WO2016114142A1 - 還元鉄粉およびその製造方法並びに軸受 - Google Patents
還元鉄粉およびその製造方法並びに軸受 Download PDFInfo
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- WO2016114142A1 WO2016114142A1 PCT/JP2016/000170 JP2016000170W WO2016114142A1 WO 2016114142 A1 WO2016114142 A1 WO 2016114142A1 JP 2016000170 W JP2016000170 W JP 2016000170W WO 2016114142 A1 WO2016114142 A1 WO 2016114142A1
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- iron powder
- powder
- reduced iron
- bearing
- iron oxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16C—SHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
- F16C33/00—Parts of bearings; Special methods for making bearings or parts thereof
- F16C33/02—Parts of sliding-contact bearings
- F16C33/04—Brasses; Bushes; Linings
- F16C33/06—Sliding surface mainly made of metal
- F16C33/10—Construction relative to lubrication
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/09—Mixtures of metallic powders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/35—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0235—Starting from compounds, e.g. oxides
Definitions
- the present invention relates to reduced iron powder, a manufacturing method thereof, and a bearing using the reduced iron powder.
- iron powders two of reduced iron powder and atomized iron powder are mainly known from the production method.
- the apparent density of the iron powder currently known a reducing iron powder 2.3 mg / m 3 or more and 2.5 mg / m 3 or more atomized iron powder.
- the specific surface area, 0.10 m 2 / g or less in a reducing iron powder is 0.07 m 2 / g or less atomized iron powder.
- the specific surface area is larger as the apparent density is lower.
- iron powder having a low apparent density is required.
- the presence of inclusions in the member may damage the other member and shorten the product life. Further, when the inclusion does not sinter with the surrounding iron powder, it becomes a cause of structural defects, and particularly when manufacturing minute machine parts, the influence on the yield and the decrease in strength is extremely large.
- Reduced iron powder is produced from iron ore or mill scale.
- the purity of the reduced iron powder that is the product is determined by the purity of the iron oxide that is the raw material.
- the most common impurity is oxygen, and most oxygen occurs as a thin film of surface oxide.
- Basic impurities include carbon, magnesium, aluminum, silicon, phosphorus, sulfur, chromium, manganese, nickel and copper, many of which exist as oxides and are called inclusions.
- JP 2001-132755 A Japanese Patent No. 4666735 Japanese Patent No. 4667937
- the conventional reduced iron powder when used as a bearing, there is a problem that the reduced iron powder contains inclusions exceeding 200 ⁇ m, so that the shaft may be damaged or its own structural defect may occur. .
- the conventional reduced iron powder has a problem that although there are fine pores, it is rejected due to a large amount of inclusions.
- a bearing having an inner diameter of 0.6 mm ⁇ and an outer diameter of 2.0 mm ⁇ can be manufactured with a relatively high yield even when using conventional reduced iron powder.
- the inner diameter is 0.4 mm ⁇ and the outer diameter is 1.4.
- atomized iron powder the surface is smooth, so that the binding force between the iron powder particles is insufficient at the time of molding, and the Rattler value is remarkably lowered. Furthermore, when oil-impregnated bearings are manufactured, there are few pores, and the fact that oil circulation is not sufficiently obtained is also a major drawback. In addition, atomized iron powder has a problem that there are few inclusions but there are few fine pores.
- reduced iron powder As a chemical reaction material, it has excellent reactivity per unit mass due to its large specific surface area, and it can be used effectively as a reaction material even inside the particles. Is required.
- the present invention advantageously solves the above-mentioned problems, reduces coarse inclusions, has excellent moldability, high porosity after sintering, excellent reactivity per unit mass, and further to the inside of the particles. It is an object of the present invention to provide reduced iron powder that can be effectively used as a reaction material, a method for producing the same, and a bearing using the reduced iron powder.
- the gist of the present invention is as follows. 1. Reduced iron powder characterized by an apparent density of 1.00 to 1.40 Mg / m 3 .
- a method for producing the reduced iron powder according to any one of 1 to 3 A process of agglomerating raw iron oxide powder having an average particle diameter of 3.0 ⁇ m or less as measured by laser diffraction method into iron oxide powder; Thereafter, reducing the iron oxide powder with hydrogen at 800 to 1000 ° C. to obtain reduced iron powder;
- a method for producing reduced iron powder characterized by comprising:
- reduced iron that reduces coarse inclusions has excellent formability, has high porosity after sintering, has excellent reactivity per unit mass, and can be effectively used as a reaction material even inside the particles.
