WO2010106964A1 - 希土類永久磁石およびその製造方法 - Google Patents
希土類永久磁石およびその製造方法 Download PDFInfo
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- WO2010106964A1 WO2010106964A1 PCT/JP2010/054162 JP2010054162W WO2010106964A1 WO 2010106964 A1 WO2010106964 A1 WO 2010106964A1 JP 2010054162 W JP2010054162 W JP 2010054162W WO 2010106964 A1 WO2010106964 A1 WO 2010106964A1
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- rare earth
- hfc
- permanent magnet
- earth permanent
- magnet
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
Definitions
- the present invention relates to a rare earth permanent magnet and a method for producing the same, and more particularly to a technique for increasing the coercive force by refining crystal grains.
- the alloy powder obtained by quenching the molten metal is subjected to a heat treatment and solidified with a resin to form an isotropic bonded magnet, or obtained by quenching the molten metal.
- a method of obtaining an isotropic bulk magnet by hot compressing an alloy powder by hot pressing discloses an anisotropic bulk magnet by performing hot working on the isotropic bulk magnet. A method of obtaining a magnet is disclosed.
- Nd 2 Fe 14 C or Nd 2 C 3 is formed or the element of Nd 2 Fe 14 B of the main phase is replaced by C, thereby reducing the magnet component. This is because it is a factor that lowers the saturation magnetization.
- the present invention provides a rare earth permanent magnet and a method for manufacturing the same that can refine the crystal grains without reducing the magnet component by containing carbide, thereby improving the coercive force without reducing the saturation magnetization. It is intended to provide.
- the inventors of the present invention have made extensive studies on compounds that can suppress the growth of crystal grains by a so-called pinning effect. And as a result of examining Nb, Mo, Cr, and a compound of Hf, B, C, and Si, attention was paid to HfC having low energy for a carbide generating reaction. Based on the assumption that Nd 2 Fe 14 C and Nd 2 C 3 are formed and that the main phase Nd 2 Fe 14 B element is unlikely to be substituted by C because the generation energy of HfC is low As a result of repeated experiments, it was found that when HfC particles having a predetermined particle diameter are contained in a certain range, growth of crystal grains due to heating is suppressed and no compound is formed with Nd 2 Fe 14 B of the main phase. Obtained.
- the rare earth permanent magnet of the present invention was made based on the above knowledge, and 0.2 to 3. HfC particles having an average particle diameter of 5 to 100 nm in an R—Fe—B alloy (R: rare earth element). It is characterized in that 0 atom% is dispersed.
- the method for producing a rare earth permanent magnet of the present invention rapidly quenches a molten R—Fe—B alloy (R: rare earth element) containing 0.2 to 3.0 atom% of HfC particles having an average particle diameter of 5 to 100 nm. And a step of obtaining a magnetic material having an amorphous or average crystal grain size of 5 ⁇ m or less, and a step of imparting magnetic anisotropy by subjecting the magnet material to hot plastic processing. To do.
- HfC 0.2-3.0% If the HfC content is less than 0.2%, the pinning effect is insufficient, and the crystal grains are likely to grow by heating. On the other hand, if the content of HfC exceeds 3.0%, the ratio of the main phase as a magnet component decreases and the saturation magnetization decreases. Therefore, the content of HfC is set to 0.2 to 3.0%. The HfC content is more preferably 0.6% or more.
- Average crystal grain size of HfC 5 to 100 nm If the average crystal grain size of HfC is less than 5 nm, the pinning effect is insufficient because it is too small with respect to the crystal grains of the main phase. As a result, the crystal grains are likely to grow by heating. On the other hand, when the average crystal grain size of HfC exceeds 100 nm, the dispersion of HfC becomes insufficient and the pinning effect becomes insufficient. Therefore, the average particle size of HfC is set to 5 to 100 nm.
- the molten metal is rapidly cooled to obtain an amorphous or magnet material having an average crystal grain size of 5 ⁇ m or less.
- this magnet material HfC particles are precipitated and dispersed in the crystal grain boundaries of the main phase.
- a molten metal extraction method can be employed as means for rapidly cooling the molten metal.
