is compressed by rotating a compressor provided on the same shaft on the opposite side of the turbine.
  • the nozzle vane is rotatably supported by a ring-shaped component called by a name such as a nozzle body or a mount nozzle.
  • the shaft of the nozzle vane passes through the nozzle body and is connected to a link mechanism. When the link mechanism is driven, the nozzle vanes rotate, and the opening degree of the flow path through which the exhaust gas flows into the turbine is adjusted.
  • Turbo components for a turbocharger as described above that is, turbo components provided in a turbine housing, such as a nozzle body (mount nozzle) and a plate nozzle attached thereto, are exhaust gas which is a high-temperature corrosive gas. Contact with. Therefore, these parts are required to have heat resistance and corrosion resistance and also wear resistance to cope with sliding contact with the nozzle vanes. For this reason, conventionally, for example, high-chromium cast steel, heat-resistant steel specified as type SCH22 in JIS standards, or heat-resistant alloy which has been subjected to chromium surface treatment for the purpose of improving corrosion resistance has been used as a material constituting a turbo component. Abrasive materials and the like are used.
  • the present invention provides a sintered alloy having excellent wear resistance, corrosion resistance and machinability, and a method for producing the same, which is suitable for application to turbocharger parts by further improving the iron-based sintered alloy.
  • the task is to provide
  • a sintered alloy having a total composition of 13.86 to 27.72% of Cr and 6.47 to 20.33% of Ni in mass%. %, Cu: 0.85 to 11.05%, Si: 0.46 to 2.77%, P: 0.15 to 1.95%, C: 0.20 to 1.00%, and the balance
  • a metallurgical structure comprising Fe and an unavoidable element and having a density of 6.8 to 7.4 Mg / m 3 , the metal structure having an iron alloy matrix in which pores are dispersed and a carbide dispersed in the iron alloy matrix.
  • the gist is that the iron alloy matrix is composed of crystal grains having an average crystal grain size of 10 to 50 ⁇ m.
  • the sintered alloy has a total composition of 13.86 to 27.72% of Cr, 6.47 to 20.33% of Ni, and 0.85% of Cu in mass%.
  • Si 0.46 to 2.77%
  • P 0.15 to 1.95%
  • C 0.20 to 1.00%
  • carbide-forming element 3.23% or less
  • a sintered alloy having a balance of Fe and inevitable elements and a density of 6.8 to 7.4 Mg / m 3 , wherein the carbide-forming element is selected from the group consisting of Mo, V, W, Nb and Ti.
  • the gist of the invention is that it is composed of crystal grains of
  • the method for producing a sintered alloy includes, in mass%, Cr: 15 to 30%, Ni: 7 to 24%, Si: 0.5 to 3.0%, and An iron alloy powder comprising the balance of Fe and unavoidable impurities is prepared, and an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass, a copper-phosphorus alloy powder having a phosphorus content of 5 to 20% by mass, and copper
  • the raw material powder By preparing a raw material powder containing phosphorus of 0.8% by mass, 0.85 to 11.05% by mass of copper, and 0.20 to 1.00% by mass of carbon, the raw material powder is compressed to have a density of 6%. From 0.0 to 6.8 Mg / m 3 , and pressing the compact in a non-oxidizing atmosphere at 1050 The essence is to sinter by heating to a temperature of 11160 ° C.
  • a method for producing a sintered alloy includes: in mass%, 15 to 30% of Cr, 7 to 24% of Ni, 0.5 to 3.0% of Si, : An iron alloy powder comprising 3% by mass or less and the balance of Fe and unavoidable impurities, wherein the carbide-forming element is at least one element selected from the group consisting of Mo, V, W, Nb and Ti
  • the above iron alloy powder is prepared, and is selected from iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass, copper-phosphorus alloy powder having a phosphorus content of 5 to 20% by mass, and copper powder.
  • a compounding material for phosphorus and copper which is composed of one or more kinds, is prepared, and the iron alloy powder, the compounding material and the graphite powder are mixed, and 0.15 to 1.95 mass% of phosphorus, 0% .85 to 11.05 mass% copper and 0.20 to 1.00 mass% charcoal
  • the raw material powder was prepared containing the raw material powder by compressing a density to form a green compact of 6.0 ⁇ 6.8Mg / m 3, 1050 ⁇ the green compact in a non-oxidizing atmosphere 1160
  • the sintering is performed by heating to a temperature of ° C.
  • the compounding material is a powder material containing phosphorus in one or both forms of iron-phosphorus alloy powder and copper-phosphorus alloy powder, and containing copper in one or both forms of copper powder and copper-phosphorus alloy powder.
  • Good to be. Any of the following (1) to (5) can be used as the compounding material. (1) a combination of an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass and a copper powder; (2) an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass; (3) an iron-phosphorus alloy powder having a phosphorus content of 10 to 30 mass%, and a copper-phosphorus alloy powder having a phosphorus content of 5 to 20 mass%.
  • the non-oxidizing atmosphere may be a mixed gas of nitrogen and hydrogen containing 10% by mass or more of nitrogen, or a normal-pressure atmosphere composed of nitrogen gas, and may be a surface of the sintered alloy and an inner surface of the pore.
  • the composition design of the iron-based alloy it is possible to improve the machinability of the sintered alloy while suppressing the influence on other material properties, thereby providing excellent wear resistance, corrosion resistance and machinability, and It is possible to provide a sintered alloy suitable for application to a charger component and a method of manufacturing the same.
  • the alloy composition so that the functions of the components constituting the sintered alloy are exhibited in a good balance, oxidation resistance, corrosion resistance, and machining Provided is a sintered alloy having improved properties.
  • the component compositions of the sintered alloy and the raw material powder of the present invention will be described.
  • the matrix of the sintered alloy is an iron alloy matrix having an austenitic stainless steel composition, and has a metal structure in which pores are dispersed in the matrix and carbide particles are precipitated and dispersed.
  • Austenitic stainless steel is an iron alloy in which chromium and nickel are dissolved in ⁇ -iron, has high corrosion resistance and heat resistance, and has the same thermal expansion coefficient as a general austenitic heat-resistant material.
  • Austenitic stainless steel improves oxidation resistance in a steam environment by suppressing the growth of crystal grains.
  • the austenitic stainless steel constituting the base of the sintered alloy is composed of crystal grains having an average crystal grain size of 10 to 50 ⁇ m. It is possible to suppress the growth of crystal grains in such a particle size range by sintering at a temperature lower than the conventional sintering temperature, and the sintering temperature is set in the range of 1050 to 1160 ° C. To enable sintering at low temperatures, it is useful to use components that generate a liquid phase at low temperatures. In this regard, the copper-phosphorus alloy powder can proceed with sintering at relatively low temperatures of 1050-1130 ° C.
  • the use of the copper-phosphorus alloy powder effectively acts to lower the sintering temperature and is useful in suppressing the growth of crystal grains.
  • the density of the sintered alloy becomes about 6.8 to 7.4 Mg / m 3 .
  • Austenite constituting the base of the sintered alloy can be produced using iron alloy powder in which chromium or nickel is dissolved in iron as a main material. That is, the austenitizing elements (chromium and nickel) are introduced into the raw material powder by alloying with iron to prepare an iron alloy powder. Thereby, the austenitizing element is uniformly distributed in the iron alloy matrix, and exhibits corrosion resistance and heat resistance.
  • Another component that alloys with iron is silicon, which acts as an antioxidant to chromium during the preparation of the iron-chromium alloy powder.
  • the iron alloy base contains chromium (Cr) in an amount of 12% by mass or more, it exhibits corrosion resistance to oxidizing acids.
  • Cr chromium
  • the chromium content of the iron alloy powder is set to 15 mass so that sufficient chromium remains in the iron alloy base. %.
  • the iron alloy powder as a raw material preferably has a chromium content of about 15 to 30% by mass.
  • the proportion of chromium in the entire composition is about 13.86 to 27.72% by mass. It is more preferably at least 16.88% by mass and at most 23.10% by mass, most preferably at least 18.48% by mass and at most 20.33% by mass.
  • the iron alloy base contains 3.5% by mass or more of nickel (Ni), it exhibits corrosion resistance to non-oxidizing acids. Further, when the nickel content of the iron alloy powder is 7% by mass or more, such an effect is suitably exhibited, and oxidation resistance is imparted to the obtained sintered alloy. However, when an iron alloy powder having a nickel content of more than 24% by mass is used, the effects on corrosion resistance and oxidation resistance do not change much. Since nickel is also an expensive material, considering the production cost, the nickel content of the iron alloy powder used as a raw material is preferably 7 to 24% by mass, preferably 10 to 22% by mass. Is used. The nickel content in the overall composition of a suitable sintered alloy obtained using such a raw material is 6.47 to 20.33% by mass. The oxidation resistance is preferably 7.39% by mass or more, and the economical efficiency is preferably 18.48% by mass or less.
  • the iron alloy base contains silicon (Si). Further, when silicon forms a solid solution in the iron alloy matrix, it has an effect of improving the oxidation resistance and heat resistance of the matrix, and the effect is remarkable at 0.46% by mass or more. However, since the iron alloy powder having a silicon content exceeding 3.0% by mass is hard, the compressibility is significantly impaired. When the amount of oxides generated from silicon increases, the progress of sintering is hindered, and the strength of the sintered alloy is reduced. Therefore, the silicon content of the iron alloy powder used as a raw material is preferably 0.5 to 3.0% by mass. The silicon content in the overall composition of the sintered alloy produced using such an iron alloy powder is 0.46 to 2.77% by mass. From the viewpoint of oxidation resistance, the silicon content in the entire composition is preferably 0.74% by mass or more and 1.85% by mass or less.
  • phosphorus (P) which generates a eutectic liquid phase of iron-phosphorus-carbon, is used to promote sintering and is blended in the form of a phosphorus alloy powder.
  • phosphorus alloy powder one or both of an iron-phosphorus alloy powder and a copper-phosphorus alloy powder can be used as the phosphorus alloy powder.
  • the iron-phosphorus alloy powder used preferably has a phosphorus content of 10 to 30% by mass.
  • the phosphorus content is less than 5% by mass, the amount of liquid phase generated is small, and sintering does not proceed sufficiently.
  • the phosphorus content exceeds 25% by mass, the copper-phosphorus alloy powder becomes hard, and the compressibility of the raw material powder is significantly impaired. Further, the generated liquid phase may easily flow out of the sintered body before being sufficiently diffused.
  • the copper-phosphorus alloy powder used preferably has a phosphorus content of 5 to 25% by mass.
  • the proportion of phosphorus is less than 0.15% by mass in the entire composition of the sintered alloy, the amount of generated liquid phase is insufficient, and the sintering promoting effect is poor.
  • the proportion of phosphorus exceeds 1.95% by mass, sintering proceeds excessively and densifies, and when the density exceeds the upper limit of the density of the sintered alloy, pores are reduced. Thereby, it becomes difficult to suppress the plastic flow of the matrix, and the wear resistance is reduced.
  • the excess phosphorus alloy powder is likely to flow out as a liquid phase to the outside, and when the liquid phase flows out, the portion where the phosphorus alloy powder was present becomes pores (so-called Kirkendall voids), and the iron alloy base is coarse. Since the pores are formed, the corrosion resistance is reduced. Further, when sintering proceeds excessively due to the increase in the generation of the eutectic liquid phase, the growth of chromium carbide is promoted, and the precipitated chromium carbide becomes coarse. Therefore, the phosphorus alloy powder is preferably blended with the raw material powder such that the proportion of phosphorus in the entire composition of the sintered alloy is 0.15 to 1.95% by mass. More preferably, the phosphorus content is 0.60% by mass or more and 1.50% by mass or less, and the more appropriate phosphorus content is 0.60% by mass or more and 1.05% by mass or less.
  • oxidation resistance and corrosion resistance are improved by the solid solution of copper (Cu) in the matrix.
  • copper hardens soft austenite and suppresses adhesion of matrix, thereby improving machinability.
  • Copper can be blended with the raw material powder as copper powder or copper-phosphorus alloy powder.
  • copper-phosphorus alloy powder When the total amount of phosphorus to promote sintering is formulated as iron-phosphorus alloy powder, copper is formulated in the form of copper powder.
  • a copper-phosphorus alloy powder is used so that the phosphorus content of the raw material powder becomes the above-mentioned proper phosphorus composition ratio. .
  • the copper-phosphorus alloy powder When the amount of copper introduced by the copper-phosphorus alloy powder is insufficient, or when the copper-phosphorus alloy powder is not used, copper powder is used.
  • the copper content in the entire composition of the sintered alloy is 0.85 to 11.05% by mass, the oxidation resistance and the corrosion resistance are favorable, so that it is preferable. More preferably, the copper content is 3.40% by mass or more and 8.50% by mass or less, and a more appropriate copper content is 3.40% by mass or more and 5.95% by mass or less.
  • one kind of powder or a combination of plural kinds of powders as shown in the following five forms can be used as the compounding material for compounding phosphorus and copper.
  • copper-phosphorus alloy powder P: 5 to 25% by mass
  • the amount of copper can be adjusted in the range of 0.75 to 12.35% by mass
  • the amount of phosphorus can be adjusted in the range of 0.05 to 3.25% by mass.
  • the copper-phosphorus alloy powder generates a eutectic liquid phase at a lower temperature than the iron-phosphorus alloy powder, so that the sintering temperature can be lowered and is suitable for suppressing the growth of crystal grains.
  • the copper-phosphorus alloy powder used preferably has a phosphorus content of 5% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 20% by mass or less, from the viewpoint of generating a liquid phase well. It becomes.
  • the copper-phosphorus alloy powder uses copper-phosphorus alloy powder since the machinability of the obtained sintered alloy tends to be improved as compared with the use of iron-phosphorus alloy powder.
  • the form (5) is preferable.
  • the amount of the compounding material can be easily determined based on the composition ratio of phosphorus and copper.
  • (1) Combination of iron-phosphorus alloy powder and copper powder (2) Combination of iron-phosphorus alloy powder and copper-phosphorus alloy powder (3) Iron-phosphorus alloy powder and copper-phosphorus alloy powder Combination with copper powder (4) Combination with copper-phosphorus alloy powder and copper powder (5) Copper-phosphorus alloy powder
  • Carbon is mixed with raw material powder as graphite powder, and generates a eutectic liquid phase of iron-phosphorus-carbon upon heating to promote sintering.
  • the carbon is dispersed and precipitated as chromium carbide in the matrix. If the amount of carbide precipitation is large, the machinability decreases, so in the present invention, the precipitation of carbide is controlled by appropriately adjusting the blending amount of the graphite powder. Specifically, graphite powder is blended so that the ratio of carbon to the entire composition is 0.20 to 1.00% by mass.
  • the proportion of carbon exceeds 1.00% by mass of the entire composition, even if sintering proceeds due to the generation of an iron-phosphorus-carbon eutectic liquid phase, a large amount of carbides will be formed, resulting in reduced machinability. I do. In addition, the amount of chromium dissolved in the matrix decreases, and heat resistance and corrosion resistance decrease.
  • the proportion of carbon is less than 0.20% by mass of the entire composition, the effect of promoting sintering and the wear resistance due to carbides cannot be obtained.
  • the carbon content is 0.20% by mass or more and 1.00% by mass or less, more preferably 0.4% by mass or more and 0.80% by mass or less of the whole composition.
  • the precipitation of chromium carbide can be suppressed by mixing an element having a higher ability to generate carbide than chromium (hereinafter referred to as a carbide-forming element) into the raw material powder.
  • the carbide-forming element reacts with graphite preferentially over chromium during sintering to form carbide, and at least a part of the carbide-forming element exists as a carbide in the sintered alloy. This suppresses a decrease in the chromium concentration in the iron alloy base, and thus has an effect of improving the heat resistance and corrosion resistance of the base. Further, when the carbide-forming element reacts with carbon to form an alloy carbide, it contributes to an improvement in wear resistance.
  • the carbide-forming element can be selected from the group consisting of molybdenum, vanadium, tungsten, niobium, and titanium, and may be used alone or in combination of two or more. However, if the carbide-forming element is added in excess of 3.23% by mass of the entire composition, the compressibility of the raw material powder is reduced, so that it is arbitrarily added within the range of 3.23% by mass or less of the entire composition of the sintered alloy. do it.
  • the content of the carbide-forming element is 0.46% by mass or more and 2.77% by mass or less of the whole composition. When a plurality of types of elements are used in combination, the total amount may be the above composition ratio.
  • the sintered alloy has a total composition of 13.86 to 27.72% of Cr, 6.47 to 20.33% of Ni, and Cu: 0 by mass%. 0.85 to 11.05%, Si: 0.46 to 2.77%, P: 0.15 to 1.95%, C: 0.20 to 1.00%, and the balance of Fe and unavoidable elements Preferably.
  • the sintered alloy has a total composition of 13.86 to 27.72% of Cr, 6.47 to 20.33% of Ni, and 0.85 to 0.8% of Cu in mass%.
  • the carbide-forming element is at least one selected from the group consisting of molybdenum, vanadium, tungsten, niobium, and titanium, and may be one or more of these.
  • the sintered alloy prepared based on the above composition ratio carbides are precipitated and dispersed in the iron alloy matrix in which pores are dispersed, and the carbides can be formed from iron, chromium, and the above-mentioned carbide-forming elements. It can be suitably produced as a sintered alloy having a density of about 6.8 to 7.4 Mg / m 3 .
  • the carbide reduces the contact between the ferrous alloy base and the mating member when the sintered alloy slides with the mating member and suppresses the plastic flow of the matrix, thereby contributing to wear resistance.
  • the alloy composition is designed so that the ratio of carbide is equal to or less than a predetermined amount.
  • the carbide be dispersed and deposited as a large number of particles without coarsening so that the function of the carbide is efficiently exhibited.
  • the ubiquitous carbide increases the region where the carbide is absent, that is, the region where the plastic flow is not suppressed, and the wear resistance is significantly reduced. It also has an adverse effect on the machinability of the sintered alloy.
  • the dispersed carbide has a size of less than 1 ⁇ m, it cannot substantially have the function of suppressing the flow of the matrix. For these reasons, carbide particles having a maximum diameter (maximum particle size) in the range of 1 to 10 ⁇ m are preferable.
  • the ratio (area ratio) of the area of the carbide particles having the maximum diameter in the range of 1 to 10 ⁇ m to the area of all the carbide particles is preferably 90% or more.
  • the heating temperature at the time of sintering can be set low, and the coarsening of the carbide particles is suppressed.
  • the maximum value of the particle size of the carbide particles is determined by image analysis software when measuring the particle size from the image of the particle cross section by image analysis of the metal structure cross section using image analysis software (WinROOF manufactured by Mitani Corporation).
  • the long length of the particle portion determined to be the maximum in the image shall be applied.
  • the average grain size of the crystal grains of the iron alloy matrix is obtained by measuring the area of the austenite matrix and the number of crystal grains in the cross section by image analysis of the metal structure cross section, and from these values, the average area of the crystal grains (number average). Is calculated, and a value converted as an area circle equivalent diameter by an approximate calculation is applied.
  • a mixed powder is prepared by mixing the raw materials so that the ratio of each component becomes the composition ratio of the sintered alloy, and the mixed powder is used as a raw material powder for molding.
  • a green compact is obtained by compression molding this, and a sintered body obtained by heating the green compact to a sintering temperature is the above-mentioned sintered alloy.
  • the iron alloy powder containing nickel, chromium, and silicon (first raw material) as described above is mixed with phosphorus and copper in any of the above-described forms (1) to (5).