- a powder is obtained.
- the inventors have succeeded in producing a novel reduced iron powder having an apparent density of 1.00 to 1.40 Mg / m 3 and a specific surface area of 0.20 m 2 / g or more by a novel production method. Since the apparent density of the reduced iron powder of the present invention is sufficiently low, it has excellent moldability, excellent reactivity per unit mass, and can be effectively used as a reaction material even inside the particles. Further, the reduced iron powder of the present invention has a fine iron structure (see the white portion of the cross-sectional image in FIG. 2), and as a result, inclusions are also finely dispersed. Therefore, by using the reduced iron powder as a raw material, a high-strength bearing can be manufactured with a high yield. For example, a bearing with an inner diameter of 0.4 mm ⁇ and an outer diameter of 1.4 mm ⁇ can be mass-produced with a high yield.
- the apparent density of the reduced iron powder is 1.40 Mg / m 3 or less, and in order to make the inclusions in the reduced iron powder fine, the raw material iron oxide powder as a starting material is refined, It is important that the average particle diameter (D50) measured by the laser diffraction method is 3.0 ⁇ m or less. This is because the pores become smaller and the inclusions become finer with the atomization.
- the average particle diameter of the raw iron oxide powder is preferably 2.0 ⁇ m or less, and there is no particular lower limit, but it is about 0.5 ⁇ m industrially.
- the process includes a method using a spray roasting furnace by the Lusner method and a fluidized roasting method by the Lurgi method.
- the raw iron oxide powder is mixed with a binder and water and dried, or the raw iron oxide powder is dissolved in water together with the binder.
- a method spray dryer in which the droplets are dried by applying hot air to the droplets after the slurry is formed is effective. In either method, PVA, starch or the like can be used as a binder.
- the average particle diameter of the iron oxide powder after agglomeration is important.
- the particle diameter of the iron oxide powder used for reduction has a correlation with the particle diameter of the reduced iron powder after the reduction. Therefore, it is preferable to classify the iron oxide powder after agglomeration and control its average particle size before subjecting it to reduction.
- the average particle diameter of the iron oxide powder after agglomeration is important as described above. However, not all particles maintain the shape, and there are some in which a plurality of particles are combined and one particle is broken. Therefore, as a result of various studies by the inventors, the average particle diameter of reduced iron powder that is practically effective is 50 to 100 ⁇ m. For this purpose, the average particle diameter of the iron oxide powder should be 50 to 200 ⁇ m. I found it preferable. Therefore, in the present invention, it is preferable that the agglomerated iron oxide powder is appropriately classified to have an average particle size of 50 to 200 ⁇ m.
- the iron content in the iron oxide powder is 68.8 mass% or more.
- the amount of oxygen in the reduced iron powder can be sufficiently suppressed, and the effect of improving the chemical reactivity and the effect of manufacturing a high-strength bearing with a high yield can be more sufficiently obtained.
- the upper limit of the iron content in an iron oxide powder it is about 77 mass%.
- the iron oxide powder after agglomeration is reduced to obtain reduced iron powder (or simply referred to as iron powder).
- reduced iron powder or simply referred to as iron powder.
- Inventors have reduced the apparent density to about half that of conventional reduced iron powder and atomized iron powder by appropriately managing the reduction temperature in this reduction step of hydrogen reduction of iron oxide, and inclusions are reduced.
- the conditions for producing finely dispersed iron powder were found. It is important that the reduction temperature during the reduction is from 800 ° C to 1000 ° C. When the reduction temperature is less than 800 ° C., it is difficult to remove oxygen in the reduced iron powder by a reduction reaction.
- the reduction time is 120 It is preferable to set it to more than minutes.
- the upper limit of the reduction time is not particularly limited, but can be about 240 minutes from the viewpoint of an efficient process.
- the manufacturing conditions of publicly known reduced iron powder are applicable to conditions other than the manufacturing conditions of above-mentioned reduced iron powder.
- Examples of the reduction method include a method of heating at atmospheric pressure using a belt furnace or the like in a reducing atmosphere such as hydrogen.