- the molten metal extraction method is a method in which a molten R-Fe-B alloy is supplied to a surface of a roll from a nozzle while rotating a roll having a water cooling jacket on the inside, and rapidly cooled and solidified.
- the molten metal supplied to the roll is instantly cooled and solidified to obtain a thin ribbon of amorphous or fine crystal grains.
- the width of the ribbon thus obtained is 0.1 to 10 mm, and the thickness is 1 to 100 ⁇ m.
- the magnet material is a ribbon
- the ribbon is pulverized into a powder before hot plastic working and then molded hot.
- a molding method in this case powder injection molding (HIP treatment) in which a powder is hotly applied with almost equal pressure from all directions, or a hot press method in which powder is compression-molded in a mold cavity can be used.
- HIP treatment powder injection molding
- a hot press method in which powder is compression-molded in a mold cavity
- hot plastic working can be easily performed.
- the amorphous structure is crystallized by hot forming.
- the easy axis of crystal grains can be aligned to some extent so as to face the pressing direction. Thereby, the degree of orientation of the easy magnetization axis is further increased by the next hot plastic working, and a high magnetic flux density can be obtained after magnetization.
- the temperature of hot plastic working is desirably 800 ° C. or less, more desirably 750 ° C. or less, and further desirably 700 ° C. or less.
- the temperature of hot plastic working is desirably 800 ° C. or less, more desirably 750 ° C. or less, and further desirably 700 ° C. or less.
- Nd is generally used as the rare earth element, but other rare earth elements such as Dy (dysprosium) and Tb (terbium) can also be used.
- the ratio of each component can be, for example, R: 5 to 20%, Fe: 65 to 85%, B: 3 to 10%, and HfC: 0.2 to 3.0%.
- the method for rapidly cooling the molten metal is not limited to the molten metal extraction method, and various methods can be used.
- the billet equivalent to the ribbon obtained by the molten metal extraction method can be obtained by increasing the cooling rate in the mold in the continuous casting method.
- a powdered magnet material can be obtained by an atomizing method.
- the crystal grains of the main phase are deformed by hot plastic working, and the grain boundaries are disturbed.
- the heat treatment temperature is desirably 600 to 900 ° C.
- the rare earth permanent magnet obtained by the above process 0.2 to 3.0 atom% of HfC particles having an average particle diameter of 5 to 100 nm is dispersed in an R—Fe—B alloy (R: rare earth element).
- R rare earth element
- the average particle size of the structure of such rare earth permanent magnets is preferably 10 to 500 nm, and the average particle size of HfC particles is preferably 5 to 20 nm.
- the present invention by containing carbide, it is possible to refine the crystal grains without reducing the magnet component, thereby obtaining the effect of improving the coercive force without reducing the saturation magnetization. .
- the obtained ribbon sample is heat-treated at 700 ° C., 750 ° C., and 800 ° C. for 10 minutes to crystallize the amorphous phase to eliminate the influence on the magnetic properties and to grow crystal grains. The degree was observed.
- Magnetization measurement was performed on each sample using a sample vibration magnetometer. The relationship between the amount of each element added and the coercive force is shown in FIG.
- the sample structure was observed with an electron microscope.
- FIG. 2 shows the relationship between the average crystal grain size and the coercivity calculated by the structure observation.
- tissue is shown in FIG.
- FIG. 1 shows the relationship between the amount of each element added and the coercive force of a sample subjected to heat treatment at 700 ° C.
- the coercive force increases as the amount of HfC added increases.
- the coercive force hardly changes, and when C is added alone, the coercive force decreases as the amount of addition of C increases. From this, it can be inferred that the simultaneous addition of Hf and C is effective in increasing the coercive force.
- FIG. 2 shows the relationship between the crystal grain size and the coercivity of the sample to which HfC was added and the sample to which HfC was not added. As shown by arrows in FIG. 2, at the same heat treatment temperature, the sample to which HfC is added has a smaller crystal grain size and a larger coercive force than the sample to which HfC is not added. This means that the growth rate of crystal grains is suppressed by the addition of HfC.