  • the second raw material and the graphite powder are uniformly mixed to prepare a mixed powder.
  • the mixed powder contains 0.15 to 1.95% by mass of phosphorus, 0.85 to 11.05% by mass of copper, and 0.20 to 1.00% by mass of carbon. Adjust the mixing ratio.
  • the obtained mixed powder can be used as a raw material powder for molding.
  • the plurality of powders may be individually charged in the preparation of a mixed powder, or they may be uniformly mixed in advance. You may throw in after mixing.
  • a raw material powder further containing a carbide-forming element so as to be 3.23% by mass or less of the whole composition is used.
  • the carbide-forming element is selected from molybdenum, vanadium, tungsten, niobium, and titanium, and may be used alone or in combination of two or more.
  • the carbide-forming element can be used in a state of being alloyed with the iron alloy as the first raw material. That is, in the second embodiment, an iron alloy powder containing nickel, chromium, silicon, and a carbide-forming element may be used as the first raw material.
  • the ratio of the carbide-forming element is preferably not more than 3.23% by mass of the entire composition. Since the effect of the addition of the carbide-forming element becomes apparent at about 0.92% by mass, it is preferable to use it in the range of 0.92 to 3.23% by mass. However, this is an optional component, and can be used in the range of 0 to 3.23% by mass depending on the design of the alloy composition, particularly the composition ratio of chromium and carbon.
  • a passivation film of chromium is formed on the surface of the sintered alloy and on the inner surface of the pores due to oxygen contained in the high-temperature exhaust gas, which results in abrasion resistance and corrosion resistance. Is improved.
  • the passivation film of chromium is hard and firmly fixed to the surface of the sintered alloy, and has an effect of preventing the iron alloy base from adhering to the mating member.
  • the pores covered with the passivation film of chromium have an effect of preventing plastic flow of the iron alloy matrix, and the wear resistance of the sintered alloy is improved.
  • the density of the sintered alloy is preferably about 6.80 to 7.40 Mg / m 3 , and when the density exceeds 7.40 Mg / m 3 , the passivation film has No effect is obtained and wear resistance is reduced. If it is less than 6.80 Mg / m 3 , the strength as a sintered alloy is reduced, and the wear resistance is reduced.
  • the compression molding of the raw material powder is preferably performed so that the green compact has a density of about 6.00 to 6.80 Mg / m 3 . Since the sintering proceeds due to the generation of a liquid phase at a low temperature due to the use of the phosphorus alloy powder, sintering proceeds by heating a green compact having such a density to 1050 to 1160 ° C., and the density becomes 6. A sintered alloy of about 80 to 7.40 Mg / m 3 is obtained.
  • the heating temperature during sintering By setting the heating temperature during sintering to the above temperature range, the growth of crystal grains in the iron alloy matrix is suppressed, and the average crystal grain size of the iron alloy matrix becomes about 10 to 50 ⁇ m. If the heating temperature is lower than 1050 ° C., sintering hardly proceeds, and if it exceeds 1160 ° C., it becomes easy to grow into coarse crystal grains having a grain size exceeding 50 ⁇ m in the iron alloy base after sintering. More preferably, the sintering temperature is 1100 ° C or higher and 1140 ° C or lower.
  • a chromium-containing alloy powder from which a passivation film on the surface has been removed is used as a raw material so that sintering proceeds actively, and sintering is performed in a vacuum atmosphere or This is performed in a reduced pressure atmosphere.
  • the sintering proceeds satisfactorily at a relatively low temperature due to the generation of the liquid phase by the phosphorus alloy powder, so that the activity during sintering can be maintained in a non-oxidizing atmosphere, and Sintering is possible even in a pressure environment. Therefore, there is no need to adjust the pressure environment to vacuum or reduced pressure, and a turbocharger component can be manufactured at low cost in a non-oxidizing environment similar to that for manufacturing a general sintered component.
  • the atmosphere gas containing nitrogen include a nitrogen gas, a mixed gas of nitrogen and hydrogen, an ammonia decomposition gas, a mixed gas obtained by mixing nitrogen with an ammonia decomposition gas, and a mixed gas obtained by mixing hydrogen with an ammonia decomposition gas.
  • the amount of nitrogen introduced into the sintered alloy from the atmosphere is extremely small, and is substantially the same as the amount of unavoidable impurities contained in the sintered alloy.
  • a sintered alloy having a density of 6.8 to 7.4 Mg / m 3 is obtained, and the obtained sintered alloy has pores and carbide precipitate particles dispersed in an iron alloy matrix having an austenitic stainless steel composition.
  • the austenite structure is hardened by the solid solution of copper, and the wear resistance and corrosion resistance of the iron alloy base are improved.
  • the structure of the iron alloy matrix becomes fine crystal grains having an average crystal grain size of about 10 to 50 ⁇ m due to the low sintering temperature, and the corrosion resistance and oxidation resistance of the matrix are improved.
  • the size of the carbide particles is about 1 to 10 ⁇ m in size, and the carbide having a particle size exceeding 10 ⁇ m is less than 10% of the area occupied by carbide in the structure cross section. Since it is manufactured based on the composition ratio determined so that the amount of carbide precipitation is suppressed, the ratio of carbide particles occupying the metal structure cross section is 10 area% or less, and the machinability of the sintered alloy is improved. Moreover, even if the amount of carbide precipitation itself decreases, the carbide particles are finely dispersed, so that the adhesion wear of the matrix can be prevented, and the suppression of the crystal grain growth of the matrix by the pinning effect of the carbide is also effective. is there.
  • Example Nos. 1 to 39 As an iron alloy powder, an alloy powder containing chromium, nickel, and silicon at the composition ratios shown in Table 1 (average particle diameter: 70 ⁇ m) was prepared. Further, as the copper-phosphorus alloy powder, a copper-phosphorus alloy powder having a phosphorus content shown in Table 1 (average particle diameter: 40 ⁇ m, containing copper and unavoidable impurities as the balance) was prepared. In addition, the median diameter based on the particle size distribution measurement was applied to the average particle diameter of the powder. These alloy powder and graphite powder (average particle diameter: 10 ⁇ m) were uniformly mixed at the mixing ratio shown in Table 1 to obtain a mixed powder having the overall composition shown in Table 2. This was used as a raw material powder for molding by the following operation.
  • the raw material powder was filled in a mold hole, and compression-molded at a pressure of 600 MPa using a punch, thereby forming two types of compacts, a columnar shape and a disc-like shape.
  • the dimensions of the cylindrical green compact were: outer diameter: 10 mm, height: 10 mm, and the dimensions of the disc-shaped green compact were: outer diameter: 24 mm, height: 8 mm.
  • the amount of the raw material powder at which the density of the green compact was 6.4 Mg / m 3 was calculated in advance, and for sample numbers 1 to 3, 5 to 8, the density of the green compact was calculated.
  • the amount of the raw material powder having the value shown in Table 2 was calculated, and the amount of the raw material powder filled in the mold cavity was adjusted by weighing.
  • the density of the obtained green compact was confirmed according to the Archimedes method.
  • the obtained two types of green compacts were heated to 1130 ° C. in a mixed gas atmosphere of hydrogen and nitrogen, sintered at the same temperature for 60 minutes, and then cooled to room temperature. At this time, the average cooling rate from the sintering temperature to 300 ° C. was 12 ° C./min. In this way, sintered bodies of sample numbers 1 to 39 were produced.
  • ⁇ Density and wear of sintered alloy The density of the sintered alloy was measured using a cylindrical sintered alloy sample according to a method for testing the sintered density of a metal sintered material specified in Japanese Industrial Standards (JIS) Z2505.
  • the wear amount of the sintered alloy was measured as a wear amount in a roll-on-disc friction wear test using a disc-shaped sintered alloy sample.
  • a sintered alloy sample was used as a disk material, and reciprocal sliding with respect to a mating member was performed at 700 ° C. for 15 minutes to measure the amount of wear of the disk material.
  • a mating member a roll (outer diameter: 15 mm, length: 22 mm) obtained by subjecting JIS SUS316L equivalent material to chromizing treatment was used.
  • ⁇ Grit of iron alloy base> Further, the columnar sintered alloy sample was cut, the cross section of the sample was mirror-polished, and the cross section was corroded with aqua regia (nitric acid: hydrochloric acid 1: 3). The tissue at the base was observed at a magnification of ⁇ 2. At this time, using a WinROOF manufactured by Mitani Shoji Co., Ltd. as image analysis software, image analysis of the tissue cross section is performed to binarize the image, the area of the austenite matrix is measured, and the number of crystal grains in the matrix is determined. The average area of the crystal grains was calculated by the measurement. The average crystal grain size of the crystal grains was determined by converting this value to the area circle equivalent diameter.
  • a strip-shaped sintered alloy sample having a major axis of 20 mm, a minor axis of 10 mm, and a height of 3 mm was cut out from a cylindrical sintered body having an outer diameter of 24 mm and a length of 8 mm by machining.
  • the sintered alloy sample was left in an atmosphere containing steam (temperature: 860 ° C., test atmosphere: 8% steam / air) for 100 hours, then collected and cut.
  • the cross section was processed and the metal structure of the cross section was observed under a microscope. In this cross-sectional observation, the thickness of the oxide film was measured. In this measurement, three points are arbitrarily selected in the oxide film portion of the cross-sectional image, the thickness is measured, and the measured value is displayed as an average value.
  • the sintered alloys of sample numbers 1 to 8 have different chromium contents.
  • the crystal grains of the iron alloy matrix are small, and the growth of the crystal grains of the matrix is suitably suppressed.
  • the chromium content increases, the crystal grain size, the amount of wear, and the thickness of the oxide film tend to decrease.
  • the chromium content is 18.48% by mass or more of the whole composition, the size of the crystal grains becomes large. It becomes substantially constant, and the amount of wear also becomes substantially constant. Even if the chromium content exceeds 30% by mass, the wear amount does not increase.
  • the preferable chromium content for achieving both abrasion resistance and oxidation resistance can be considered to be in the range of 13.86% by mass or more and 27.72% by mass or less, and more preferably 16.88% by mass. % And 23.10% by mass or less, most preferably 18.48% by mass and 20.33% by mass or less.
  • the sintered alloys of Sample Nos. 4 and 9 to 15 have different nickel contents, and in each sample, the crystal grains of the iron alloy matrix are small, and the growth of the crystal grains of the matrix is suitably suppressed.
  • the addition of nickel sharply reduces the thickness of the oxide film, indicating that nickel improves the oxidation resistance of the sintered alloy.
  • the increase in the density of the sintered body is considered to be due to the large specific gravity of nickel. From the results in Table 3, it can be expected that even if the nickel content is 22.18% by mass (sample No. 15) or more, there is no inconvenience in the material properties.
  • a nickel content of 6.47% by mass or more It is understood that a sintered alloy having wear resistance and oxidation resistance can be obtained. It can be said that a nickel content of 7.39% by mass or more is more preferable in terms of oxidation resistance.
  • the sintered alloys of sample numbers 4, 16 to 21 have different silicon contents. Since the thickness of the oxide film sharply decreases as the silicon content increases, it is understood that silicon is effective for improving the oxidation resistance. However, when the silicon content exceeds 2.77% by mass, the thickness of the oxide film rapidly increases. The reason for this is considered to be a decrease in the density of the sintered alloy due to a decrease in the compressibility of the raw material powder, and a decrease in the oxidation resistance due to the coarsening of the crystal grains. And it can be understood from the tendency seen in the crystal grain size of the iron alloy matrix. The density of the green compact and the sintered body decreases as the silicon content increases, which is considered to be due to the decrease in the compressibility of the iron alloy powder.
  • the crystal grain size of the iron alloy matrix increases as the silicon content increases. From these results, it is considered that the oxidation resistance is lowered due to insufficient density of the sintered body and coarsening of the crystal grains. Therefore, the silicon content is preferably 0.46% by mass or more and 2.77% by mass or less, and more preferably 0.74% by mass or more and 1.85% by mass or less.
  • the sintered alloys of sample numbers 4, 22 to 27 have different mixing ratios of the copper-phosphorus alloy powder, and accordingly, the contents of copper and phosphorus in the alloy composition change with the mixing ratio. It is understood that the addition of the copper-phosphorus alloy powder and the increase in the proportion thereof increase the density of the obtained sintered alloy, and promote the sintering of the matrix by the copper-phosphorus alloy powder. In addition, it is understood that the oxidation resistance is improved because the thickness of the oxide film is significantly reduced. Further, when the compounding ratio of the copper-phosphorus alloy powder exceeds 4% by mass, the wear amount is reduced, and the wear resistance is improved.
  • the copper content is 3.40% by mass or more and 8.50% by mass or less
  • the phosphorus content is 0.60% by mass or more and 1.50% by mass or less. It is 40% by mass or more and 5.95% by mass or less, and a more appropriate phosphorus content is 0.60% by mass or more and 1.05% by mass or less.
  • the sintered alloys of sample numbers 4, 28 to 33 have different alloy compositions in the used copper-phosphorus alloy powder.
  • the copper content decreases as the phosphorus content increases, but in any of the samples, the copper content of the obtained sintered alloy is in the above-mentioned preferred range. It is considered that the density of the sintered body in Sample No. 28 was relatively low and the thickness of the oxide film was large, so that the phosphorus content was insufficient and the sintering promotion effect was small. Further, the decrease in the sintering density in Sample No. 33 is due to the excessive generation of the liquid phase during sintering. For this reason, the measurement of the crystal grain size and the material properties of sample No. 33 was omitted. From these results, the copper-phosphorus alloy powder used preferably has a phosphorus content of 5% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 20% by mass or less.
  • the sintered alloys of sample numbers 4, 34 to 39 have different carbon contents, and the carbon content is designed to be as low as 0.10 to 1.50 mass% in order to enhance the machinability of the sintered alloy. Have been. In this range, when the carbon content decreases, the density of the sintered body decreases, and the crystal grain size of the iron alloy matrix tends to increase. However, even if the carbon content is reduced to 0.20% by mass, the wear amount and The thickness of the oxide film is kept low. That is, it is understood that the wear resistance and the oxidation resistance are maintained. In sample No. 39, it is considered that the oxidation resistance of the matrix decreased because the amount of chromium dissolved in the matrix during the formation of the iron-phosphorus-carbon eutectic liquid phase decreased. Therefore, the preferable carbon content is 0.20% by mass or more and 1.00% by mass or less, and more preferably 0.4% by mass or more and 0.80% by mass or less.
  • Example numbers 40 to 46 In the sample No. 4 of Example 1, instead of the copper-phosphorus alloy powder, 3.00% by mass of an iron-phosphorus alloy powder (phosphorus content: 35.00% by mass, average particle size: 40 ⁇ m) and 0 to 13 A mixed powder as shown in Table 4 was prepared in the same manner except that 0.000% by mass of copper powder (average particle diameter: 30 ⁇ m) was blended. This was used as a raw material powder for molding, and was molded into disk-shaped and column-shaped green compacts as shown in Table 5 by the same operation as in Example 1 (density of the green compact: 6.4 Mg / m 3 ). These were sintered under the same conditions as in Example 1 to produce a sintered alloy sample, and the density, the wear amount, the crystal grain size of the iron alloy base, and the thickness of the oxide film were measured. Table 6 shows the results.
  • sample No. 43 of Table 6 the density of the sintered alloy was 7.1 Mg / m 3 , the average crystal grain size of the iron alloy matrix was 22 ⁇ m, the wear amount was 23 ⁇ m, and the thickness of the oxide film was 6 ⁇ m.
  • the overall composition of Sample No. 43 is almost the same as that of Sample No. 4, and when these samples are compared, it is understood that the properties of the sintered alloy are also the same. Accordingly, it can be seen that a sintered alloy having the same wear resistance and oxidation resistance can be obtained even when the iron-phosphorus alloy powder and the copper powder are used in combination instead of the copper-phosphorus alloy powder.
  • the density of the sintered alloy decreases as the composition ratio of copper increases. Such a tendency is not observed in Sample Nos. 22 to 25 using the copper-phosphorus alloy powder, and is considered to be related to the balance between the generation of the liquid phase and the progress of sintering. In this regard, the use of copper-phosphorus alloy powder is considered to be more preferable than the combined use of iron-phosphorus alloy powder and copper powder.
  • Example numbers 47 to 52 A mixed powder similar to that of Sample No. 4 of Example 1 was prepared. This was used as a raw material powder for molding, and the same operation as in Example 1 was performed except that the amount of the raw material powder filled into the mold cavity was changed so that the green density of the green compact became the value shown in Table 7. Was repeated to form a disc-shaped and column-shaped green compact. These were sintered under the same conditions to produce a sintered alloy sample. The density of the sample, the amount of wear, the crystal grain size of the iron alloy matrix, and the thickness of the oxide film were measured. Table 7 shows the results.
  • Example numbers 53 to 58 The same operation as in Sample No. 4 of Example 1 was repeated to prepare a mixed powder. This was used as a raw material powder for molding, and was molded into a disc-shaped and column-shaped green compact in the same manner as in Example 1. Using these, sintered alloy samples were produced under the same conditions as in Example 1 except that the sintering temperature was changed to the temperature shown in Table 7. The density of the sample, the amount of wear, the crystal grain size of the iron alloy matrix, and the thickness of the oxide film were measured. Table 7 shows the results.
  • the sintered alloy obtained by sintering the green compact having a density of 6.00 to 6.80 Mg / m 3 has good wear resistance and oxidation resistance. I understand. When the density of the green compact is low, the oxidation resistance is reduced due to insufficient density of the sintered alloy. In sample 52, it was difficult to form a green compact, and a green compact having a density exceeding 6.80 Mg / m 3 was not obtained.
  • the results in Table 7, the density of the sintered body, 6.90Mg / m 3 or more and 7.40Mg / m 3 or less are preferred, preferably 7.00 mg / m 3 or more and 7.40Mg / m 3 or less It is good to adjust so that it becomes. It is more appropriate that the sintered density is not less than 7.20 Mg / m 3 and not more than 7.40 Mg / m 3 .
  • a more preferred sintering temperature can be considered to be 1100 ° C or higher and 1140 ° C or lower.
  • Example numbers 59 to 65 A mixed powder was prepared in the same manner except that the iron alloy powder in Sample No. 4 of Example 1 was changed to an iron alloy powder obtained by alloying molybdenum so as to have an overall composition shown in Table 8 (average particle diameter: 70 ⁇ m). Prepared. This was used as a raw material powder for molding, and the same operation as in Example 1 was repeated to form a disc-shaped and a column-shaped compact (molding pressure: 600 MPa). These were sintered under the same conditions as in Sample No. 4 to prepare a sintered alloy sample, and the density, wear amount, crystal grain size of the iron alloy matrix, and thickness of the oxide film were measured. Table 8 shows the results.
  • a sintered alloy with excellent oxidation resistance, heat resistance and wear resistance and improved machinability is provided, so it can be applied to turbo parts for turbochargers, and it is highly corrosive at high temperatures such as nozzle bodies.
  • the present invention can be advantageously applied to parts requiring durability against gas.

