EP4187558A1 - Additive and application thereof, and samarium-cobalt 2: 17 type magnet and preparation method thereof - Google Patents
Additive and application thereof, and samarium-cobalt 2: 17 type magnet and preparation method thereof Download PDFInfo
- Publication number
- EP4187558A1 EP4187558A1 EP22206155.8A EP22206155A EP4187558A1 EP 4187558 A1 EP4187558 A1 EP 4187558A1 EP 22206155 A EP22206155 A EP 22206155A EP 4187558 A1 EP4187558 A1 EP 4187558A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- samarium
- additive
- cobalt
- alloy powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 title claims abstract description 95
- 239000000654 additive Substances 0.000 title claims abstract description 81
- 230000000996 additive effect Effects 0.000 title claims abstract description 77
- KPLQYGBQNPPQGA-UHFFFAOYSA-N cobalt samarium Chemical compound [Co].[Sm] KPLQYGBQNPPQGA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 92
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000004014 plasticizer Substances 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 73
- 229910045601 alloy Inorganic materials 0.000 claims description 65
- 239000000956 alloy Substances 0.000 claims description 65
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 235000012424 soybean oil Nutrition 0.000 claims description 27
- 239000003549 soybean oil Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 18
- 235000019198 oils Nutrition 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- -1 copper carboxylate Chemical class 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- 238000005245 sintering Methods 0.000 claims description 14
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 13
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002480 mineral oil Substances 0.000 claims description 13
- 235000010446 mineral oil Nutrition 0.000 claims description 13
- 238000007493 shaping process Methods 0.000 claims description 11
- GYPBUYJSHBFNEJ-UHFFFAOYSA-L copper;hexadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GYPBUYJSHBFNEJ-UHFFFAOYSA-L 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 8
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 8
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 claims description 8
- HCRZXNOSPPHATK-UHFFFAOYSA-L copper;3-oxobutanoate Chemical compound [Cu+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HCRZXNOSPPHATK-UHFFFAOYSA-L 0.000 claims description 7
- XGAUKDLPTUQUJD-UHFFFAOYSA-K P(=S)([O-])([O-])[O-].[Cu+3] Chemical compound P(=S)([O-])([O-])[O-].[Cu+3] XGAUKDLPTUQUJD-UHFFFAOYSA-K 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- RAOMGUIVEVUUOG-UHFFFAOYSA-M butoxy-butylsulfanyl-oxido-sulfanylidene-lambda5-phosphane copper(1+) Chemical compound [Cu+].CCCCOP([O-])(=S)SCCCC RAOMGUIVEVUUOG-UHFFFAOYSA-M 0.000 claims description 6
- JSOOQHKASJAVGX-UHFFFAOYSA-M copper(1+) hexoxy-hexylsulfanyl-oxido-sulfanylidene-lambda5-phosphane Chemical compound CCCCCCOP(=S)([O-])SCCCCCC.[Cu+] JSOOQHKASJAVGX-UHFFFAOYSA-M 0.000 claims description 6
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 229940120693 copper naphthenate Drugs 0.000 claims description 5
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 5
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical group [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000010902 jet-milling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 4
- 150000004699 copper complex Chemical group 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000009750 centrifugal casting Methods 0.000 claims description 3
- 238000002074 melt spinning Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JZCAHRHZFBBFRZ-WCCKRBBISA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;copper Chemical compound [Cu].CSCC[C@H](N)C(O)=O JZCAHRHZFBBFRZ-WCCKRBBISA-N 0.000 claims description 2
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical compound SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 claims description 2
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 claims description 2
- YCEJYAHZUQTYGN-FJOGWHKWSA-L C(\C=C/C(=O)[O-])(=O)[O-].[Cu+2].C=CC1=CC=CC=C1 Chemical compound C(\C=C/C(=O)[O-])(=O)[O-].[Cu+2].C=CC1=CC=CC=C1 YCEJYAHZUQTYGN-FJOGWHKWSA-L 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- JNZSJDBNBJWXMZ-UHFFFAOYSA-N carbon diselenide Chemical compound [Se]=C=[Se] JNZSJDBNBJWXMZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- CXGHLNDIGXESIH-GRVYQHKQSA-L copper;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Cu+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O CXGHLNDIGXESIH-GRVYQHKQSA-L 0.000 claims description 2
- QHECZRAGQOGJLT-UHFFFAOYSA-N copper;1h-quinolin-2-one Chemical compound [Cu].C1=CC=CC2=NC(O)=CC=C21 QHECZRAGQOGJLT-UHFFFAOYSA-N 0.000 claims description 2
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 claims description 2
- SEKCXMNFUDONGJ-UHFFFAOYSA-L copper;2-ethylhexanoate Chemical compound [Cu+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O SEKCXMNFUDONGJ-UHFFFAOYSA-L 0.000 claims description 2