- FIG. 3 shows a TEM photograph of the structure of a sample to which HfC was not added and a sample to which HfC was added and which was heat-treated at 700 ° C. Also in the TEM photograph of the structure, it can be confirmed that the sample added with HfC has finer crystal grains. Moreover, as a result of performing element mapping on the sample to which HfC was added, it was confirmed that fine crystal grains of about 10 nm containing Hf were uniformly precipitated and dispersed. This precipitate suppresses the growth of the main phase crystal grains, thereby making the crystal grains fine and improving the coercive force.
- the present invention can improve the coercive force without reducing the saturation magnetization by refining the crystal grains, it can be used in technical fields such as motors.
Abstract
Description
HfC:0.2~3.0%
HfCの含有量が0.2%未満ではピン止め効果が不充分となり加熱により結晶粒が成長し易くなる。一方、HfCの含有量が3.0%を超えると、磁石成分としての主相の割合が少なくなって飽和磁化が低下する。よって、HfCの含有量は0.2~3.0%とした。なお、HfCの含有量は0.6%以上であるとさらに好適である。
HfCの平均結晶粒径が5nmを下回ると、主相の結晶粒に対して小さすぎるためピン止め効果が不充分となり、その結果、加熱により結晶粒が成長し易くなる。一方、HfCの平均結晶粒径が100nmを超えると、HfCの分散が不充分となり、ピン止め効果が不充分となる。よって、HfCの平均粒径は5~100nmとした。
Claims (2)
- R−Fe−B系合金(R:希土類元素)中に、平均粒径が5~100nmのHfC粒子を0.2~3.0atom%分散させたことを特徴とする希土類永久磁石。
- 平均粒径が5~100nmのHfC粒子を0.2~3.0atom%含有するR−Fe−B系合金(R:希土類元素)の溶湯を急冷することにより非晶質または平均結晶粒径が5μm以下の磁石材料を得る工程と、
前記磁石材料を熱間で塑性加工することにより磁気異方性を付与する工程と、
を備えたことを特徴とする希土類永久磁石の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/257,052 US20120048431A1 (en) | 2009-03-19 | 2010-03-05 | Rare-earth permanent magnet and production process for the same |
EP10753456A EP2410067A4 (en) | 2009-03-19 | 2010-03-05 | Rare earth polymer magenta magnet and method of making same |
CN2010800122992A CN102356172A (zh) | 2009-03-19 | 2010-03-05 | 稀土永久磁石及其制造方法 |
Applications Claiming Priority (2)
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JP2009-068418 | 2009-03-19 | ||
JP2009068418A JP2010222601A (ja) | 2009-03-19 | 2009-03-19 | 希土類永久磁石およびその製造方法 |
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WO2010106964A1 true WO2010106964A1 (ja) | 2010-09-23 |
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PCT/JP2010/054162 WO2010106964A1 (ja) | 2009-03-19 | 2010-03-05 | 希土類永久磁石およびその製造方法 |
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US (1) | US20120048431A1 (ja) |
EP (1) | EP2410067A4 (ja) |
JP (1) | JP2010222601A (ja) |
CN (1) | CN102356172A (ja) |
WO (1) | WO2010106964A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017150022A (ja) * | 2016-02-23 | 2017-08-31 | Jfeスチール株式会社 | 積層造形方法、積層造形体製造方法、および積層造形体 |
Families Citing this family (4)
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JP5708242B2 (ja) * | 2011-05-24 | 2015-04-30 | トヨタ自動車株式会社 | 希土類磁石の製造方法 |
JP6472640B2 (ja) * | 2014-11-13 | 2019-02-20 | 本田技研工業株式会社 | 熱間加工磁石とその原料粉末および該原料粉末を成形した成形体ならびにそれらの製造方法 |
CN104376946B (zh) * | 2014-12-14 | 2016-08-17 | 浙江南磁实业股份有限公司 | 一种高强韧烧结钕铁硼磁体及其制备方法 |