Abstract

Provided is a sintered alloy, which has a total composition comprising, by mass%: 13.86 to 27.72% of Cr; 6.47 to 20.33% of Ni; 0.85 to 11.05% of Cu; 0.46 to 2.77% of Si; 0.15 to 1.95% of P; 0.2 to 1.0% of C; and Fe and inevitable impurities as the balance. The sintered alloy has a density of 6.8 to 7.4 mg/m3, and displays a metal structure having an iron alloy substrate in which pores are dispersed and a carbide dispersed in the iron alloy substrate, the iron alloy substrate having an average crystal particle diameter of 10 to 50 µm.

Description

焼結合金及びその製造方法Sintered alloy and method for producing the same
 本発明は、ターボチャージャー用ターボ部品等に適した焼結合金及びその製造方法に関し、特に、耐熱性、耐食性及び耐摩耗性が要求されるノズルボディ等に好適な焼結合金及びその製造方法に関する。 The present invention relates to a sintered alloy suitable for a turbocharger turbo component or the like and a method for producing the same, and more particularly, to a sintered alloy suitable for a nozzle body or the like which requires heat resistance, corrosion resistance and wear resistance, and a method for producing the same. .
 一般に、内燃機関に付設されるターボチャージャーでは、内燃機関のエキゾーストマニホールドに接続されたタービンハウジングに、タービンが回転自在に支持され、タービンの外周側を囲むように複数のノズルベーンが回動可能に支持されている。タービンハウジングに流入する排気ガスは、外周側からタービンに流れ込んで軸方向へ排出され、その際にタービンを回転させる。そして、タービンの反対側で同じ軸に設けられたコンプレッサが回転することにより、内燃機関へ供給する空気が圧縮される。 Generally, in a turbocharger attached to an internal combustion engine, a turbine is rotatably supported by a turbine housing connected to an exhaust manifold of the internal combustion engine, and a plurality of nozzle vanes are rotatably supported so as to surround an outer peripheral side of the turbine. Have been. Exhaust gas flowing into the turbine housing flows into the turbine from the outer peripheral side and is discharged in the axial direction, and at that time, rotates the turbine. The air supplied to the internal combustion engine is compressed by rotating a compressor provided on the same shaft on the opposite side of the turbine.
 ノズルベーンは、ノズルボディ又はマウントノズルといった名称で呼ばれるリング状の部品に回動可能に支持されている。ノズルベーンの軸は、ノズルボディを貫通し、リンク機構に接続されている。そして、リンク機構が駆動されることによって、ノズルベーンが回動して、排気ガスがタービンに流れ込む流路の開度が調整される。 The nozzle vane is rotatably supported by a ring-shaped component called by a name such as a nozzle body or a mount nozzle. The shaft of the nozzle vane passes through the nozzle body and is connected to a link mechanism. When the link mechanism is driven, the nozzle vanes rotate, and the opening degree of the flow path through which the exhaust gas flows into the turbine is adjusted.
 上記のようなターボチャージャー用ターボ部品、つまり、ノズルボディ(マウントノズル)及びこれに装着されるプレートノズルなどのような、タービンハウジング内に設けられるターボ部品は、高温の腐食性ガスである排気ガスと接触する。従って、これらの部品は、耐熱性及び耐食性が要求されると共に、ノズルベーンとの摺接に対応するための耐摩耗性も要求される。このため、従来、ターボ部品を構成する材料として、例えば、高クロム鋳鋼、JIS規格で種類SCH22として規定される耐熱鋼、又は、耐熱合金に耐食性の向上を目的とするクロム表面処理を施した耐摩耗性材料等が使用されている。 Turbo components for a turbocharger as described above, that is, turbo components provided in a turbine housing, such as a nozzle body (mount nozzle) and a plate nozzle attached thereto, are exhaust gas which is a high-temperature corrosive gas. Contact with. Therefore, these parts are required to have heat resistance and corrosion resistance and also wear resistance to cope with sliding contact with the nozzle vanes. For this reason, conventionally, for example, high-chromium cast steel, heat-resistant steel specified as type SCH22 in JIS standards, or heat-resistant alloy which has been subjected to chromium surface treatment for the purpose of improving corrosion resistance has been used as a material constituting a turbo component. Abrasive materials and the like are used.
 一方、粉末冶金法においても、各種機械部品用途に適用するための焼結合金が開発され、上述のターボ部品向けの耐熱耐摩耗性焼結合金が提案されている(特許文献1参照)。粉末冶金法においては、鋳造等によって得られる溶製鋼では形成されない特殊な金属組織を呈する焼結合金が得られる。 On the other hand, also in the powder metallurgy method, sintered alloys for application to various machine parts have been developed, and the above-mentioned heat- and wear-resistant sintered alloys for turbo parts have been proposed (see Patent Document 1). In the powder metallurgy method, a sintered alloy having a special metal structure that cannot be formed by molten steel obtained by casting or the like is obtained.
特開2013-199695号公報JP 2013-19965 A
 しかし、ノズルベーンと摺接するノズルボディ等のように他部材と摺接するターボチャージャー用部品においては、他部材との凝着摩耗を防止するために、より一層の耐摩耗性の向上が望まれている。また、高温の排気ガス中に含まれる水蒸気により酸化が進行し易いため、耐食性についても更なる向上が望まれている。さらに、複雑化する形状の要求に応えるため、機械加工性(被削性)の向上が望まれている。 However, in a turbocharger component that slides in contact with another member, such as a nozzle body that slides in contact with a nozzle vane, further improvement in wear resistance is desired in order to prevent cohesive wear with another member. . Further, since oxidation is easily progressed by steam contained in high-temperature exhaust gas, further improvement in corrosion resistance is desired. Further, in order to meet the demand for complicated shapes, improvement in machinability (machinability) is desired.
 上述のように、本発明は、鉄基焼結合金のより一層の改善によって、ターボチャージャー用部品への適用に適した、耐摩耗性、耐食性及び被削性に優れる焼結合金及びその製造方法を提供することを課題とする。 As described above, the present invention provides a sintered alloy having excellent wear resistance, corrosion resistance and machinability, and a method for producing the same, which is suitable for application to turbocharger parts by further improving the iron-based sintered alloy. The task is to provide
 上記課題を解決するために、本発明の一態様によれば、焼結合金は、全体組成が、質量%で、Cr:13.86~27.72%、Ni:6.47~20.33%、Cu:0.85~11.05%、Si:0.46~2.77%、P:0.15~1.95%、C:0.20~1.00%、及び、残部のFe及び不可避元素からなり、密度が6.8~7.4Mg/mである焼結合金であって、気孔が分散する鉄合金基地と、前記鉄合金基地に分散する炭化物とを有する金属組織を示し、前記鉄合金基地は、平均結晶粒径が10~50μmの結晶粒で構成されることを要旨とする。 According to one embodiment of the present invention, there is provided a sintered alloy having a total composition of 13.86 to 27.72% of Cr and 6.47 to 20.33% of Ni in mass%. %, Cu: 0.85 to 11.05%, Si: 0.46 to 2.77%, P: 0.15 to 1.95%, C: 0.20 to 1.00%, and the balance A metallurgical structure comprising Fe and an unavoidable element and having a density of 6.8 to 7.4 Mg / m 3 , the metal structure having an iron alloy matrix in which pores are dispersed and a carbide dispersed in the iron alloy matrix. The gist is that the iron alloy matrix is composed of crystal grains having an average crystal grain size of 10 to 50 μm.
 本発明の他の態様によれば、焼結合金は、全体組成が、質量%で、Cr:13.86~27.72%、Ni:6.47~20.33%、Cu:0.85~11.05%、Si:0.46~2.77%、P:0.15~1.95%、C:0.20~1.00%、炭化物生成元素:3.23%以下、及び、残部のFe及び不可避元素からなり、密度が6.8~7.4Mg/mである焼結合金であって、前記炭化物生成元素は、Mo、V、W、Nb及びTiからなる群より選択される少なくとも1種の元素であり、気孔が分散する鉄合金基地と、前記鉄合金基地に分散する炭化物とを有する金属組織を示し、前記鉄合金基地は、平均結晶粒径が10~50μmの結晶粒で構成されることを要旨とする。 According to another aspect of the present invention, the sintered alloy has a total composition of 13.86 to 27.72% of Cr, 6.47 to 20.33% of Ni, and 0.85% of Cu in mass%. To 11.05%, Si: 0.46 to 2.77%, P: 0.15 to 1.95%, C: 0.20 to 1.00%, carbide-forming element: 3.23% or less, and A sintered alloy having a balance of Fe and inevitable elements and a density of 6.8 to 7.4 Mg / m 3 , wherein the carbide-forming element is selected from the group consisting of Mo, V, W, Nb and Ti. At least one element selected from the group consisting of an iron alloy matrix in which pores are dispersed and a metal structure having carbides dispersed in the iron alloy matrix, wherein the iron alloy matrix has an average crystal grain size of 10 to 50 μm. The gist of the invention is that it is composed of crystal grains of
 また、本発明の一態様によれば、焼結合金の製造方法は、質量%で、Cr:15~30%、Ni:7~24%、Si:0.5~3.0%、及び、残部のFe及び不可避不純物からなる鉄合金粉末を用意し、リン含有量が10~30質量%の鉄-リン合金粉末、リン含有量が5~20質量%の銅-リン合金粉末、及び、銅粉末から選択される1種又は複数種の組み合わせからなる、リン及び銅配合用の配合材を用意し、前記鉄合金粉末、前記配合材及び黒鉛粉末を混合して、0.15~1.95質量%のリン、0.85~11.05質量%の銅、及び、0.20~1.00質量%の炭素を含有する原料粉末を調製し、前記原料粉末を圧縮して、密度が6.0~6.8Mg/mの圧粉体を形成し、前記圧粉体を非酸化性雰囲気において1050~1160℃の温度に加熱して焼結することを要旨とする。 According to one embodiment of the present invention, the method for producing a sintered alloy includes, in mass%, Cr: 15 to 30%, Ni: 7 to 24%, Si: 0.5 to 3.0%, and An iron alloy powder comprising the balance of Fe and unavoidable impurities is prepared, and an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass, a copper-phosphorus alloy powder having a phosphorus content of 5 to 20% by mass, and copper A compounding material for compounding phosphorus and copper, which is composed of one or more kinds selected from powders, is prepared, and the iron alloy powder, the compounding material, and the graphite powder are mixed to form 0.15 to 1.95. By preparing a raw material powder containing phosphorus of 0.8% by mass, 0.85 to 11.05% by mass of copper, and 0.20 to 1.00% by mass of carbon, the raw material powder is compressed to have a density of 6%. From 0.0 to 6.8 Mg / m 3 , and pressing the compact in a non-oxidizing atmosphere at 1050 The essence is to sinter by heating to a temperature of 11160 ° C.
 本発明の他の態様によれば、焼結合金の製造方法は、質量%で、Cr:15~30%、Ni:7~24%、Si:0.5~3.0%、炭化物生成元素:3質量%以下、及び、残部のFe及び不可避不純物からなる鉄合金粉末であって、前記炭化物生成元素は、Mo、V、W、Nb及びTiからなる群より選択される少なくとも1種の元素である前記鉄合金粉末を用意し、リン含有量が10~30質量%の鉄-リン合金粉末、リン含有量が5~20質量%の銅-リン合金粉末、及び、銅粉末から選択される1種又は複数種の組み合わせからなる、リン及び銅用の配合材を用意し、前記鉄合金粉末、前記配合材及び黒鉛粉末を混合して、0.15~1.95質量%のリン、0.85~11.05質量%の銅、及び、0.20~1.00質量%の炭素を含有する原料粉末を調製し、前記原料粉末を圧縮して、密度が6.0~6.8Mg/mの圧粉体を形成し、前記圧粉体を非酸化性雰囲気において1050~1160℃の温度に加熱して焼結することを要旨とする。 According to another aspect of the present invention, a method for producing a sintered alloy includes: in mass%, 15 to 30% of Cr, 7 to 24% of Ni, 0.5 to 3.0% of Si, : An iron alloy powder comprising 3% by mass or less and the balance of Fe and unavoidable impurities, wherein the carbide-forming element is at least one element selected from the group consisting of Mo, V, W, Nb and Ti The above iron alloy powder is prepared, and is selected from iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass, copper-phosphorus alloy powder having a phosphorus content of 5 to 20% by mass, and copper powder. A compounding material for phosphorus and copper, which is composed of one or more kinds, is prepared, and the iron alloy powder, the compounding material and the graphite powder are mixed, and 0.15 to 1.95 mass% of phosphorus, 0% .85 to 11.05 mass% copper and 0.20 to 1.00 mass% charcoal The raw material powder was prepared containing the raw material powder by compressing a density to form a green compact of 6.0 ~ 6.8Mg / m 3, 1050 ~ the green compact in a non-oxidizing atmosphere 1160 The sintering is performed by heating to a temperature of ° C.
 前記配合材は、鉄-リン合金粉末及び銅-リン合金粉末の一方又は両方の形態でリンを含有し、銅粉末及び銅-リン合金粉末の一方又は両方の形態で銅を含有する粉末材料であるとよい。前記配合材は、下記(1)~(5)の何れかを利用できる。(1)リン含有量が10~30質量%の鉄-リン合金粉末と銅粉末との組み合わせ、(2)リン含有量が10~30質量%の鉄-リン合金粉末と、リン含有量が5~20質量%の銅-リン合金粉末との組み合わせ、(3)リン含有量が10~30質量%の鉄-リン合金粉末と、リン含有量が5~20質量%の銅-リン合金粉末と、銅粉末との組み合わせ、(4)リン含有量が5~20質量%の銅-リン合金粉末と銅粉末との組み合わせ、(5)リン含有量が5~20質量%の銅-リン合金粉末。前記非酸化性雰囲気は、窒素を10質量%以上含む窒素と水素との混合ガス、又は、窒素ガスからなる常圧の雰囲気であってよく、前記焼結合金の表面、及び、前記気孔の内面に窒化物が形成されている上記焼結合金が得られる。 The compounding material is a powder material containing phosphorus in one or both forms of iron-phosphorus alloy powder and copper-phosphorus alloy powder, and containing copper in one or both forms of copper powder and copper-phosphorus alloy powder. Good to be. Any of the following (1) to (5) can be used as the compounding material. (1) a combination of an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass and a copper powder; (2) an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass; (3) an iron-phosphorus alloy powder having a phosphorus content of 10 to 30 mass%, and a copper-phosphorus alloy powder having a phosphorus content of 5 to 20 mass%. (4) a combination of a copper-phosphorus alloy powder having a phosphorus content of 5 to 20% by mass and a copper powder, (5) a copper-phosphorus alloy powder having a phosphorus content of 5 to 20% by mass . The non-oxidizing atmosphere may be a mixed gas of nitrogen and hydrogen containing 10% by mass or more of nitrogen, or a normal-pressure atmosphere composed of nitrogen gas, and may be a surface of the sintered alloy and an inner surface of the pore. Thus, the above sintered alloy in which a nitride is formed is obtained.
 鉄基合金の組成設計に基づいて焼結合金の被削性を改善しつつ他の材料特性への影響を抑制することができ、これによって、耐摩耗性、耐食性及び被削性に優れ、ターボチャージャー用部品への適用に適した焼結合金及びその製造方法の提供が可能になる。 Based on the composition design of the iron-based alloy, it is possible to improve the machinability of the sintered alloy while suppressing the influence on other material properties, thereby providing excellent wear resistance, corrosion resistance and machinability, and It is possible to provide a sintered alloy suitable for application to a charger component and a method of manufacturing the same.
 焼結合金の金属組織に分散する炭化物粒子は、機械加工時に切削の障害になり易く、炭化物粒子の量が増加すると、焼結合金の被削性は低下する。従って、焼結合金の被削性を改善するには、炭化物粒子の生成を抑制することが有効と考えられる。この方針に従って、炭化物の割合が低い組成の焼結合金について検討したところ、炭化物の減量が被削性の改善に有効である反面、炭化物によるピン止め効果が低下して鉄合金基地の結晶粒が粗大化し、これにより耐酸化性が低下することが判明した。 炭化 Carbide particles dispersed in the metal structure of the sintered alloy tend to hinder cutting during machining, and as the amount of carbide particles increases, the machinability of the sintered alloy decreases. Therefore, in order to improve the machinability of the sintered alloy, it is considered effective to suppress the generation of carbide particles. In accordance with this policy, a study was conducted on sintered alloys having a composition with a low proportion of carbides.While weight reduction of carbides was effective in improving machinability, the pinning effect of carbides was reduced and crystal grains of the iron alloy base were reduced. It was found that the grains became coarse, which led to a decrease in oxidation resistance.
 このため、上記欠点を補う手法について検討したところ、銅が鉄合金基地に固溶すると、水蒸気環境における基地の耐酸化性が向上し、耐食性の向上が可能であることが判明した。また、銅の基地への固溶は、軟質なオーステナイトを硬化して基地と他の部材との凝着を抑制し、これにより被削性の向上が可能であることも判明した。更に、焼結温度を下げることによって、結晶粒の成長を抑制して耐酸化性を高めることが可能であることも明らかになった。この点に関して、銅-リン合金粉末は、低温での液相発生が可能であるので、銅を導入する原料として使用すると、焼結温度を低く設定するための有効な手段となる。 For this reason, a study was made of a method for compensating for the above-mentioned drawbacks, and it was found that when copper forms a solid solution in the iron alloy matrix, the oxidation resistance of the matrix in a steam environment is improved, and the corrosion resistance can be improved. It has also been found that the solid solution of copper in the matrix hardens soft austenite and suppresses adhesion between the matrix and other members, thereby improving machinability. Furthermore, it has been clarified that by lowering the sintering temperature, it is possible to suppress the growth of crystal grains and increase the oxidation resistance. In this regard, since the copper-phosphorus alloy powder can generate a liquid phase at a low temperature, if it is used as a raw material for introducing copper, it is an effective means for setting the sintering temperature low.