- the reduced iron powder of the present invention has an apparent density of 1.00 to 1.40 Mg / m 3 , which can be produced for the first time by the production method as described above.
- the apparent density of the reduced iron powder is less than 1.00 Mg / m 3 , the specific surface area becomes excessive, and the risk of dust explosion in which the reaction with oxygen in the atmosphere proceeds rapidly increases.
- the apparent density of the reduced iron powder is larger than 1.40 Mg / m 3 , the chemical reactivity becomes insufficient. Further, since the strength of the green compact is reduced, breakage in subsequent processes is likely to occur, and the yield at the time of producing the bearing is also deteriorated.
- the apparent density of the reduced iron powder is in the range of 1.00 to 1.40 Mg / m 3 , the strength of the molded body increases and the bearing can be manufactured with a high yield. Further, by making the apparent density within this range, coarse inclusions are effectively reduced and the strength after sintering is improved, so that the quality of the bearing is improved. Furthermore, the reduced iron powder of the present invention is excellent in reactivity per unit mass, and can be effectively used as a reaction material even inside the particles.
- the apparent density in the present invention is measured according to JIS-Z-2504.
- the oxygen content of the reduced iron powder of the present invention is preferably 0.38 mass% or less.
- the effect of improving the chemical reactivity and the effect of manufacturing a high-strength bearing with a high yield can be obtained more sufficiently.
- the specific surface area of the reduced iron powder is less than 0.20 m 2 / g, the iron powder particles characteristic of the present invention are not sufficiently formed, and the chemical reactivity is insufficient. Therefore, the specific surface area of the reduced iron powder is preferably 0.20 m 2 / g or more.
- the upper limit of the specific surface area of the iron powder is not particularly limited, but is preferably about 0.4 m 2 / g in consideration of handling and the like.
- the specific surface area in the present invention is measured by the BET method using nitrogen gas.
- a bearing can be manufactured using the reduced iron powder according to the present invention as a raw material.
- the bearing is excellent in the yield at the time of producing the bearing, the strength of the bearing, the porosity, and has high chemical reactivity, as described in Examples described later.
- the manufacturing method of the bearing which used the reduced iron powder of this invention as a raw material can be based on a conventional method except using the reduced iron powder of this invention as a raw material.
- the evaluation items of iron powder shown in Table 1 were carried out by the following method.
- the average particle diameter of the raw iron oxide powder was measured by a volume-based laser diffraction method.
- the iron content in the iron oxide powder was a value measured according to JIS-M-8212.
- the average particle size of the iron oxide powder after agglomeration was measured by a laser diffraction method, and a 50% particle size was used.
- the apparent density of the reduced iron powder was measured according to JIS-Z-2504.
- the average particle size of the reduced iron powder was measured by a volume-based laser diffraction method, and a 50% particle size was used.
- the specific surface area of the reduced iron powder by the BET method was measured using nitrogen gas.
- the amount of oxygen in the reduced iron powder was measured by the inert gas fusion infrared absorption method (GFA).
- Yield during bearing production is 5% or less (yield) from compacting into a cylindrical shape with an inner diameter of 0.4mm ⁇ , outer diameter: 1.4mm ⁇ , and height: 2 to 2.5mm until sintering is completed. 95% or higher) was accepted.
- the strength is the strength when compressed in a state in which the cylinder is tilted, with 17N / mm 2 or more passing and less than 17N / mm 2 failing.
- the porosity is a factor that determines the performance of the oil-impregnated bearing, and an appropriate value is 18 to 22%.
- the porosity was measured by the mercury intrusion method.
- FIG. 2 the external appearance image and the cross-sectional image of the reduced iron powder of Examples 1 and 2 of the present invention are shown in comparison with the conventional reduced iron powder. Appearance images were taken using a scanning electron microscope, and cross-sectional images were taken using an optical microscope. Compared to conventional reduced iron powder, Invention Example 1 and Invention Example 2 contain more pores inside the particles.
- Comparative Example 1 is an iron powder obtained by reducing iron oxide powder at 1050 ° C., and its apparent density is 1.48 Mg / m 3, which is outside the scope of the present invention. Although the reduction rate is relatively good, the yield at the time of making the bearing is unacceptable. Moreover, chemical reactivity is also unacceptable.