CN107275025B (zh) * | 2016-04-08 | 2019-04-02 | 沈阳中北通磁科技股份有限公司 | 一种含铈钕铁硼磁钢及制造方法 |
Citations (5)
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JPS60100402A (ja) | 1983-08-04 | 1985-06-04 | ゼネラル モ−タ−ズ コ−ポレ−シヨン | 磁気異方性の鉄‐希土類系永久磁石を作る方法 |
JPS63196014A (ja) | 1987-02-10 | 1988-08-15 | Hitachi Metals Ltd | 磁気異方性磁石及びその製造方法 |
JPH024941A (ja) | 1987-12-18 | 1990-01-09 | Kubota Ltd | 二ホウ化ハフニウムを含有した鉄―ネオジム―ホウ素基永久磁石合金及び製法 |
JP2002124407A (ja) * | 2000-10-16 | 2002-04-26 | Hitachi Metals Ltd | 異方性希土類焼結磁石及びその製造方法 |
JP2006210893A (ja) * | 2004-12-27 | 2006-08-10 | Shin Etsu Chem Co Ltd | Nd−Fe−B系希土類永久磁石材料 |
Family Cites Families (7)
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JPS62181402A (ja) * | 1986-02-05 | 1987-08-08 | Hitachi Metals Ltd | R−B−Fe系焼結磁石およびその製造方法 |
JPS6398105A (ja) * | 1986-10-15 | 1988-04-28 | Mitsubishi Metal Corp | 金属炭化物分散型Fe基焼結合金製永久磁石 |
US5486240A (en) * | 1994-04-25 | 1996-01-23 | Iowa State University Research Foundation, Inc. | Carbide/nitride grain refined rare earth-iron-boron permanent magnet and method of making |
CN1210344A (zh) * | 1997-08-30 | 1999-03-10 | 中国科学院金属研究所 | 一种钕铁硼纳米永磁材料 |
JP2002025810A (ja) * | 2000-07-06 | 2002-01-25 | Hitachi Metals Ltd | 異方性希土類焼結磁石及びその製造方法 |
US8012269B2 (en) * | 2004-12-27 | 2011-09-06 | Shin-Etsu Chemical Co., Ltd. | Nd-Fe-B rare earth permanent magnet material |
CN101364465B (zh) * | 2008-06-06 | 2013-07-10 | 浙江西子富沃德电机有限公司 | 稀土永磁材料及其制备方法 |
-
2009
- 2009-03-19 JP JP2009068418A patent/JP2010222601A/ja active Pending
-
2010
- 2010-03-05 EP EP10753456A patent/EP2410067A4/en not_active Withdrawn
- 2010-03-05 WO PCT/JP2010/054162 patent/WO2010106964A1/ja active Application Filing
- 2010-03-05 US US13/257,052 patent/US20120048431A1/en not_active Abandoned
- 2010-03-05 CN CN2010800122992A patent/CN102356172A/zh active Pending
Patent Citations (5)
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JPS60100402A (ja) | 1983-08-04 | 1985-06-04 | ゼネラル モ−タ−ズ コ−ポレ−シヨン | 磁気異方性の鉄‐希土類系永久磁石を作る方法 |
JPS63196014A (ja) | 1987-02-10 | 1988-08-15 | Hitachi Metals Ltd | 磁気異方性磁石及びその製造方法 |
JPH024941A (ja) | 1987-12-18 | 1990-01-09 | Kubota Ltd | 二ホウ化ハフニウムを含有した鉄―ネオジム―ホウ素基永久磁石合金及び製法 |
JP2002124407A (ja) * | 2000-10-16 | 2002-04-26 | Hitachi Metals Ltd | 異方性希土類焼結磁石及びその製造方法 |
JP2006210893A (ja) * | 2004-12-27 | 2006-08-10 | Shin Etsu Chem Co Ltd | Nd−Fe−B系希土類永久磁石材料 |
Non-Patent Citations (1)
Title |
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See also references of EP2410067A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2017150022A (ja) * | 2016-02-23 | 2017-08-31 | Jfeスチール株式会社 | 積層造形方法、積層造形体製造方法、および積層造形体 |
Also Published As
Publication number | Publication date |
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EP2410067A1 (en) | 2012-01-25 |
EP2410067A4 (en) | 2012-08-01 |
US20120048431A1 (en) | 2012-03-01 |
JP2010222601A (ja) | 2010-10-07 |
CN102356172A (zh) | 2012-02-15 |
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