 上述の点を考慮して、本発明においては、焼結合金を構成する成分の機能が良好なバランスで発揮されるように合金組成の設計を工夫することによって、耐酸化性、耐食性及び被削性を共に向上させた焼結合金を提供する。以下に、本発明の焼結合金及び原料粉末の成分組成について説明する。 In consideration of the above points, in the present invention, by designing the alloy composition so that the functions of the components constituting the sintered alloy are exhibited in a good balance, oxidation resistance, corrosion resistance, and machining Provided is a sintered alloy having improved properties. Hereinafter, the component compositions of the sintered alloy and the raw material powder of the present invention will be described.
 <焼結合金及び原料粉末の成分組成>
 本発明において、焼結合金の基地は、オーステナイト系ステンレス鋼の組成を有する鉄合金基地であり、基地中に気孔が分散すると共に炭化物粒子が析出分散する金属組織を示す。オーステナイト系ステンレス鋼は、クロム及びニッケルがγ-鉄に固溶した鉄合金であり、耐食性及び耐熱性が高く、熱膨張係数も一般的なオーステナイト系耐熱材料と同等である。
<Component composition of sintered alloy and raw material powder>
In the present invention, the matrix of the sintered alloy is an iron alloy matrix having an austenitic stainless steel composition, and has a metal structure in which pores are dispersed in the matrix and carbide particles are precipitated and dispersed. Austenitic stainless steel is an iron alloy in which chromium and nickel are dissolved in γ-iron, has high corrosion resistance and heat resistance, and has the same thermal expansion coefficient as a general austenitic heat-resistant material.
 オーステナイト系ステンレス鋼は、結晶粒の成長を抑制することよって、水蒸気環境における耐酸化性が向上する。本発明において焼結合金の基地を構成するオーステナイト系ステンレス鋼は、平均結晶粒径が10~50μmの結晶粒で構成される。このような粒径範囲への結晶粒の成長抑制は、従来の焼結温度より低い温度で焼結することによって可能であり、焼結温度は、1050~1160℃の範囲に設定される。低い温度での焼結を可能にするには、低温で液相を発生する成分を使用することが有用である。この点に関して、銅-リン合金粉末は、1050~1130℃の比較的低い温度で焼結を進行させることが可能である。従って、銅-リン合金粉末の使用は、焼結温度の低温化に有効に作用し、結晶粒の成長を抑制する上で有用である。このような温度設定による好適な焼結の進行によって、焼結合金の密度は、6.8~7.4Mg/m程度になる。 Austenitic stainless steel improves oxidation resistance in a steam environment by suppressing the growth of crystal grains. In the present invention, the austenitic stainless steel constituting the base of the sintered alloy is composed of crystal grains having an average crystal grain size of 10 to 50 μm. It is possible to suppress the growth of crystal grains in such a particle size range by sintering at a temperature lower than the conventional sintering temperature, and the sintering temperature is set in the range of 1050 to 1160 ° C. To enable sintering at low temperatures, it is useful to use components that generate a liquid phase at low temperatures. In this regard, the copper-phosphorus alloy powder can proceed with sintering at relatively low temperatures of 1050-1130 ° C. Therefore, the use of the copper-phosphorus alloy powder effectively acts to lower the sintering temperature and is useful in suppressing the growth of crystal grains. With the appropriate sintering proceeding at such a temperature setting, the density of the sintered alloy becomes about 6.8 to 7.4 Mg / m 3 .
 焼結合金の基地を構成するオーステナイトは、クロム又はニッケルが鉄に固溶した鉄合金粉末を主原料として用いて生成することができる。つまり、オーステナイト化する元素(クロム、ニッケル)は、鉄に合金化して鉄合金粉末に調製することによって原料粉末に導入される。これによって、オーステナイト化元素は、鉄合金基地中に均一に分布し、耐食性及び耐熱性を発揮する。鉄に合金化する他の成分としては、ケイ素があり、鉄-クロム合金粉末の調製時にクロムの酸化防止剤として機能する。 オ ー Austenite constituting the base of the sintered alloy can be produced using iron alloy powder in which chromium or nickel is dissolved in iron as a main material. That is, the austenitizing elements (chromium and nickel) are introduced into the raw material powder by alloying with iron to prepare an iron alloy powder. Thereby, the austenitizing element is uniformly distributed in the iron alloy matrix, and exhibits corrosion resistance and heat resistance. Another component that alloys with iron is silicon, which acts as an antioxidant to chromium during the preparation of the iron-chromium alloy powder.
 鉄合金基地は、12質量%以上のクロム(Cr)を含有すると、酸化性の酸に対して耐食性を示す。原料として用いる鉄合金粉末に含有されるクロムの一部が焼結時に炭化物として析出する点を考慮すると、鉄合金基地に十分なクロムが残留するように、鉄合金粉末のクロム含有量が15質量%以上であるとよい。但し、鉄合金粉末のクロム含有量が30質量%を超えると、脆いσ相が形成されて、鉄合金粉末の圧縮性が著しく損なわれる。従って、原料としての鉄合金粉末は、クロム含有量が15~30質量%程度であると好ましい。このような粉末を用いて得られる好適な焼結合金において、全体組成におけるクロムの割合は、13.86~27.72質量%程度となる。より好ましくは16.88質量%以上且つ23.10質量%以下、最も好ましくは18.48質量%以上且つ20.33質量%以下となる。 When the iron alloy base contains chromium (Cr) in an amount of 12% by mass or more, it exhibits corrosion resistance to oxidizing acids. Considering that a part of chromium contained in the iron alloy powder used as a raw material precipitates as carbides during sintering, the chromium content of the iron alloy powder is set to 15 mass so that sufficient chromium remains in the iron alloy base. %. However, if the chromium content of the iron alloy powder exceeds 30% by mass, a brittle σ phase is formed, and the compressibility of the iron alloy powder is significantly impaired. Therefore, the iron alloy powder as a raw material preferably has a chromium content of about 15 to 30% by mass. In a preferred sintered alloy obtained using such a powder, the proportion of chromium in the entire composition is about 13.86 to 27.72% by mass. It is more preferably at least 16.88% by mass and at most 23.10% by mass, most preferably at least 18.48% by mass and at most 20.33% by mass.
 鉄合金基地は、3.5質量%以上のニッケル(Ni)を含有すると、非酸化性の酸に対して耐食性を示す。また、鉄合金粉末のニッケル含有量が7質量%以上であると、このような効果が好適に発揮されて、得られる焼結合金に耐酸化性が付与される。但し、ニッケル含有量が24質量%を超える鉄合金粉末を使用した場合、耐食性及び耐酸化性における効果はさほど変化しなくなる。ニッケルは、高価な素材でもあるので、製造費を考慮すると、原料として使用する鉄合金粉末のニッケル含有量は、7~24質量%であると好適であり、好ましくは10~22質量%のニッケルを含む鉄合金粉末が使用される。このような原料を用いて得られる好適な焼結合金の全体組成におけるニッケル含有量は、6.47~20.33質量%となる。耐酸化性の点において、好ましくは7.39質量%以上であり、経済性の点で好ましくは18.48質量%以下となる。 If the iron alloy base contains 3.5% by mass or more of nickel (Ni), it exhibits corrosion resistance to non-oxidizing acids. Further, when the nickel content of the iron alloy powder is 7% by mass or more, such an effect is suitably exhibited, and oxidation resistance is imparted to the obtained sintered alloy. However, when an iron alloy powder having a nickel content of more than 24% by mass is used, the effects on corrosion resistance and oxidation resistance do not change much. Since nickel is also an expensive material, considering the production cost, the nickel content of the iron alloy powder used as a raw material is preferably 7 to 24% by mass, preferably 10 to 22% by mass. Is used. The nickel content in the overall composition of a suitable sintered alloy obtained using such a raw material is 6.47 to 20.33% by mass. The oxidation resistance is preferably 7.39% by mass or more, and the economical efficiency is preferably 18.48% by mass or less.
 オーステナイト組織を示す鋼は、結晶学的に原子密度が高いので、その耐食性は、フェライト組織のものよりも優れている。このため、焼結後に得られる鉄合金基地が好適にオーステナイト組織を呈するように、クロム含有量及びニッケル含有量を適正に調整した鉄合金粉末を原料として使用することが好ましい。具体的には、横軸をクロム量(質量%)、縦軸をニッケル量(質量%)とするFe-Cr-Ni系合金の焼き鈍し組織図において、A点(Cr:15、Ni:7.5)、B点(Cr:18、Ni:6.5)及びC点(Cr:24、Ni:18)を結んだ折れ線よりニッケル量が多い領域でオーステナイト組織が形成される。従って、このような領域のクロム量及びニッケル量になるように、原料として使用する鉄合金粉末の組成を調整するとよい。 鋼 Steel exhibiting an austenitic structure has a higher atomic density crystallographically, so its corrosion resistance is better than that of a ferritic structure. For this reason, it is preferable to use as a raw material an iron alloy powder whose chromium content and nickel content are appropriately adjusted so that the iron alloy matrix obtained after sintering suitably exhibits an austenite structure. Specifically, in the annealed structure diagram of the Fe—Cr—Ni-based alloy in which the abscissa represents the amount of chromium (% by mass) and the ordinate represents the amount of nickel (% by mass), point A (Cr: 15, Ni: 7. 5) An austenite structure is formed in a region where the amount of nickel is larger than a broken line connecting point B (Cr: 18, Ni: 6.5) and point C (Cr: 24, Ni: 18). Therefore, it is preferable to adjust the composition of the iron alloy powder used as a raw material so that the chromium amount and the nickel amount in such a region are obtained.
 鉄合金粉末は、酸化し易いクロムを含むので、鉄合金粉末を調製する溶湯にケイ素が脱酸剤として添加される。このため、鉄合金基地は、ケイ素(Si)を含有する。また、ケイ素が鉄合金基地に固溶すると、基地の耐酸化性及び耐熱性を高める効果があり、0.46質量%以上において効果が顕著である。但し、ケイ素含有量が3.0質量%を超える鉄合金粉末は硬いため、圧縮性が著しく損なわれる。ケイ素から生じる酸化物が増加すると、焼結の進行を阻害して焼結合金の強度を低下させる。従って、原料として使用する鉄合金粉末のケイ素含有量は0.5~3.0質量%であるとよい。このような鉄合金粉末を用いて製造される焼結合金の全体組成におけるケイ素含有量は、0.46~2.77質量%となる。耐酸化性の観点から、好ましくは、全体組成におけるケイ素含有量が0.74質量%以上且つ1.85質量%以下であるとよい。 Since iron alloy powder contains chromium which is easily oxidized, silicon is added as a deoxidizing agent to the molten metal for preparing iron alloy powder. For this reason, the iron alloy base contains silicon (Si). Further, when silicon forms a solid solution in the iron alloy matrix, it has an effect of improving the oxidation resistance and heat resistance of the matrix, and the effect is remarkable at 0.46% by mass or more. However, since the iron alloy powder having a silicon content exceeding 3.0% by mass is hard, the compressibility is significantly impaired. When the amount of oxides generated from silicon increases, the progress of sintering is hindered, and the strength of the sintered alloy is reduced. Therefore, the silicon content of the iron alloy powder used as a raw material is preferably 0.5 to 3.0% by mass. The silicon content in the overall composition of the sintered alloy produced using such an iron alloy powder is 0.46 to 2.77% by mass. From the viewpoint of oxidation resistance, the silicon content in the entire composition is preferably 0.74% by mass or more and 1.85% by mass or less.
 クロム含有量が多い鉄合金粉末は、焼結が進行し難い。従って、焼結を促進するために、鉄-リン-炭素の共晶液相を発生するリン(P)が使用され、リン合金粉末の形態で配合される。本発明においては、リン合金粉末として、鉄-リン合金粉末及び銅-リン合金粉末の一方又は両方を使用することができる。鉄-リン合金粉末を使用する場合、リン含有量が10質量%未満の粉末であると、液相の発生量が少なく、焼結が十分に進行し難い。一方、リン含有量が30質量%を超えると、鉄-リン合金粉末が硬くなるため、原料粉末の圧縮性を著しく損なう。従って、使用する鉄-リン合金粉末のリン含有量は10~30質量%であることが好ましい。銅-リン合金粉末を使用する場合、リン含有量が5質量%未満であると、液相の発生量が少なく、焼結が十分に進行し難い。一方、リン含有量が25質量%を超えると、銅-リン合金粉末が硬くなって、原料粉末の圧縮性を著しく損なう。また、発生する液相が十分に拡散する前に焼結体の外部に流出し易くなる場合がある。従って、使用する銅-リン合金粉末のリン含有量は5~25質量%であることが好ましい。また、焼結合金の全体組成において、リンの割合が0.15質量%未満であると、液相の発生量が不足して焼結促進効果が乏しくなる。一方、リンの割合が1.95質量%を超えると、焼結が過度に進行して緻密化し、焼結合金としての密度の上限を超えると気孔が縮小する。これにより、基地の塑性流動を抑制し難くなり、耐摩耗性が低下する。また、余剰のリン合金粉末は、液相として外部に流出し易く、液相流出が生じると、リン合金粉末が存在した箇所が気孔(所謂カーケンダルボイド)になって、鉄合金基地に粗大な気孔が形成されるので、耐食性が低下する。更に、共晶液相の生成増加によって過度に焼結が進行すると、クロム炭化物の成長が促進されて、析出するクロム炭化物が粗大化する。故に、リン合金粉末は、焼結合金の全体組成中のリンの割合が0.15~1.95質量%となるように、原料粉末に配合することが好ましい。より好ましくは、リン含有量が0.60質量%以上且つ1.50質量%以下となる配合であり、より適正なリン含有量は0.60質量%以上且つ1.05質量%以下となる。 鉄 Sintering of iron alloy powder with high chromium content is difficult to progress. Therefore, phosphorus (P), which generates a eutectic liquid phase of iron-phosphorus-carbon, is used to promote sintering and is blended in the form of a phosphorus alloy powder. In the present invention, one or both of an iron-phosphorus alloy powder and a copper-phosphorus alloy powder can be used as the phosphorus alloy powder. When an iron-phosphorus alloy powder is used, if the phosphorus content is less than 10% by mass, the amount of liquid phase generated is small, and sintering does not proceed sufficiently. On the other hand, if the phosphorus content exceeds 30% by mass, the iron-phosphorus alloy powder becomes hard, so that the compressibility of the raw material powder is significantly impaired. Accordingly, the iron-phosphorus alloy powder used preferably has a phosphorus content of 10 to 30% by mass. When a copper-phosphorus alloy powder is used, if the phosphorus content is less than 5% by mass, the amount of liquid phase generated is small, and sintering does not proceed sufficiently. On the other hand, when the phosphorus content exceeds 25% by mass, the copper-phosphorus alloy powder becomes hard, and the compressibility of the raw material powder is significantly impaired. Further, the generated liquid phase may easily flow out of the sintered body before being sufficiently diffused. Therefore, the copper-phosphorus alloy powder used preferably has a phosphorus content of 5 to 25% by mass. When the proportion of phosphorus is less than 0.15% by mass in the entire composition of the sintered alloy, the amount of generated liquid phase is insufficient, and the sintering promoting effect is poor. On the other hand, when the proportion of phosphorus exceeds 1.95% by mass, sintering proceeds excessively and densifies, and when the density exceeds the upper limit of the density of the sintered alloy, pores are reduced. Thereby, it becomes difficult to suppress the plastic flow of the matrix, and the wear resistance is reduced. In addition, the excess phosphorus alloy powder is likely to flow out as a liquid phase to the outside, and when the liquid phase flows out, the portion where the phosphorus alloy powder was present becomes pores (so-called Kirkendall voids), and the iron alloy base is coarse. Since the pores are formed, the corrosion resistance is reduced. Further, when sintering proceeds excessively due to the increase in the generation of the eutectic liquid phase, the growth of chromium carbide is promoted, and the precipitated chromium carbide becomes coarse. Therefore, the phosphorus alloy powder is preferably blended with the raw material powder such that the proportion of phosphorus in the entire composition of the sintered alloy is 0.15 to 1.95% by mass. More preferably, the phosphorus content is 0.60% by mass or more and 1.50% by mass or less, and the more appropriate phosphorus content is 0.60% by mass or more and 1.05% by mass or less.
 本発明における焼結合金においては、銅(Cu)が基地に固溶することによって、耐酸化性及び耐食性が向上する。これと共に、銅が軟質なオーステナイトを硬化して基地の凝着を抑制することにより被削性が改善される。銅は、銅粉末又は銅-リン合金粉末として、原料粉末に配合することができる。焼結を促進するためのリンの全量が鉄-リン合金粉末として配合される場合、銅は、銅粉末の形態で配合される。リンの一部又は全部を鉄-リン合金粉末の形態で配合しない場合には、原料粉末のリン含有量が上述の適正なリンの組成割合になるように、銅-リン合金粉末が使用される。そして、銅-リン合金粉末によって導入される銅の量が不足する場合、又は、銅-リン合金粉末を使用しない場合には、銅粉末が使用される。焼結合金の全体組成中の銅含有量が0.85~11.05質量%において、耐酸化性及び耐食性が良好であるので好ましい。より好ましくは、銅含有量が3.40質量%以上且つ8.50質量%以下であり、より適正な銅含有量は3.40質量%以上且つ5.95質量%以下となる。 酸化 In the sintered alloy of the present invention, oxidation resistance and corrosion resistance are improved by the solid solution of copper (Cu) in the matrix. At the same time, copper hardens soft austenite and suppresses adhesion of matrix, thereby improving machinability. Copper can be blended with the raw material powder as copper powder or copper-phosphorus alloy powder. When the total amount of phosphorus to promote sintering is formulated as iron-phosphorus alloy powder, copper is formulated in the form of copper powder. When part or all of phosphorus is not blended in the form of an iron-phosphorus alloy powder, a copper-phosphorus alloy powder is used so that the phosphorus content of the raw material powder becomes the above-mentioned proper phosphorus composition ratio. . When the amount of copper introduced by the copper-phosphorus alloy powder is insufficient, or when the copper-phosphorus alloy powder is not used, copper powder is used. When the copper content in the entire composition of the sintered alloy is 0.85 to 11.05% by mass, the oxidation resistance and the corrosion resistance are favorable, so that it is preferable. More preferably, the copper content is 3.40% by mass or more and 8.50% by mass or less, and a more appropriate copper content is 3.40% by mass or more and 5.95% by mass or less.