- Comparative Example 2 is an iron powder obtained by reducing iron oxide powder at 780 ° C., and its apparent density is 0.98 Mg / m 3, which is outside the scope of the present invention. The yield and chemical reactivity at the time of making the bearing are unacceptable.
- Comparative Example 3 is an iron powder obtained by reducing the agglomerated iron oxide powder at 850 ° C. with an average particle diameter of the raw iron oxide powder of 3.2 ⁇ m and an apparent density of 0.95 Mg / m 3 . Yes, outside the scope of the present invention. The reduction rate was relatively low, the yield at the time of bearing production was inferior, and the chemical reactivity was also unacceptable.
- Comparative Example 4 is a reduced iron powder produced by setting the average particle diameter of the agglomerated iron oxide powder to 45 ⁇ m, and its apparent density is 1.49 Mg / m 3, which is outside the scope of the present invention.
- the reduction rate is high and the strength of the bearing is acceptable, but the yield at the time of making the bearing is unacceptable.
- the chemical reactivity was also unacceptable.
- Comparative Example 5 is a reduced iron powder produced by setting the average particle size of the iron oxide powder after agglomeration to 220 ⁇ m, and its apparent density is 0.95 Mg / m 3, which is outside the scope of the present invention.
- the strength of the bearing is acceptable, but the yield at the time of making the bearing is unacceptable.
- the porosity was excessive and the chemical reactivity was also rejected.
- Invention Example 1 is an iron powder obtained by reducing the agglomerated iron oxide powder at 1000 ° C. with an average particle diameter of the agglomerated iron oxide powder being 50 ⁇ m, and its apparent density is 1.38 Mg / m is 3. The reduction rate is high, and the yield, bearing strength, and porosity at the time of making the bearing are all acceptable. The chemical reactivity also showed good performance.
- Invention Example 2 is an iron powder obtained by reducing the agglomerated iron oxide powder at an average particle diameter of 120 ⁇ m at 1000 ° C., and its apparent density is 1.32 Mg / m is 3. The reduction rate is good, and the yield, bearing strength, and porosity at the time of making the bearing are all acceptable. The chemical reactivity also showed good performance.
- Invention Example 3 is an iron powder obtained by reducing the agglomerated iron oxide powder at 800 ° C. with an average particle diameter of the agglomerated iron oxide powder being 120 ⁇ m, and its apparent density is 1.03 Mg / m is 3. The reduction rate is good, and the yield, bearing strength, and porosity at the time of making the bearing are all acceptable. The chemical reactivity also showed good performance.
- Invention Example 4 is an iron powder in which the iron content in the iron oxide powder after agglomeration is 68.2 mass%, and the oxygen content of the iron powder after reduction is 0.43 mass%, but its apparent density is 1.12 Mg / m 3 The chemical reactivity showed good performance, and the yield, bearing strength and porosity at the time of making the bearing were all acceptable.
- Invention Example 5 is a case where the average particle diameter of the raw iron oxide powder is 0.7 ⁇ m, and the average particle diameter of the iron oxide powder is 90 ⁇ m, but the apparent density is 1.05 Mg / m 3 .
- the chemical reactivity showed good performance, and the yield, bearing strength and porosity at the time of making the bearing were all acceptable.