 従って、リン及び銅配合用の配合材として、下記の5つの形態で示すような、1種の粉末又は複数種の粉末の組み合わせを使用可能である。(5)の形態として、銅-リン合金粉末(P:5~25質量%)を利用する場合、原料粉末の1.0~13質量%となる割合で銅-リン合金粉末を配合すると、全体組成中、銅量は、0.75~12.35質量%、リン量は、0.05~3.25質量%の範囲で調整可能である。銅-リン合金粉末は、鉄-リン合金粉末よりも低温で共晶液相を発生させるので、焼結温度の低下が可能であり、結晶粒の成長を抑制する上で好適である。液相を良好に生成する点から、使用する銅-リン合金粉末は、リンの含有量が5質量%以上且つ25質量%以下であると好ましく、より好ましくは10質量%以上且つ20質量%以下となる。また、銅-リン合金粉末は、鉄-リン合金粉末を使用するよりも、得られる焼結合金の被削性が向上する傾向があることから、銅-リン合金粉末を利用する(2)~(5)の形態が好ましい。また、(1)及び(5)の形態では、リン及び銅の組成割合に基づいて配合材の使用量を簡単に決定することができる。
 (1)鉄-リン合金粉末と、銅粉末との組み合わせ
 (2)鉄-リン合金粉末と、銅-リン合金粉末との組み合わせ
 (3)鉄-リン合金粉末と、銅-リン合金粉末と、銅粉末との組み合わせ
 (4)銅-リン合金粉末と、銅粉末との組み合わせ
 (5)銅-リン合金粉末
Therefore, one kind of powder or a combination of plural kinds of powders as shown in the following five forms can be used as the compounding material for compounding phosphorus and copper. In the case of using copper-phosphorus alloy powder (P: 5 to 25% by mass) as the form of (5), when the copper-phosphorus alloy powder is blended at a ratio of 1.0 to 13% by mass of the raw material powder, In the composition, the amount of copper can be adjusted in the range of 0.75 to 12.35% by mass, and the amount of phosphorus can be adjusted in the range of 0.05 to 3.25% by mass. The copper-phosphorus alloy powder generates a eutectic liquid phase at a lower temperature than the iron-phosphorus alloy powder, so that the sintering temperature can be lowered and is suitable for suppressing the growth of crystal grains. The copper-phosphorus alloy powder used preferably has a phosphorus content of 5% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 20% by mass or less, from the viewpoint of generating a liquid phase well. It becomes. The copper-phosphorus alloy powder uses copper-phosphorus alloy powder since the machinability of the obtained sintered alloy tends to be improved as compared with the use of iron-phosphorus alloy powder. The form (5) is preferable. Further, in the embodiments (1) and (5), the amount of the compounding material can be easily determined based on the composition ratio of phosphorus and copper.
(1) Combination of iron-phosphorus alloy powder and copper powder (2) Combination of iron-phosphorus alloy powder and copper-phosphorus alloy powder (3) Iron-phosphorus alloy powder and copper-phosphorus alloy powder Combination with copper powder (4) Combination with copper-phosphorus alloy powder and copper powder (5) Copper-phosphorus alloy powder
 炭素は、黒鉛粉末として原料粉末に配合され、加熱時に、鉄-リン-炭素の共晶液相を発生して焼結を促進する。鉄-リン-炭素の共晶液相から鉄合金基地に拡散した炭素がクロムと結合すると、クロム炭化物として基地中に分散して析出する。炭化物の析出量が多いと、被削性が低下するので、本発明においては、黒鉛粉末の配合量を適正に調整することによって、炭化物の析出を制御する。具体的には、全体組成に対する炭素の割合が0.20~1.00質量%となるように黒鉛粉末を配合する。炭素の割合が全体組成の1.00質量%を超えると、鉄-リン-炭素共晶液相の発生によって焼結が進行しても、炭化物が多量に形成されるために被削性が低下する。また、基地中に固溶するクロム量が低下して耐熱性及び耐食性が低下する。炭素の割合が全体組成の0.20質量%未満においては、焼結の促進効果及び炭化物による耐摩耗性が得られなくなる。好ましくは、炭素含有量が全体組成の0.20質量%以上且つ1.00質量%以下、より好ましくは0.4質量%以上且つ0.80質量%以下となるように配合するとよい。 Carbon is mixed with raw material powder as graphite powder, and generates a eutectic liquid phase of iron-phosphorus-carbon upon heating to promote sintering. When carbon diffused from the iron-phosphorus-carbon eutectic liquid phase to the iron alloy matrix is combined with chromium, the carbon is dispersed and precipitated as chromium carbide in the matrix. If the amount of carbide precipitation is large, the machinability decreases, so in the present invention, the precipitation of carbide is controlled by appropriately adjusting the blending amount of the graphite powder. Specifically, graphite powder is blended so that the ratio of carbon to the entire composition is 0.20 to 1.00% by mass. If the proportion of carbon exceeds 1.00% by mass of the entire composition, even if sintering proceeds due to the generation of an iron-phosphorus-carbon eutectic liquid phase, a large amount of carbides will be formed, resulting in reduced machinability. I do. In addition, the amount of chromium dissolved in the matrix decreases, and heat resistance and corrosion resistance decrease. When the proportion of carbon is less than 0.20% by mass of the entire composition, the effect of promoting sintering and the wear resistance due to carbides cannot be obtained. Preferably, the carbon content is 0.20% by mass or more and 1.00% by mass or less, more preferably 0.4% by mass or more and 0.80% by mass or less of the whole composition.
 更に、必要に応じて、クロムより炭化物の生成能が高い元素(以下、炭化物生成元素と称する)を原料粉末に配合することによって、クロム炭化物の析出を抑制することができる。炭化物生成元素は、焼結時にクロムより優先的に黒鉛と反応して炭化物を生成し、炭化物生成元素の少なくとも一部は焼結合金中において炭化物として存在する。これにより、鉄合金基地におけるクロム濃度の低下が抑制されるので、基地の耐熱性及び耐食性を向上させる効果がある。また、炭化物生成元素が炭素と反応して合金炭化物が生成すると、耐摩耗性の向上に寄与する。炭化物生成元素は、モリブデン、バナジウム、タングステン、ニオブ及びチタンからなる群より選択して使用することができ、1種又は2種以上を組み合わせて使用してもよい。但し、炭化物生成元素を、全体組成の3.23質量%を超えて配合すると、原料粉末の圧縮性が低下するので、焼結合金の全体組成の3.23質量%以下の範囲において任意に配合すればよい。好ましくは、炭化物生成元素の含有量が全体組成の0.46質量%以上且つ2.77質量%以下であるとよい。複数種の元素を組み合わせて用いる場合は、その合計量が、上記組成割合であればよい。 析出 Furthermore, if necessary, the precipitation of chromium carbide can be suppressed by mixing an element having a higher ability to generate carbide than chromium (hereinafter referred to as a carbide-forming element) into the raw material powder. The carbide-forming element reacts with graphite preferentially over chromium during sintering to form carbide, and at least a part of the carbide-forming element exists as a carbide in the sintered alloy. This suppresses a decrease in the chromium concentration in the iron alloy base, and thus has an effect of improving the heat resistance and corrosion resistance of the base. Further, when the carbide-forming element reacts with carbon to form an alloy carbide, it contributes to an improvement in wear resistance. The carbide-forming element can be selected from the group consisting of molybdenum, vanadium, tungsten, niobium, and titanium, and may be used alone or in combination of two or more. However, if the carbide-forming element is added in excess of 3.23% by mass of the entire composition, the compressibility of the raw material powder is reduced, so that it is arbitrarily added within the range of 3.23% by mass or less of the entire composition of the sintered alloy. do it. Preferably, the content of the carbide-forming element is 0.46% by mass or more and 2.77% by mass or less of the whole composition. When a plurality of types of elements are used in combination, the total amount may be the above composition ratio.
 従って、本発明の第1の実施形態として、焼結合金は、全体組成が、質量%で、Cr:13.86~27.72%、Ni:6.47~20.33%、Cu:0.85~11.05%、Si:0.46~2.77%、P:0.15~1.95%、C:0.20~1.00%、及び、残部のFe及び不可避元素からなることが好ましい。また、第2の実施形態として、焼結合金は、全体組成が、質量%で、Cr:13.86~27.72%、Ni:6.47~20.33%、Cu:0.85~11.05%、Si:0.46~2.77%、P:0.15~1.95%、C:0.20~1.00%、炭化物生成元素:3.23%以下、及び、残部のFe及び不可避元素からなることが好ましい。炭化物生成元素は、モリブデン、バナジウム、タングステン、ニオブ及びチタンからなる群より選択される少なくとも1種であり、これらのうちの1種又は2種以上であってよい。 Therefore, as a first embodiment of the present invention, the sintered alloy has a total composition of 13.86 to 27.72% of Cr, 6.47 to 20.33% of Ni, and Cu: 0 by mass%. 0.85 to 11.05%, Si: 0.46 to 2.77%, P: 0.15 to 1.95%, C: 0.20 to 1.00%, and the balance of Fe and unavoidable elements Preferably. As a second embodiment, the sintered alloy has a total composition of 13.86 to 27.72% of Cr, 6.47 to 20.33% of Ni, and 0.85 to 0.8% of Cu in mass%. 11.05%, Si: 0.46 to 2.77%, P: 0.15 to 1.95%, C: 0.20 to 1.00%, carbide forming element: 3.23% or less, and It is preferable that the balance consists of Fe and unavoidable elements. The carbide-forming element is at least one selected from the group consisting of molybdenum, vanadium, tungsten, niobium, and titanium, and may be one or more of these.
 上述の組成割合に基づいて調製される焼結合金においては、気孔が分散する鉄合金基地中に、炭化物が析出分散し、炭化物は、鉄、クロム及び上記炭化物生成元素から形成され得る。密度が6.8~7.4Mg/m程度の焼結合金として好適に生成することができる。炭化物は、焼結合金が相手部材と摺動する際に鉄合金基地と相手部材との接触を軽減して基地の塑性流動を抑制するので、耐摩耗性に寄与する。本発明においては、被削性を改善するために、炭化物の割合が所定量以下になるように合金組成が設計されている。このため、炭化物の機能が効率的に発揮されるように、炭化物が粗大化せずに多数の粒子として分散して析出することが好ましい。具体的には、炭化物が10μmを超えて粗大化すると、炭化物の遍在によって、炭化物の不存在領域、つまり、塑性流動が抑制されない領域が増加し、耐摩耗性が著しく低下する。また、焼結合金の被削性にも悪影響を与える。但し、分散する炭化物が、1μm未満の大きさであると、基地の流動を抑制する機能を実質的に有し得ない。このようなことから、最大径(粒径の最大値)が1~10μmの範囲にあるような炭化物粒子が好適である。焼結合金の組織断面において、最大径が1~10μmの範囲にある炭化物粒子の面積が、全炭化物粒子の面積に占める割合(面積率)が90%以上であると好ましい。本発明においては、リン合金(特に銅-リン合金)の焼結促進によって、焼結時の加熱温度を低く設定可能であり、炭化物粒子の粗大化は抑制される。 In the sintered alloy prepared based on the above composition ratio, carbides are precipitated and dispersed in the iron alloy matrix in which pores are dispersed, and the carbides can be formed from iron, chromium, and the above-mentioned carbide-forming elements. It can be suitably produced as a sintered alloy having a density of about 6.8 to 7.4 Mg / m 3 . The carbide reduces the contact between the ferrous alloy base and the mating member when the sintered alloy slides with the mating member and suppresses the plastic flow of the matrix, thereby contributing to wear resistance. In the present invention, in order to improve the machinability, the alloy composition is designed so that the ratio of carbide is equal to or less than a predetermined amount. For this reason, it is preferable that the carbide be dispersed and deposited as a large number of particles without coarsening so that the function of the carbide is efficiently exhibited. Specifically, when the carbide is coarsened to exceed 10 μm, the ubiquitous carbide increases the region where the carbide is absent, that is, the region where the plastic flow is not suppressed, and the wear resistance is significantly reduced. It also has an adverse effect on the machinability of the sintered alloy. However, if the dispersed carbide has a size of less than 1 μm, it cannot substantially have the function of suppressing the flow of the matrix. For these reasons, carbide particles having a maximum diameter (maximum particle size) in the range of 1 to 10 μm are preferable. In the microstructure section of the sintered alloy, the ratio (area ratio) of the area of the carbide particles having the maximum diameter in the range of 1 to 10 μm to the area of all the carbide particles is preferably 90% or more. In the present invention, by promoting the sintering of the phosphorus alloy (particularly, the copper-phosphorus alloy), the heating temperature at the time of sintering can be set low, and the coarsening of the carbide particles is suppressed.
 尚、炭化物粒子の粒径の最大値は、画像解析ソフト(三谷商事株式会社製WinROOF)を用いた金属組織断面の画像解析によって粒子断面の画像から粒径を測定する際に、画像解析ソフトによって画像中における最大と判定される粒子部分の長尺長さを適用するものとする。また、鉄合金基地の結晶粒の平均結晶粒径は、金属組織断面の画像解析によって断面におけるオーステナイト基地の面積及び結晶粒の数を計測し、これらの値から結晶粒の平均面積(数平均)を算出して近似計算によって面積円相当径として換算される値を適用する。 Note that the maximum value of the particle size of the carbide particles is determined by image analysis software when measuring the particle size from the image of the particle cross section by image analysis of the metal structure cross section using image analysis software (WinROOF manufactured by Mitani Corporation). The long length of the particle portion determined to be the maximum in the image shall be applied. The average grain size of the crystal grains of the iron alloy matrix is obtained by measuring the area of the austenite matrix and the number of crystal grains in the cross section by image analysis of the metal structure cross section, and from these values, the average area of the crystal grains (number average). Is calculated, and a value converted as an area circle equivalent diameter by an approximate calculation is applied.
 <焼結合金の製造方法>
 各成分の割合が上記焼結合金の組成割合になるように、原料の配合によって混合粉末を調製し、この混合粉末を成形用の原料粉末として用いる。これを圧縮成形することで圧粉体が得られ、圧粉体を焼結温度に加熱することによって得られる焼結体が上記焼結合金である。
<Production method of sintered alloy>
A mixed powder is prepared by mixing the raw materials so that the ratio of each component becomes the composition ratio of the sintered alloy, and the mixed powder is used as a raw material powder for molding. A green compact is obtained by compression molding this, and a sintered body obtained by heating the green compact to a sintering temperature is the above-mentioned sintered alloy.
 第1の実施形態においては、上述したようなニッケル、クロム及びケイ素を含有する鉄合金粉末(第1原料)に、前述の(1)~(5)の何れかの形態のリン及び銅配合用の配合材(第2原料)、及び、黒鉛粉末を均一に混合して混合粉末を調製する。この際、混合粉末が、0.15~1.95質量%のリン、0.85~11.05質量%の銅、及び、0.20~1.00質量%の炭素を含有するように、混合割合を調整する。得られた混合粉末を成形用の原料粉末として用いることができる。第2原料として複数種の粉末の組み合わせ((1)~(4)の形態)を利用する場合、複数種の粉末を個別に混合粉末の調製に投入しても、或いは、予めこれらを均一に混合した後に投入してもよい。 In the first embodiment, the iron alloy powder containing nickel, chromium, and silicon (first raw material) as described above is mixed with phosphorus and copper in any of the above-described forms (1) to (5). (The second raw material) and the graphite powder are uniformly mixed to prepare a mixed powder. At this time, the mixed powder contains 0.15 to 1.95% by mass of phosphorus, 0.85 to 11.05% by mass of copper, and 0.20 to 1.00% by mass of carbon. Adjust the mixing ratio. The obtained mixed powder can be used as a raw material powder for molding. When a combination of a plurality of powders (forms (1) to (4)) is used as the second raw material, the plurality of powders may be individually charged in the preparation of a mixed powder, or they may be uniformly mixed in advance. You may throw in after mixing.
 第2の実施形態においては、更に、全体組成の3.23質量%以下となるように炭化物生成元素が配合された原料粉末が使用される。炭化物生成元素は、モリブデン、バナジウム、タングステン、ニオブ及びチタンから選択され、1種又は2種以上を組み合わせて使用してもよい。炭化物生成元素は、第1原料である鉄合金に合金化された状態で使用することができる。つまり、第2の実施形態においては、ニッケル、クロム、ケイ素及び炭化物生成元素を含有する鉄合金粉末を第1原料として使用するとよい。炭化物生成元素の割合が全体組成の3.23質量%を超えると、鉄合金粉末の圧縮性が低下し、原料粉末を所望の圧粉密度に成形することが難しくなる。従って、炭化物生成元素の割合は、全体組成の3.23質量%以下であるとよい。尚、炭化物生成元素の添加による効果は、0.92質量%程度において顕かになるので、0.92~3.23質量%の範囲で使用すると好ましい。但し、これは任意成分であり、合金組成の設計、特にクロム及び炭素の組成割合に応じて、0~3.23質量%の範囲で使用可能である。 {Circle around (2)} In the second embodiment, a raw material powder further containing a carbide-forming element so as to be 3.23% by mass or less of the whole composition is used. The carbide-forming element is selected from molybdenum, vanadium, tungsten, niobium, and titanium, and may be used alone or in combination of two or more. The carbide-forming element can be used in a state of being alloyed with the iron alloy as the first raw material. That is, in the second embodiment, an iron alloy powder containing nickel, chromium, silicon, and a carbide-forming element may be used as the first raw material. If the ratio of the carbide-forming element exceeds 3.23% by mass of the entire composition, the compressibility of the iron alloy powder decreases, and it becomes difficult to form the raw material powder to a desired green density. Therefore, the ratio of the carbide forming element is preferably not more than 3.23% by mass of the entire composition. Since the effect of the addition of the carbide-forming element becomes apparent at about 0.92% by mass, it is preferable to use it in the range of 0.92 to 3.23% by mass. However, this is an optional component, and can be used in the range of 0 to 3.23% by mass depending on the design of the alloy composition, particularly the composition ratio of chromium and carbon.