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Abstract
Description
1.見掛密度が1.00~1.40Mg/m3であることを特徴とする還元鉄粉。
レーザー回折法による測定による平均粒子径が3.0μm以下である原料酸化鉄粉を塊成化して酸化鉄粉とする工程と、
その後、前記酸化鉄粉を800~1000℃で水素を用いて還元して還元鉄粉とする工程と、
を有することを特徴とする還元鉄粉の製造方法。
原料酸化鉄粉の平均粒子径は、体積基準のレーザー回折法で測定した。
酸化鉄粉中の鉄分は、JIS-M-8212に則り測定した値を用いた。
塊成化後の酸化鉄粉の平均粒子径は、レーザー回折法で測定し、50%粒子径を用いた。
還元鉄粉の平均粒子径は、体積基準のレーザー回折法で測定し、50%粒子径を用いた。
還元鉄粉のBET法による比表面積は、窒素ガスを用いて測定した。
還元鉄粉中の酸素量は、不活性ガス燃焼-赤外線吸収法(the inert gas fusion infrared absorption method;GFA)により測定した。
気孔率の測定は水銀圧入法により行った。
Claims (7)
- 見掛密度が1.00~1.40Mg/m3であることを特徴とする還元鉄粉。
- 前記還元鉄粉中の酸素量が0.38mass%以下であることを特徴とする請求項1に記載の還元鉄粉。
- 前記還元鉄粉の比表面積が0.20m2/g以上であることを特徴とする請求項1または2に記載の還元鉄粉。
- 請求項1~3のいずれか1項に記載の還元鉄粉を製造する方法であって、
レーザー回折法による測定による平均粒子径が3.0μm以下である原料酸化鉄粉を塊成化して酸化鉄粉とする工程と、
その後、前記酸化鉄粉を800~1000℃で水素を用いて還元して還元鉄粉とする工程と、
を有することを特徴とする還元鉄粉の製造方法。 - 前記酸化鉄粉の還元前に、前記酸化鉄粉を分級して、前記酸化鉄粉のレーザー回折法による測定による平均粒子径を50~200μmとすることを特徴とする請求項4に記載の還元鉄粉の製造方法。
- 前記酸化鉄粉中の鉄分を68.8mass%以上とすることを特徴とする請求項4または5に記載の還元鉄粉の製造方法。
- 請求項1~3のいずれか1項に記載の還元鉄粉を原料とする軸受。
Priority Applications (6)
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CN201680005894.0A CN107107186B (zh) | 2015-01-14 | 2016-01-14 | 还原铁粉及其制造方法以及轴承 |
SE1750827A SE542056C2 (en) | 2015-01-14 | 2016-01-14 | Method for preparing reduced iron powder |
US15/542,459 US20180221960A1 (en) | 2015-01-14 | 2016-01-14 | Reduced iron powder and method for preparing same and bearing |
JP2016521370A JP6197953B2 (ja) | 2015-01-14 | 2016-01-14 | 還元鉄粉の製造方法および軸受の製造方法 |
CA2972864A CA2972864C (en) | 2015-01-14 | 2016-01-14 | Reduced iron powder and method for preparing same and bearing |
KR1020177021779A KR102022947B1 (ko) | 2015-01-14 | 2016-01-14 | 환원철분의 제조 방법 및 베어링의 제조 방법 |
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CN (1) | CN107107186B (ja) |
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US10710155B2 (en) * | 2015-09-18 | 2020-07-14 | Jfe Steel Corporation | Mixed powder for powder metallurgy, sintered body, and method of manufacturing sintered body |
JP7036216B2 (ja) | 2019-05-24 | 2022-03-15 | Jfeスチール株式会社 | 鉄基合金焼結体及び粉末冶金用鉄基混合粉 |
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- 2016-01-14 CA CA2972864A patent/CA2972864C/en active Active
- 2016-01-14 JP JP2016521370A patent/JP6197953B2/ja not_active Expired - Fee Related
- 2016-01-14 SE SE1750827A patent/SE542056C2/en unknown
- 2016-01-14 CN CN201680005894.0A patent/CN107107186B/zh active Active
- 2016-01-14 US US15/542,459 patent/US20180221960A1/en not_active Abandoned
- 2016-01-14 WO PCT/JP2016/000170 patent/WO2016114142A1/ja active Application Filing
- 2016-01-14 KR KR1020177021779A patent/KR102022947B1/ko active IP Right Grant
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KR101878604B1 (ko) * | 2017-06-20 | 2018-07-13 | 현대자동차주식회사 | 레이저 초음파 측정을 이용한 환원 케이크 분쇄 방법 |
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KR20170102942A (ko) | 2017-09-12 |
CA2972864A1 (en) | 2016-07-21 |
JPWO2016114142A1 (ja) | 2017-04-27 |
CN107107186B (zh) | 2019-05-31 |
CA2972864C (en) | 2020-08-11 |
US20180221960A1 (en) | 2018-08-09 |
SE542056C2 (en) | 2020-02-18 |
CN107107186A (zh) | 2017-08-29 |
JP6197953B2 (ja) | 2017-09-20 |
SE1750827A1 (en) | 2017-06-27 |
KR102022947B1 (ko) | 2019-11-04 |
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