 <圧粉密度及び焼結合金の密度>
 圧縮成形によって得られる圧粉体内の粉末粒子間の気孔は、焼結後の焼結合金にも残存し、気孔量が多いと強度及び耐摩耗性が低下する。但し、ターボチャージャー用部品として使用する焼結合金においては、高温の排気ガスに含まれる酸素によって、焼結合金の表面及び気孔内面にクロムの不動態被膜が形成され、これにより耐摩耗性及び耐食性が向上する。クロムの不動態被膜は、硬く、且つ、焼結合金表面に強固に固着しており、鉄合金基地が相手部材へ凝着するのを防止する効果がある。従って、適量の気孔が焼結合金中に分散すると、クロムの不動態被膜が内面を覆う気孔は、鉄合金基地の塑性流動を防止する作用を有し、焼結合金の耐摩耗性が向上する。この点を考慮すると、焼結合金の密度は、6.80~7.40Mg/m程度が好適であり、7.40Mg/mを超えると、気孔量の低下に伴って不動態被膜の効果が得られず、耐摩耗性が低下する。6.80Mg/mに満たないと、焼結合金としての強度が低下して、耐摩耗性が低下する。好ましくは7.00Mg/m以上且つ7.40Mg/m以下であるとよく、7.20Mg/m以上且つ7.40Mg/m以下の焼結密度であるとより適正である。
<Green density and sintered alloy density>
Pores between the powder particles in the green compact obtained by compression molding remain in the sintered alloy after sintering, and when the amount of the pores is large, the strength and wear resistance are reduced. However, in a sintered alloy used as a turbocharger component, a passivation film of chromium is formed on the surface of the sintered alloy and on the inner surface of the pores due to oxygen contained in the high-temperature exhaust gas, which results in abrasion resistance and corrosion resistance. Is improved. The passivation film of chromium is hard and firmly fixed to the surface of the sintered alloy, and has an effect of preventing the iron alloy base from adhering to the mating member. Therefore, when an appropriate amount of pores are dispersed in the sintered alloy, the pores covered with the passivation film of chromium have an effect of preventing plastic flow of the iron alloy matrix, and the wear resistance of the sintered alloy is improved. . In consideration of this point, the density of the sintered alloy is preferably about 6.80 to 7.40 Mg / m 3 , and when the density exceeds 7.40 Mg / m 3 , the passivation film has No effect is obtained and wear resistance is reduced. If it is less than 6.80 Mg / m 3 , the strength as a sintered alloy is reduced, and the wear resistance is reduced. Preferably may When it is 7.00 mg / m 3 or more and 7.40Mg / m 3 or less, it is more appropriate when there in sintered density of 7.20Mg / m 3 or more and 7.40Mg / m 3 or less.
 <成形及び焼結>
 上記のような密度の焼結合金を得るために、原料粉末の圧縮成形は、圧粉体の密度が6.00~6.80Mg/m程度になるように行うとよい。リン合金粉末の使用によって、低温での液相発生により焼結が進行するので、このような密度の圧粉体を、1050~1160℃に加熱することによって焼結が進行し、密度が6.80~7.40Mg/m程度の焼結合金が得られる。焼結時の加熱温度を上記の温度範囲に設定することによって、鉄合金基地における結晶粒の成長が抑制され、鉄合金基地の平均結晶粒径は10~50μm程度になる。加熱温度が1050℃未満であると、焼結が進行し難く、1160℃を超えると、焼結後の鉄合金基地において、粒径が50μmを超える粗大な結晶粒に成長し易くなる。より好ましくは、焼結温度が1100℃以上且つ1140℃以下であるとよい。
<Molding and sintering>
In order to obtain a sintered alloy having the above density, the compression molding of the raw material powder is preferably performed so that the green compact has a density of about 6.00 to 6.80 Mg / m 3 . Since the sintering proceeds due to the generation of a liquid phase at a low temperature due to the use of the phosphorus alloy powder, sintering proceeds by heating a green compact having such a density to 1050 to 1160 ° C., and the density becomes 6. A sintered alloy of about 80 to 7.40 Mg / m 3 is obtained. By setting the heating temperature during sintering to the above temperature range, the growth of crystal grains in the iron alloy matrix is suppressed, and the average crystal grain size of the iron alloy matrix becomes about 10 to 50 μm. If the heating temperature is lower than 1050 ° C., sintering hardly proceeds, and if it exceeds 1160 ° C., it becomes easy to grow into coarse crystal grains having a grain size exceeding 50 μm in the iron alloy base after sintering. More preferably, the sintering temperature is 1100 ° C or higher and 1140 ° C or lower.
 一般に、クロム含有量が高い焼結合金の製造においては、焼結が活性に進行するように、表面の不動態被膜を除去したクロム含有合金粉末を原料として使用し、焼結は、真空雰囲気又は減圧雰囲気において行われる。この点に関して、本発明においては、リン合金粉末による液相発生によって焼結が比較的低温で良好に進行するので、非酸化性雰囲気中であれば焼結時の活性は維持可能であり、常圧環境でも焼結が可能である。従って、圧力環境を真空又は減圧に整える必要がなく、一般の焼結部品の製造と同様の非酸化性環境下で、安価にターボチャージャー用部品を製造することができる。 Generally, in the production of a sintered alloy having a high chromium content, a chromium-containing alloy powder from which a passivation film on the surface has been removed is used as a raw material so that sintering proceeds actively, and sintering is performed in a vacuum atmosphere or This is performed in a reduced pressure atmosphere. In this regard, in the present invention, the sintering proceeds satisfactorily at a relatively low temperature due to the generation of the liquid phase by the phosphorus alloy powder, so that the activity during sintering can be maintained in a non-oxidizing atmosphere, and Sintering is possible even in a pressure environment. Therefore, there is no need to adjust the pressure environment to vacuum or reduced pressure, and a turbocharger component can be manufactured at low cost in a non-oxidizing environment similar to that for manufacturing a general sintered component.
 尚、焼結雰囲気として、窒素を10容積%程度以上含むガスを使用すると、焼結合金の表面及び気孔内面に硬い窒化物(主にクロム窒化物)が形成され、焼結合金の耐摩耗性を向上させることができるので好ましい。窒素を含む雰囲気ガスとしては、窒素ガス、窒素と水素との混合ガス、アンモニア分解ガス、アンモニア分解ガスに窒素を混合した混合ガス、アンモニア分解ガスに水素を混合した混合ガス等が挙げられる。尚、この場合に雰囲気中から焼結合金に導入される窒素量は極微量であり、焼結合金に含有される不可避不純物の量と同程度である。 When a gas containing about 10% by volume or more of nitrogen is used as a sintering atmosphere, hard nitride (mainly chromium nitride) is formed on the surface of the sintered alloy and the inner surface of the pores, and the wear resistance of the sintered alloy is reduced. Is preferred because the Examples of the atmosphere gas containing nitrogen include a nitrogen gas, a mixed gas of nitrogen and hydrogen, an ammonia decomposition gas, a mixed gas obtained by mixing nitrogen with an ammonia decomposition gas, and a mixed gas obtained by mixing hydrogen with an ammonia decomposition gas. In this case, the amount of nitrogen introduced into the sintered alloy from the atmosphere is extremely small, and is substantially the same as the amount of unavoidable impurities contained in the sintered alloy.
 上述に従って、密度が6.8~7.4Mg/mの焼結合金が得られ、得られる焼結合金は、オーステナイト系ステンレス鋼の組成を有する鉄合金基地に気孔及び炭化物の析出粒子が分散した組織構造を呈する。銅の固溶によってオーステナイト組織が硬化し、鉄合金基地の耐摩耗性及び耐食性が向上する。鉄合金基地の組織は、焼結温度の低さによって、平均結晶粒径が10~50μm程度の細かい結晶粒になり、基地の耐食性及び耐酸化性が向上する。また、炭化物粒子の大きさは、粒径が1~10μm程度の大きさであり、10μmを超える粒径の炭化物は、組織断面において炭化物が占める面積のうちの10%未満である。炭化物の析出量が抑制されるように定めた組成割合に基づいて製造されるので、炭化物粒子が金属組織断面を占める割合は、10面積%以下となり、焼結合金の被削性が向上する。しかも、炭化物の析出量自体は減少しても、炭化物粒子が微細に分散することにより、基地の凝着摩耗は防止可能であり、炭化物のピン止め効果による基地の結晶粒成長の抑制も有効である。 As described above, a sintered alloy having a density of 6.8 to 7.4 Mg / m 3 is obtained, and the obtained sintered alloy has pores and carbide precipitate particles dispersed in an iron alloy matrix having an austenitic stainless steel composition. Presents an organized tissue structure. The austenite structure is hardened by the solid solution of copper, and the wear resistance and corrosion resistance of the iron alloy base are improved. The structure of the iron alloy matrix becomes fine crystal grains having an average crystal grain size of about 10 to 50 μm due to the low sintering temperature, and the corrosion resistance and oxidation resistance of the matrix are improved. Further, the size of the carbide particles is about 1 to 10 μm in size, and the carbide having a particle size exceeding 10 μm is less than 10% of the area occupied by carbide in the structure cross section. Since it is manufactured based on the composition ratio determined so that the amount of carbide precipitation is suppressed, the ratio of carbide particles occupying the metal structure cross section is 10 area% or less, and the machinability of the sintered alloy is improved. Moreover, even if the amount of carbide precipitation itself decreases, the carbide particles are finely dispersed, so that the adhesion wear of the matrix can be prevented, and the suppression of the crystal grain growth of the matrix by the pinning effect of the carbide is also effective. is there.
 (試料番号1~39)
 鉄合金粉末として、表1に示す組成割合でクロム、ニッケル及びケイ素を含有する合金粉末(平均粒子径:70μm)を用意した。また、銅-リン合金粉末として、表1に示すリン含有量の銅-リン合金粉末(平均粒子径:40μm、残部として銅及び不可避不純物を含む)を用意した。尚、粉末の平均粒子径は、粒度分布測定に基づくメジアン径を適用した。これらの合金粉末及び黒鉛粉末(平均粒子径:10μm)を表1に示す配合割合で均一に混合して、表2に示す全体組成の混合粉末を得た。これを成形用の原料粉末として、以下の操作で使用した。
(Sample Nos. 1 to 39)
As an iron alloy powder, an alloy powder containing chromium, nickel, and silicon at the composition ratios shown in Table 1 (average particle diameter: 70 μm) was prepared. Further, as the copper-phosphorus alloy powder, a copper-phosphorus alloy powder having a phosphorus content shown in Table 1 (average particle diameter: 40 μm, containing copper and unavoidable impurities as the balance) was prepared. In addition, the median diameter based on the particle size distribution measurement was applied to the average particle diameter of the powder. These alloy powder and graphite powder (average particle diameter: 10 μm) were uniformly mixed at the mixing ratio shown in Table 1 to obtain a mixed powder having the overall composition shown in Table 2. This was used as a raw material powder for molding by the following operation.
 原料粉末を型孔に充填し、パンチを用いて600MPaの圧力で圧縮成形することにより、円柱状及び円板状の2種類の圧粉体に成形した。円柱状の圧粉体の寸法は、外径:10mm、高さ:10mm、円板状の圧粉体の寸法は、外径:24mm、高さ:8mmとした。尚、試料番号4,9~39では、圧粉体の密度が6.4Mg/mとなる原料粉末の量を予め計算し、試料番号1~3,5~8では、圧粉体の密度が表2の値になる原料粉末の量を計算して、型孔へ原料粉末を充填する量を秤量によって調節した。また、得られた圧粉体の密度はアルキメデス法に従って確認した。 The raw material powder was filled in a mold hole, and compression-molded at a pressure of 600 MPa using a punch, thereby forming two types of compacts, a columnar shape and a disc-like shape. The dimensions of the cylindrical green compact were: outer diameter: 10 mm, height: 10 mm, and the dimensions of the disc-shaped green compact were: outer diameter: 24 mm, height: 8 mm. For sample numbers 4, 9 to 39, the amount of the raw material powder at which the density of the green compact was 6.4 Mg / m 3 was calculated in advance, and for sample numbers 1 to 3, 5 to 8, the density of the green compact was calculated. The amount of the raw material powder having the value shown in Table 2 was calculated, and the amount of the raw material powder filled in the mold cavity was adjusted by weighing. The density of the obtained green compact was confirmed according to the Archimedes method.
 得られた二種類の圧粉体を水素と窒素の混合ガス雰囲気中で1130℃に加熱し、温度を維持して60分間焼結し、その後、室温まで冷却した。この際、焼結温度から300℃までの平均冷却速度は12℃/分であった。このようにして試料番号1~39の焼結体を作製した。 The obtained two types of green compacts were heated to 1130 ° C. in a mixed gas atmosphere of hydrogen and nitrogen, sintered at the same temperature for 60 minutes, and then cooled to room temperature. At this time, the average cooling rate from the sintering temperature to 300 ° C. was 12 ° C./min. In this way, sintered bodies of sample numbers 1 to 39 were produced.
 得られた焼結体を焼結合金試料として用いて、以下のような操作によって、密度、摩耗量、鉄合金基地の結晶粒径及び酸化被膜の厚さを測定した。測定結果を表3に示す。 密度 Using the obtained sintered body as a sintered alloy sample, the density, the wear amount, the crystal grain size of the iron alloy base, and the thickness of the oxide film were measured by the following operations. Table 3 shows the measurement results.
 <焼結合金の密度及び摩耗量>
 焼結合金の密度は、円柱状の焼結合金試料を用いて、日本工業規格(JIS)Z2505に規定された金属焼結材料の焼結密度試験方法に従って測定した。
 焼結合金の摩耗量は、円板状の焼結合金試料を用いたロールオンディスク摩擦摩耗試験における摩耗量として測定した。ロールオンディスク摩擦摩耗試験では、ディスク材として焼結合金試料を使用し、相手部材に対する往復摺動を700℃で15分間行って、ディスク材の摩耗量を測定した。相手部材として、JIS規格のSUS316L相当材にクロマイズ処理を施したロール(外径:15mm、長さ:22mm)を使用した。
<Density and wear of sintered alloy>
The density of the sintered alloy was measured using a cylindrical sintered alloy sample according to a method for testing the sintered density of a metal sintered material specified in Japanese Industrial Standards (JIS) Z2505.
The wear amount of the sintered alloy was measured as a wear amount in a roll-on-disc friction wear test using a disc-shaped sintered alloy sample. In the roll-on-disk friction and wear test, a sintered alloy sample was used as a disk material, and reciprocal sliding with respect to a mating member was performed at 700 ° C. for 15 minutes to measure the amount of wear of the disk material. As a mating member, a roll (outer diameter: 15 mm, length: 22 mm) obtained by subjecting JIS SUS316L equivalent material to chromizing treatment was used.
 <鉄合金基地の結晶粒>
 更に、円柱状の焼結合金試料を切断して、試料の断面を鏡面研磨し、王水(硝酸:塩酸=1:3)で断面を腐食させた後、断面の金属組織の顕微鏡観察を200倍の倍率で行って基地の組織を観察した。この際、画像解析ソフトウエアとして三谷商事株式会社製のWinROOFを用いて、組織断面の画像解析を行って画像を二値化し、オーステナイトの基地の面積を測定して、基地の結晶粒の数を計測することによって結晶粒の平均面積を計算した。この値を面積円相当径に換算することによって結晶粒の平均結晶粒径を決定した。
<Grit of iron alloy base>
Further, the columnar sintered alloy sample was cut, the cross section of the sample was mirror-polished, and the cross section was corroded with aqua regia (nitric acid: hydrochloric acid = 1: 3). The tissue at the base was observed at a magnification of × 2. At this time, using a WinROOF manufactured by Mitani Shoji Co., Ltd. as image analysis software, image analysis of the tissue cross section is performed to binarize the image, the area of the austenite matrix is measured, and the number of crystal grains in the matrix is determined. The average area of the crystal grains was calculated by the measurement. The average crystal grain size of the crystal grains was determined by converting this value to the area circle equivalent diameter.
 <酸化被膜の厚さ>
 また、外径:24mm、長さ:8mmの円柱状の焼結体から、長軸:20mm、短軸:10mm、高さ:3mmの短冊状の焼結合金試料を機械加工によって切り出した。この焼結合金試料を、水蒸気を含む雰囲気(温度:860℃、試験雰囲気:8%水蒸気/空気)中に100時間放置した後に回収して切断し、上述の結晶粒の測定と同様に、試料断面の処理を行って断面の金属組織の顕微鏡観察を行った。この断面観察において、酸化被膜の厚さを測定した。この測定は、断面画像の酸化被膜部分において任意に3箇所を選定して厚さを計測し、計測値の平均値として表示している。
<Thickness of oxide film>
A strip-shaped sintered alloy sample having a major axis of 20 mm, a minor axis of 10 mm, and a height of 3 mm was cut out from a cylindrical sintered body having an outer diameter of 24 mm and a length of 8 mm by machining. The sintered alloy sample was left in an atmosphere containing steam (temperature: 860 ° C., test atmosphere: 8% steam / air) for 100 hours, then collected and cut. The cross section was processed and the metal structure of the cross section was observed under a microscope. In this cross-sectional observation, the thickness of the oxide film was measured. In this measurement, three points are arbitrarily selected in the oxide film portion of the cross-sectional image, the thickness is measured, and the measured value is displayed as an average value.
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000001
 
Figure JPOXMLDOC01-appb-T000002
 
Figure JPOXMLDOC01-appb-T000002
 
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000003
 
 試料番号1~8の焼結合金は、クロム含有量が異なる。何れの試料においても、鉄合金基地の結晶粒は小さく、基地の結晶粒の成長が好適に抑制されている。クロム含有量が増加するにつれて、結晶粒径、摩耗量及び酸化被膜の厚さが減少する傾向が見られ、クロム含有量が全体組成の18.48質量%以上においては、結晶粒の大きさはほぼ一定になり、摩耗量も同様にほぼ一定になる。クロム含有量が30質量%を超えても、摩耗量の増加は起こらない。これは、黒鉛の添加量が少ないために炭化クロムの生成及び粒子成長が抑制されることに起因すると考えられ、基地中のクロム量が維持されて基地の強度低下が防止されることで摩耗が抑制されると思われる。但し、クロム含有量が20質量%を超える範囲では、酸化被膜の厚さが増加する。これは、クロム含有量が過度に高い鉄合金粉末の圧縮性の低下により、圧粉体及び焼結体の密度が低下し、これにより表面からの酸化が進行し易くなるためと考えられる。これらの結果から、耐摩耗性及び耐酸化性を兼ね備える上で好ましいクロム含有量は、13.86質量%以上且つ27.72質量%以下の範囲と見なすことができ、より好ましくは16.88質量%以上且つ23.10質量%以下、最も好ましくは18.48質量%且つ20.33質量%以下とすることができる。 焼 結 The sintered alloys of sample numbers 1 to 8 have different chromium contents. In each sample, the crystal grains of the iron alloy matrix are small, and the growth of the crystal grains of the matrix is suitably suppressed. As the chromium content increases, the crystal grain size, the amount of wear, and the thickness of the oxide film tend to decrease. When the chromium content is 18.48% by mass or more of the whole composition, the size of the crystal grains becomes large. It becomes substantially constant, and the amount of wear also becomes substantially constant. Even if the chromium content exceeds 30% by mass, the wear amount does not increase. This is considered to be due to the fact that the amount of graphite added is small, so that the generation of chromium carbide and the particle growth are suppressed, and the amount of chromium in the matrix is maintained to prevent a decrease in the strength of the matrix, resulting in wear. Seems to be suppressed. However, when the chromium content exceeds 20% by mass, the thickness of the oxide film increases. This is considered to be because the compressibility of the iron alloy powder having an excessively high chromium content is reduced, so that the densities of the green compact and the sintered body are reduced, whereby oxidation from the surface is apt to proceed. From these results, the preferable chromium content for achieving both abrasion resistance and oxidation resistance can be considered to be in the range of 13.86% by mass or more and 27.72% by mass or less, and more preferably 16.88% by mass. % And 23.10% by mass or less, most preferably 18.48% by mass and 20.33% by mass or less.
 試料番号4,9~15の焼結合金は、ニッケル含有量が異なり、何れの試料においても、鉄合金基地の結晶粒は小さく、基地の結晶粒の成長が好適に抑制されている。ニッケルの添加によって酸化被膜の厚さが急激に減少することから、ニッケルによって焼結合金の耐酸化性が向上することが判る。焼結体の密度の増加は、ニッケルの比重が大きいことに起因すると思われる。表3の結果からは、ニッケル含有量が22.18質量%(試料番号15)以上であっても、材料特性上の不都合はないと予想でき、6.47質量%以上のニッケル含有量において、耐摩耗性及び耐酸化性を有する焼結合金を得られることが理解される。耐酸化性の点で7.39質量%以上のニッケル含有量がより好ましいといえる。 焼 結 The sintered alloys of Sample Nos. 4 and 9 to 15 have different nickel contents, and in each sample, the crystal grains of the iron alloy matrix are small, and the growth of the crystal grains of the matrix is suitably suppressed. The addition of nickel sharply reduces the thickness of the oxide film, indicating that nickel improves the oxidation resistance of the sintered alloy. The increase in the density of the sintered body is considered to be due to the large specific gravity of nickel. From the results in Table 3, it can be expected that even if the nickel content is 22.18% by mass (sample No. 15) or more, there is no inconvenience in the material properties. At a nickel content of 6.47% by mass or more, It is understood that a sintered alloy having wear resistance and oxidation resistance can be obtained. It can be said that a nickel content of 7.39% by mass or more is more preferable in terms of oxidation resistance.
 試料番号4,16~21の焼結合金は、ケイ素含有量が異なる。ケイ素含有量の増加に従って酸化被膜の厚さが急激に減少することから、耐酸化性の向上にケイ素が有効であることがわかる。但し、ケイ素含有量が2.77質量%を超えると、酸化被膜の厚さが急激に増加する。この理由は、原料粉末の圧縮性低下に伴う焼結合金の密度低下、及び、結晶粒の粗大化による耐酸化性の低下によると考えられ、これは、圧粉体及び焼結体の密度、及び、鉄合金基地の結晶粒径に見られる傾向から理解することができる。圧粉体及び焼結体の密度は、ケイ素含有量の増加に従って低下し、これは、鉄合金粉末の圧縮性の低下によると見なされる。また、鉄合金基地の結晶粒径は、ケイ素含有量の増加に従って増大する。これらの結果から、焼結体の密度不足及び結晶粒の粗大化によって耐酸化性が低下すると考えられる。従って、ケイ素含有量は0.46質量%以上且つ2.77質量%以下が好適であり、好ましくは0.74質量%以上且つ1.85質量%以下に設定するとよい。 焼 結 The sintered alloys of sample numbers 4, 16 to 21 have different silicon contents. Since the thickness of the oxide film sharply decreases as the silicon content increases, it is understood that silicon is effective for improving the oxidation resistance. However, when the silicon content exceeds 2.77% by mass, the thickness of the oxide film rapidly increases. The reason for this is considered to be a decrease in the density of the sintered alloy due to a decrease in the compressibility of the raw material powder, and a decrease in the oxidation resistance due to the coarsening of the crystal grains. And it can be understood from the tendency seen in the crystal grain size of the iron alloy matrix. The density of the green compact and the sintered body decreases as the silicon content increases, which is considered to be due to the decrease in the compressibility of the iron alloy powder. Also, the crystal grain size of the iron alloy matrix increases as the silicon content increases. From these results, it is considered that the oxidation resistance is lowered due to insufficient density of the sintered body and coarsening of the crystal grains. Therefore, the silicon content is preferably 0.46% by mass or more and 2.77% by mass or less, and more preferably 0.74% by mass or more and 1.85% by mass or less.
 試料番号4,22~27の焼結合金は、銅-リン合金粉末の配合割合が異なり、従って配合割合に伴って合金組成中の銅及びリンの含有量が変化する。銅-リン合金粉末の添加及びその割合の増加によって、得られる焼結合金の密度が増加し、銅-リン合金粉末によって基地の焼結が促進されることが理解される。また、酸化被膜の厚さが著しく減少することから、耐酸化性が向上することが理解される。更に、銅-リン合金粉末の配合割合が4質量%を超えると、摩耗量が減少し、耐摩耗性が向上する。但し、銅-リン合金粉末の配合割合が13質量%を超えると、焼結密度が減少し、これは、焼結中に液相が過剰に発生したことに起因する。このため、試料番号27においては、結晶粒径及び材料特性の測定は省略した。表3の結果においては、銅-リン合金粉末の配合割合が1.00~13.00質量%である試料番号4,23~26の焼結合金において、耐摩耗性及び耐酸化性が良好である。これらの焼結合金における銅含有量は0.85~11.05質量%であり、リン含有量は0.15~1.95%となるので、これらの範囲を銅及びリンの好適な含有量と見なすことができる。より好ましくは、銅含有量が3.40質量%以上且つ8.50質量%以下、リン含有量が0.60質量%以上且つ1.50質量%以下となり、より適正な銅含有量は3.40質量%以上且つ5.95質量%以下、より適正なリン含有量は0.60質量%以上且つ1.05質量%以下となる。 焼 結 The sintered alloys of sample numbers 4, 22 to 27 have different mixing ratios of the copper-phosphorus alloy powder, and accordingly, the contents of copper and phosphorus in the alloy composition change with the mixing ratio. It is understood that the addition of the copper-phosphorus alloy powder and the increase in the proportion thereof increase the density of the obtained sintered alloy, and promote the sintering of the matrix by the copper-phosphorus alloy powder. In addition, it is understood that the oxidation resistance is improved because the thickness of the oxide film is significantly reduced. Further, when the compounding ratio of the copper-phosphorus alloy powder exceeds 4% by mass, the wear amount is reduced, and the wear resistance is improved. However, when the compounding ratio of the copper-phosphorus alloy powder exceeds 13% by mass, the sintering density decreases, which is due to the excessive generation of the liquid phase during sintering. Therefore, in Sample No. 27, the measurement of the crystal grain size and the material properties were omitted. The results in Table 3 show that the sintered alloys of Sample Nos. 4 and 23 to 26 in which the mixing ratio of the copper-phosphorus alloy powder is 1.00 to 13.00% by mass have good wear resistance and oxidation resistance. is there. The copper content of these sintered alloys is 0.85 to 11.05% by mass, and the phosphorus content is 0.15 to 1.95%. Can be considered. More preferably, the copper content is 3.40% by mass or more and 8.50% by mass or less, and the phosphorus content is 0.60% by mass or more and 1.50% by mass or less. It is 40% by mass or more and 5.95% by mass or less, and a more appropriate phosphorus content is 0.60% by mass or more and 1.05% by mass or less.
 試料番号4,28~33の焼結合金は、使用した銅-リン合金粉末における合金組成が異なる。これらの試料においては、リン含有割合が増加するに従って銅含有割合が低下するが、何れの試料においても、得られる焼結合金の銅含有量は上述の好適な範囲にある。試料番号28における焼結体の密度は相対的に低く、酸化被膜の厚さも厚いことから、リン含有量が不足して焼結促進効果が小さいためと考えられる。また、試料番号33における焼結密度の低下は、焼結中に液相が過剰に発生したことに起因する。このため、試料番号33については、結晶粒径及び材料特性の測定は省略した。これらの結果から、使用する銅-リン合金粉末は、リンの含有量が5質量%以上且つ25質量%以下であると好ましく、より好ましくは10質量%以上且つ20質量%以下となる。 焼 結 The sintered alloys of sample numbers 4, 28 to 33 have different alloy compositions in the used copper-phosphorus alloy powder. In these samples, the copper content decreases as the phosphorus content increases, but in any of the samples, the copper content of the obtained sintered alloy is in the above-mentioned preferred range. It is considered that the density of the sintered body in Sample No. 28 was relatively low and the thickness of the oxide film was large, so that the phosphorus content was insufficient and the sintering promotion effect was small. Further, the decrease in the sintering density in Sample No. 33 is due to the excessive generation of the liquid phase during sintering. For this reason, the measurement of the crystal grain size and the material properties of sample No. 33 was omitted. From these results, the copper-phosphorus alloy powder used preferably has a phosphorus content of 5% by mass or more and 25% by mass or less, more preferably 10% by mass or more and 20% by mass or less.
 試料番号4,34~39の焼結合金は、炭素含有量が異なり、焼結合金の被削性を高めるために、炭素含有量は、0.10~1.50質量%の低い範囲に設計されている。この範囲において、炭素含有量が低下すると、焼結体の密度が低下し、鉄合金基地の結晶粒径が増加する傾向が見られるが、0.20質量%まで低下させても、摩耗量及び酸化被膜の厚さは低く抑えられている。つまり、耐摩耗性及び耐酸化性が維持されていることがわかる。試料番号39においては、鉄-リン-炭素共晶液相の生成時に基地中に固溶するクロム量が低下したために基地の耐酸化性が低下したと考えられる。従って、好ましい炭素含有量は、0.20質量%以上且つ1.00質量%以下であり、0.4質量%以上且つ0.80質量%以下であるとより好ましい。 The sintered alloys of sample numbers 4, 34 to 39 have different carbon contents, and the carbon content is designed to be as low as 0.10 to 1.50 mass% in order to enhance the machinability of the sintered alloy. Have been. In this range, when the carbon content decreases, the density of the sintered body decreases, and the crystal grain size of the iron alloy matrix tends to increase. However, even if the carbon content is reduced to 0.20% by mass, the wear amount and The thickness of the oxide film is kept low. That is, it is understood that the wear resistance and the oxidation resistance are maintained. In sample No. 39, it is considered that the oxidation resistance of the matrix decreased because the amount of chromium dissolved in the matrix during the formation of the iron-phosphorus-carbon eutectic liquid phase decreased. Therefore, the preferable carbon content is 0.20% by mass or more and 1.00% by mass or less, and more preferably 0.4% by mass or more and 0.80% by mass or less.
 (試料番号40~46)
 実施例1の試料番号4において、銅-リン合金粉末の代わりに、3.00質量%の鉄-リン合金粉末(リン含有量:35.00質量%、平均粒子径:40μm)及び0~13.00質量%の銅粉末(平均粒子径:30μm)を配合したこと以外は同様にして、表4に示すような混合粉末を調製した。これを成形用の原料粉末として用いて、実施例1と同様の操作によって、表5に示すような円板状及び円柱状の圧粉体に成形した(圧粉体の密度:6.4Mg/m)。これらを実施例1と同様の条件で焼結して焼結合金試料を作製し、密度、摩耗量、鉄合金基地の結晶粒径及び酸化被膜の厚さの測定を行った。その結果を表6に示す。
(Sample numbers 40 to 46)
In the sample No. 4 of Example 1, instead of the copper-phosphorus alloy powder, 3.00% by mass of an iron-phosphorus alloy powder (phosphorus content: 35.00% by mass, average particle size: 40 μm) and 0 to 13 A mixed powder as shown in Table 4 was prepared in the same manner except that 0.000% by mass of copper powder (average particle diameter: 30 μm) was blended. This was used as a raw material powder for molding, and was molded into disk-shaped and column-shaped green compacts as shown in Table 5 by the same operation as in Example 1 (density of the green compact: 6.4 Mg / m 3 ). These were sintered under the same conditions as in Example 1 to produce a sintered alloy sample, and the density, the wear amount, the crystal grain size of the iron alloy base, and the thickness of the oxide film were measured. Table 6 shows the results.
Figure JPOXMLDOC01-appb-T000004
 
Figure JPOXMLDOC01-appb-T000004
 
Figure JPOXMLDOC01-appb-T000005
 
Figure JPOXMLDOC01-appb-T000005
 
Figure JPOXMLDOC01-appb-T000006
 
Figure JPOXMLDOC01-appb-T000006
 
 表6の試料番号43において、焼結合金の密度は、7.1Mg/m、鉄合金基地の平均結晶粒径は、22μm、摩耗量は、23μm、酸化被膜の厚さは、6μmであった。試料番号43の全体組成は、試料番号4とほぼ同様であり、これらの試料を比較すると、焼結合金の特性においても同等であることが理解される。従って、銅-リン合金粉末の代わりに鉄-リン合金粉末と銅粉末とを組み合わせて利用しても、同様に耐摩耗性及び耐酸化性を備えた焼結合金が得られることがわかる。 In sample No. 43 of Table 6, the density of the sintered alloy was 7.1 Mg / m 3 , the average crystal grain size of the iron alloy matrix was 22 μm, the wear amount was 23 μm, and the thickness of the oxide film was 6 μm. Was. The overall composition of Sample No. 43 is almost the same as that of Sample No. 4, and when these samples are compared, it is understood that the properties of the sintered alloy are also the same. Accordingly, it can be seen that a sintered alloy having the same wear resistance and oxidation resistance can be obtained even when the iron-phosphorus alloy powder and the copper powder are used in combination instead of the copper-phosphorus alloy powder.
 表6においては、銅の組成割合の増加に従って、合金基地の結晶粒径、摩耗量及び酸化被膜の厚さが減少する傾向が見られる。これは、銅が基地に固溶することによって表層の不動態被膜が保護され耐酸化性が向上すると考えられる。但し、銅の割合が更に増加すると、基地の結晶粒径、摩耗量及び酸化被膜の厚さの何れも増加に転じることから、銅の組成割合は0.85~11.05質量%の範囲に設定するとよい。 In Table 6, there is a tendency that the crystal grain size, the amount of wear, and the thickness of the oxide film of the alloy matrix tend to decrease as the composition ratio of copper increases. This is considered to be due to the fact that the solid solution of copper in the matrix protects the passivation film on the surface layer and improves oxidation resistance. However, when the proportion of copper further increases, the crystal grain size of the matrix, the amount of wear and the thickness of the oxide film all begin to increase, so that the proportion of copper is in the range of 0.85 to 11.05% by mass. It is good to set.
 試料番号40~46において、銅の組成割合の増加に従って、焼結合金の密度が低下する。このような傾向は、銅-リン合金粉末を使用した試料番号22~25においては見られず、液相発生及び焼結進行のバランスに関連すると考えられる。この点において、銅-リン合金粉末の使用は、鉄-リン合金粉末と銅粉末の併用より好ましいと考えられる。 に お い て In sample numbers 40 to 46, the density of the sintered alloy decreases as the composition ratio of copper increases. Such a tendency is not observed in Sample Nos. 22 to 25 using the copper-phosphorus alloy powder, and is considered to be related to the balance between the generation of the liquid phase and the progress of sintering. In this regard, the use of copper-phosphorus alloy powder is considered to be more preferable than the combined use of iron-phosphorus alloy powder and copper powder.
 (試料番号47~52)
 実施例1の試料番号4と同様の混合粉末を調製した。これを成形用の原料粉末として使用して、圧粉体の成形密度が表7に示す値となるように型孔へ原料粉末を充填する量を変更したこと以外は実施例1と同様の操作を繰り返して、円板状及び円柱状の圧粉体に成形した。これらを同様の条件で焼結して、焼結合金試料を製した。試料の密度、摩耗量、鉄合金基地の結晶粒径及び酸化被膜の厚さの測定を行った。結果を表7に示す。
(Sample numbers 47 to 52)
A mixed powder similar to that of Sample No. 4 of Example 1 was prepared. This was used as a raw material powder for molding, and the same operation as in Example 1 was performed except that the amount of the raw material powder filled into the mold cavity was changed so that the green density of the green compact became the value shown in Table 7. Was repeated to form a disc-shaped and column-shaped green compact. These were sintered under the same conditions to produce a sintered alloy sample. The density of the sample, the amount of wear, the crystal grain size of the iron alloy matrix, and the thickness of the oxide film were measured. Table 7 shows the results.
 (試料番号53~58)
 実施例1の試料番号4と同様の操作を繰り返して混合粉末を調製した。これを成形用の原料粉末として使用して、実施例1と同様に円板状及び円柱状の圧粉体に成形した。これらを用いて、焼結温度を表7に示す温度に変更したこと以外は実施例1と同様の条件で、焼結合金試料を作製した。試料の密度、摩耗量、鉄合金基地の結晶粒径及び酸化被膜の厚さの測定を行った。結果を表7に示す。
(Sample numbers 53 to 58)
The same operation as in Sample No. 4 of Example 1 was repeated to prepare a mixed powder. This was used as a raw material powder for molding, and was molded into a disc-shaped and column-shaped green compact in the same manner as in Example 1. Using these, sintered alloy samples were produced under the same conditions as in Example 1 except that the sintering temperature was changed to the temperature shown in Table 7. The density of the sample, the amount of wear, the crystal grain size of the iron alloy matrix, and the thickness of the oxide film were measured. Table 7 shows the results.
Figure JPOXMLDOC01-appb-T000007
 
Figure JPOXMLDOC01-appb-T000007
 
 試料番号4,47~52の結果から、密度が6.00~6.80Mg/mの圧粉体の焼結によって得られる焼結合金は、耐摩耗性及び耐酸化性が良好であることが判る。圧粉体の密度が低いと、焼結合金の密度不足によって耐酸化性が低下する。尚、試料番号52においては、圧粉体の成形は困難であり、密度が6.80Mg/mを超える圧粉体は、得られなかった。表7の結果から、焼結体の密度は、6.90Mg/m以上且つ7.40Mg/m以下が好適であり、好ましくは7.00Mg/m以上且つ7.40Mg/m以下となるように調整するとよい。7.20Mg/m以上且つ7.40Mg/m以下の焼結密度であるとより適正である。 From the results of sample numbers 4, 47 to 52, the sintered alloy obtained by sintering the green compact having a density of 6.00 to 6.80 Mg / m 3 has good wear resistance and oxidation resistance. I understand. When the density of the green compact is low, the oxidation resistance is reduced due to insufficient density of the sintered alloy. In sample 52, it was difficult to form a green compact, and a green compact having a density exceeding 6.80 Mg / m 3 was not obtained. The results in Table 7, the density of the sintered body, 6.90Mg / m 3 or more and 7.40Mg / m 3 or less are preferred, preferably 7.00 mg / m 3 or more and 7.40Mg / m 3 or less It is good to adjust so that it becomes. It is more appropriate that the sintered density is not less than 7.20 Mg / m 3 and not more than 7.40 Mg / m 3 .
 試料番号4,53~58の結果から、焼結温度が高くなるに従って、鉄合金基地の平均結晶粒径が大きくなり、焼結温度の上昇によって焼結の進行が促進されると理解される。1050℃以上且つ1160℃以下の温度で焼結した焼結合金は、耐摩耗性及び耐酸化性が良好である。焼結温度が1050℃未満である試料番号53においては、耐摩耗性及び耐酸化性が低い。これは、共晶液相が十分に発生せず、鉄合金基地の強度が得られないためと見なせる。焼結温度が1160℃を超える試料番号58においては、焼結中に液相が過剰に生じたために、焼結密度が低下しており、このため、結晶粒径及び材料特性の測定は省略した。より好ましい焼結温度は1100℃以上且つ1140℃以下と見なすことができる。 か ら From the results of Sample Nos. 4, 53 to 58, it is understood that as the sintering temperature increases, the average crystal grain size of the iron alloy matrix increases, and the increase in the sintering temperature promotes the progress of sintering. A sintered alloy sintered at a temperature of 1050 ° C. or more and 1160 ° C. or less has excellent wear resistance and oxidation resistance. Sample No. 53 having a sintering temperature of less than 1050 ° C. has low wear resistance and oxidation resistance. This can be considered to be because the eutectic liquid phase was not sufficiently generated and the strength of the iron alloy matrix could not be obtained. In sample No. 58 having a sintering temperature of more than 1160 ° C., the liquid density was excessively generated during sintering, and the sintering density was reduced. Therefore, the measurement of the crystal grain size and the material properties were omitted. . A more preferred sintering temperature can be considered to be 1100 ° C or higher and 1140 ° C or lower.
 (試料番号59~65)
 実施例1の試料番号4における鉄合金粉末を、表8に示す全体組成となるようにモリブデンを合金化した鉄合金粉末(平均粒子径:70μm)に変更したこと以外は同様にして混合粉末を調製した。これを成形用の原料粉末として使用して、実施例1と同様の操作を繰り返して円板状及び円柱状の圧粉体に成形した(成形圧力:600MPa)。これらを試料番号4と同様の条件で焼結して、焼結合金試料を作製し、密度、摩耗量、鉄合金基地の結晶粒径及び酸化被膜の厚さの測定を行った。結果を表8に示す。
(Sample numbers 59 to 65)
A mixed powder was prepared in the same manner except that the iron alloy powder in Sample No. 4 of Example 1 was changed to an iron alloy powder obtained by alloying molybdenum so as to have an overall composition shown in Table 8 (average particle diameter: 70 μm). Prepared. This was used as a raw material powder for molding, and the same operation as in Example 1 was repeated to form a disc-shaped and a column-shaped compact (molding pressure: 600 MPa). These were sintered under the same conditions as in Sample No. 4 to prepare a sintered alloy sample, and the density, wear amount, crystal grain size of the iron alloy matrix, and thickness of the oxide film were measured. Table 8 shows the results.
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000008
 
 試料番号4,59~65の結果によれば、何れの試料においても、安定した耐摩耗性を示し、耐酸化性も優れている。但し、圧粉体及び焼結体の密度について、モリブデン含有量が増加するに従って減少する傾向が見られる。これは、モリブデンの合金化によって鉄合金粉末の圧縮性が多少低下することに起因すると考えられるので、3.23質量%以下の範囲でモリブデン、つまり、炭化物生成元素を配合することが好ましいと考えられる。より好ましくは、モリブデン含有量が0.46質量%以上且つ2.77質量%以下であるとよい。 According to the results of Sample Nos. 4, 59 to 65, all of the samples exhibited stable wear resistance and excellent oxidation resistance. However, the densities of the green compact and the sintered body tend to decrease as the molybdenum content increases. This is considered to be due to the fact that the compressibility of the iron alloy powder is slightly reduced due to alloying of molybdenum. Therefore, it is preferable to add molybdenum, that is, a carbide-forming element in a range of 3.23% by mass or less. Can be More preferably, the molybdenum content is 0.46% by mass or more and 2.77% by mass or less.
 試料番号4,22~27,34~46の焼結合金の被削性を調べるために、超硬合金製の旋盤加工用刃具を用意し、円柱状の焼結合金試料を用いて以下のような旋削加工を施した。即ち、試料の端面を外周側から内周へ向かって刃具による旋盤加工(切削速度:50m/分、切り込み深さ:0.2mm、送り速度:0.05mm/回転)を行い、合計切削距離が1000mに達した段階で刃具の逃げ面の摩耗量(工具摩耗量)を測定した。この測定値を、被削性を評価する目安として表9に記載する。 In order to examine the machinability of the sintered alloys of Sample Nos. 4, 22 to 27, and 34 to 46, a turning tool made of cemented carbide was prepared, and a cylindrical sintered alloy sample was used as follows. Turning. That is, lathe processing (cutting speed: 50 m / min, cutting depth: 0.2 mm, feed speed: 0.05 mm / rotation) is performed on the end face of the sample from the outer peripheral side to the inner peripheral side with a cutting tool, and the total cutting distance is reduced. At the stage when the height reached 1000 m, the wear amount of the flank of the cutting tool (tool wear amount) was measured. The measured values are shown in Table 9 as a guide for evaluating the machinability.
Figure JPOXMLDOC01-appb-T000009
 
Figure JPOXMLDOC01-appb-T000009
 
 試料番号4,22~27,40~46の結果によれば、銅の添加によって工具摩耗量が減少し、被削性が改善されることが理解される。銅の含有量が0.85質量%以上において、被削性が良好である。但し、銅の添加量が更に増加すると、工具摩耗量は増加に転じ、これは、銅の固溶による基地の硬化が過度に進行するためと考えられる。表9の結果においては、銅の含有量が0.85~11.05質量%の範囲において、焼結合金の被削性が向上すると見なせる。 れ ば According to the results of Sample Nos. 4, 22 to 27, and 40 to 46, it is understood that the addition of copper reduces the tool wear and improves machinability. When the copper content is 0.85% by mass or more, the machinability is good. However, when the addition amount of copper further increases, the wear amount of the tool starts to increase, and this is considered to be due to excessive hardening of the matrix due to solid solution of copper. In the results of Table 9, it can be considered that the machinability of the sintered alloy is improved when the content of copper is in the range of 0.85 to 11.05% by mass.
 また、試料番号4,34~39の結果によれば、炭素含有量の増加によって工具摩耗量が増加する傾向が見られる。つまり、黒鉛の配合量を従来よりも低く設定することが被削性の改善に有効であることが明らかであり、焼結合金の炭素含有量が1.00質量%以下となるように設定することによって、被削性を向上させて工具摩耗を抑制できることが理解される。 Also, according to the results of Sample Nos. 4, 34 to 39, there is a tendency that the tool wear amount tends to increase as the carbon content increases. In other words, it is clear that setting the blending amount of graphite lower than before is effective in improving machinability, and the carbon content of the sintered alloy is set so as to be 1.00% by mass or less. Thus, it is understood that the machinability can be improved and tool wear can be suppressed.
 本願の開示は、2018年7月11日に出願された特願2018-131364号に記載の主題と関連しており、それらのすべての開示内容は引用によりここに援用される。
 既に述べられたもの以外に、本発明の新規かつ有利な特徴から外れることなく、上記の実施形態に様々な修正や変更を加えてもよいことに注意すべきである。したがって、そのような全ての修正や変更は、添付の請求の範囲に含まれることが意図されている。
The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 2018-131364 filed on Jul. 11, 2018, the entire disclosures of which are incorporated herein by reference.
It should be noted that various modifications and alterations may be made to the above-described embodiments without departing from the novel and advantageous features of the invention, other than those already described. Accordingly, all such modifications and changes are intended to be included within the scope of the appended claims.
 耐酸化性、耐熱性及び耐摩耗性に優れ、被削性が向上した焼結合金が提供されるので、ターボチャージャー用ターボ部品に適用することができ、ノズルボディ等のような高温の腐食性ガスに対する耐久性が要求される部品に有利に適用することができる。
 
A sintered alloy with excellent oxidation resistance, heat resistance and wear resistance and improved machinability is provided, so it can be applied to turbo parts for turbochargers, and it is highly corrosive at high temperatures such as nozzle bodies. The present invention can be advantageously applied to parts requiring durability against gas.

Claims (8)

  1.  全体組成が、質量%で、Cr:13.86~27.72%、Ni:6.47~20.33%、Cu:0.85~11.05%、Si:0.46~2.77%、P:0.15~1.95%、C:0.20~1.00%、及び、残部のFe及び不可避元素からなり、密度が6.8~7.4Mg/mである焼結合金であって、
     気孔が分散する鉄合金基地と、前記鉄合金基地に分散する炭化物とを有する金属組織を示し、前記鉄合金基地は、平均結晶粒径が10~50μmの結晶粒で構成される、焼結合金。
    The overall composition is, in mass%, Cr: 13.86 to 27.72%, Ni: 6.47 to 20.33%, Cu: 0.85 to 11.05%, Si: 0.46 to 2.77. %, P: 0.15 to 1.95%, C: 0.20 to 1.00%, and the balance consisting of Fe and unavoidable elements and having a density of 6.8 to 7.4 Mg / m 3. Binding gold,
    A sintered alloy, comprising: a metal structure having an iron alloy matrix in which pores are dispersed and a carbide dispersed in the iron alloy matrix, wherein the iron alloy matrix is composed of crystal grains having an average crystal grain size of 10 to 50 μm. .
  2.  全体組成が、質量%で、Cr:13.86~27.72%、Ni:6.47~20.33%、Cu:0.85~11.05%、Si:0.46~2.77%、P:0.15~1.95%、C:0.20~1.00%、炭化物生成元素:3.23%以下、及び、残部のFe及び不可避元素からなり、密度が6.8~7.4Mg/mである焼結合金であって、
     前記炭化物生成元素は、Mo、V、W、Nb及びTiからなる群より選択される少なくとも1種の元素であり、
     気孔が分散する鉄合金基地と、前記鉄合金基地に分散する炭化物とを有する金属組織を示し、前記鉄合金基地は、平均結晶粒径が10~50μmの結晶粒で構成される、焼結合金。
    The overall composition is, in mass%, Cr: 13.86 to 27.72%, Ni: 6.47 to 20.33%, Cu: 0.85 to 11.05%, Si: 0.46 to 2.77. %, P: 0.15 to 1.95%, C: 0.20 to 1.00%, carbide forming element: 3.23% or less, and the balance of Fe and unavoidable elements, and the density is 6.8. A sintered alloy of up to 7.4 Mg / m 3 ,
    The carbide-forming element is at least one element selected from the group consisting of Mo, V, W, Nb, and Ti;
    A sintered alloy, comprising: a metal structure having an iron alloy matrix in which pores are dispersed and a carbide dispersed in the iron alloy matrix, wherein the iron alloy matrix is composed of crystal grains having an average crystal grain size of 10 to 50 μm. .
  3.  前記焼結合金の表面、及び、前記気孔の内面に窒化物が形成されている、請求項1又は2に記載の焼結合金。 The sintered alloy according to claim 1 or 2, wherein a nitride is formed on a surface of the sintered alloy and an inner surface of the pore.
  4.  質量%で、Cr:15~30%、Ni:7~24%、Si:0.5~3.0%、及び、残部のFe及び不可避不純物からなる鉄合金粉末を用意し、
     リン含有量が10~30質量%の鉄-リン合金粉末、リン含有量が5~25質量%の銅-リン合金粉末、及び、銅粉末から選択される1種又は複数種の組み合わせからなる、リン及び銅配合用の配合材を用意し、
     前記鉄合金粉末、前記配合材及び黒鉛粉末を混合して、0.15~1.95質量%のリン、0.85~11.05質量%の銅、及び、0.20~1.00質量%の炭素を含有する原料粉末を調製し、
     前記原料粉末を圧縮して、密度が6.0~6.8Mg/mの圧粉体を形成し、
     前記圧粉体を非酸化性雰囲気において1050~1160℃の温度に加熱して焼結する、焼結合金の製造方法。
    In mass%, Cr: 15 to 30%, Ni: 7 to 24%, Si: 0.5 to 3.0%, and an iron alloy powder comprising the balance of Fe and unavoidable impurities is prepared.
    The iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass, the copper-phosphorus alloy powder having a phosphorus content of 5 to 25% by mass, and one or more combinations selected from copper powders; Prepare compounding materials for phosphorus and copper compounding,
    The iron alloy powder, the compounding material and the graphite powder are mixed to form 0.15 to 1.95% by mass of phosphorus, 0.85 to 11.05% by mass of copper, and 0.20 to 1.00% by mass. % Raw material powder containing carbon,
    Compressing the raw material powder to form a green compact having a density of 6.0 to 6.8 Mg / m 3 ;
    A method for producing a sintered alloy, wherein the green compact is heated to a temperature of 1050 to 1160 ° C. in a non-oxidizing atmosphere and sintered.
  5.  質量%で、Cr:15~30%、Ni:7~24%、Si:0.5~3.0%、炭化物生成元素:3質量%以下、及び、残部のFe及び不可避不純物からなる鉄合金粉末であって、前記炭化物生成元素は、Mo、V、W、Nb及びTiからなる群より選択される少なくとも1種の元素である前記鉄合金粉末を用意し、
     リン含有量が10~30質量%の鉄-リン合金粉末、リン含有量が5~25質量%の銅-リン合金粉末、及び、銅粉末から選択される1種又は複数種の組み合わせからなる、リン及び銅配合用の配合材を用意し、
     前記鉄合金粉末、前記配合材及び黒鉛粉末を混合して、0.15~1.95質量%のリン、0.85~11.05質量%の銅、及び、0.20~1.00質量%の炭素を含有する原料粉末を調製し、
     前記原料粉末を圧縮して、密度が6.0~6.8Mg/mの圧粉体を形成し、
     前記圧粉体を非酸化性雰囲気において1050~1160℃の温度に加熱して焼結する、焼結合金の製造方法。
    Fe: 15 to 30% by mass, Ni: 7 to 24%, Si: 0.5 to 3.0%, carbide-forming element: 3% by mass or less, and the balance of Fe and iron and inevitable impurities A powder, wherein the carbide-forming element is at least one element selected from the group consisting of Mo, V, W, Nb, and Ti;
    The iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass, the copper-phosphorus alloy powder having a phosphorus content of 5 to 25% by mass, and one or more combinations selected from copper powders; Prepare compounding materials for phosphorus and copper compounding,
    The iron alloy powder, the compounding material and the graphite powder are mixed to form 0.15 to 1.95% by mass of phosphorus, 0.85 to 11.05% by mass of copper, and 0.20 to 1.00% by mass. % Raw material powder containing carbon,
    Compressing the raw material powder to form a green compact having a density of 6.0 to 6.8 Mg / m 3 ;
    A method for producing a sintered alloy, wherein the green compact is heated to a temperature of 1050 to 1160 ° C. in a non-oxidizing atmosphere and sintered.
  6.  前記配合材は、鉄-リン合金粉末及び銅-リン合金粉末の一方又は両方の形態でリンを含有し、銅粉末及び銅-リン合金粉末の一方又は両方の形態で銅を含有する粉末である、請求項4又は5に記載の焼結合金の製造方法。 The compounding material is a powder containing phosphorus in one or both forms of iron-phosphorus alloy powder and copper-phosphorus alloy powder, and a powder containing copper in one or both forms of copper powder and copper-phosphorus alloy powder. The method for producing a sintered alloy according to claim 4.
  7.  前記配合材は、下記の(1)~(5)の何れかである、請求項4~6の何れか一項に記載の焼結合金の製造方法。
     (1)リン含有量が10~30質量%の鉄-リン合金粉末と銅粉末との組み合わせ
     (2)リン含有量が10~30質量%の鉄-リン合金粉末と、リン含有量が5~25質量%の銅-リン合金粉末との組み合わせ
     (3)リン含有量が10~30質量%の鉄-リン合金粉末と、リン含有量が5~25質量%の銅-リン合金粉末と、銅粉末との組み合わせ
     (4)リン含有量が5~25質量%の銅-リン合金粉末と銅粉末との組み合わせ
     (5)リン含有量が5~25質量%の銅-リン合金粉末
    The method for producing a sintered alloy according to any one of claims 4 to 6, wherein the compounding material is any of the following (1) to (5).
    (1) Combination of an iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass and a copper powder (2) An iron-phosphorus alloy powder having a phosphorus content of 10 to 30% by mass and a phosphorus content of 5 to 30% Combination with 25 mass% copper-phosphorus alloy powder (3) Iron-phosphorus alloy powder having a phosphorus content of 10 to 30 mass%, copper-phosphorus alloy powder having a phosphorus content of 5 to 25 mass%, copper Combination with powder (4) Combination of copper-phosphorus alloy powder having a phosphorus content of 5 to 25% by mass and copper powder (5) Copper-phosphorus alloy powder having a phosphorus content of 5 to 25% by mass
  8.  前記非酸化性雰囲気は、窒素を10質量%以上含む窒素と水素との混合ガス、又は、窒素ガスからなる常圧の雰囲気である、請求項4~7の何れか一項に記載の焼結合金の製造方法。
     
    The sinter bonding according to any one of claims 4 to 7, wherein the non-oxidizing atmosphere is a mixed gas of nitrogen and hydrogen containing 10% by mass or more of nitrogen, or a normal pressure atmosphere made of nitrogen gas. Gold manufacturing method.
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