- VZWHXRLOECMQDD-UHFFFAOYSA-L copper;2-methylprop-2-enoate Chemical compound [Cu+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O VZWHXRLOECMQDD-UHFFFAOYSA-L 0.000 claims description 2
- PAPICMNCZXAJQT-UHFFFAOYSA-L copper;methanethioate Chemical class [Cu+2].[O-]C=S.[O-]C=S PAPICMNCZXAJQT-UHFFFAOYSA-L 0.000 claims description 2
- GSCLWPQCXDSGBU-UHFFFAOYSA-L copper;phthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O GSCLWPQCXDSGBU-UHFFFAOYSA-L 0.000 claims description 2
- CPDQQOYHCXKRBR-UHFFFAOYSA-L copper;pyrazine-2-carboxylate Chemical compound [Cu+2].[O-]C(=O)C1=CN=CC=N1.[O-]C(=O)C1=CN=CC=N1 CPDQQOYHCXKRBR-UHFFFAOYSA-L 0.000 claims description 2
- GNWVUSJJFONIKF-UHFFFAOYSA-L copper;pyridine-2-carboxylate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=N1.[O-]C(=O)C1=CC=CC=N1 GNWVUSJJFONIKF-UHFFFAOYSA-L 0.000 claims description 2
- JJKSAEHNIHMQKQ-UHFFFAOYSA-N copper;quinoline Chemical compound [Cu].N1=CC=CC2=CC=CC=C21 JJKSAEHNIHMQKQ-UHFFFAOYSA-N 0.000 claims description 2
- FDIRIOAEXPIEBL-UHFFFAOYSA-L copper;thiophene-2-carboxylate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CS1.[O-]C(=O)C1=CC=CS1 FDIRIOAEXPIEBL-UHFFFAOYSA-L 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000005498 phthalate group Chemical group 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 2
- 229960004592 isopropanol Drugs 0.000 description 15
- 239000000314 lubricant Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 2
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910017076 Fe Zr Inorganic materials 0.000 description 1
- 239000005640 Methyl decanoate Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- SMDHCQAYESWHAE-UHFFFAOYSA-N benfluralin Chemical compound CCCCN(CC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O SMDHCQAYESWHAE-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
Images
Classifications
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- 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
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/015—Metals or alloys
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- 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
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- 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
- H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
- H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
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- 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
-
- 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
- H01F41/0273—Imparting anisotropy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F7/00—Magnets
- H01F7/02—Permanent magnets [PM]
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Definitions
- the present invention relates to an additive and application thereof, and a samarium-cobalt 2: 17 type magnet and a preparation method thereof.
- the grain boundary structure with copper depletion has a weak domain wall pinning field, which can easily form a reversal magnetization center during demagnetization, thereby reducing the coercivity, squareness, and magnetic energy product of magnets.
- CN111145973A discloses a preparation method of a magnet containing a Cu grain boundary phase, in which CuO powder is mixed with samarium-cobalt powder, and the mixture is pressed and sintered.
- the method can improve the coercivity and squareness to certain extents, the oversize micro powder and introduction of a nonmagnetic grain boundary phase cause the reduction of remanence.
- the micro powder cannot be uniformly dispersed, so that an achieved effect is limited.
- a copper diffusion method for regulating and controlling grain boundaries has also been reported, but this diffusion method is only effective for sheet samples only, so its use is limited.
- the present invention provides an additive and application thereof, and a samarium-cobalt 2: 17 type magnet and a preparation method thereof.
- the preparation method of a Sm 2 Co 17 permanent magnet of the present invention can greatly eliminate adverse effects brought by the phenomenon of copper depletion at grain boundaries without reducing the remanence, thereby improving the coercivity, squareness, and magnetic energy product of products.
- the present invention adopts the following technical solutions to solve the above technical problem.
- the present invention provides an additive, which includes the following components by mass percentage: 20-30% of organocopper complex, 0.5-1% of plasticizer, and an organic solvent, and the sum of the mass percentages of the components is 100%, wherein the organocopper complex is an oil-soluble substance, the mass percentage of Cu in the organocopper complex is greater than 10%, and the organocopper complex contains a polar group and/or an alkyl chain having more than 3 C atoms.
- the organocopper complex may be a conventional oil-soluble organocopper complex in the art, for example, may be completely dissolved in an inert solvent such as toluene and mineral oil.
- the inert solvent generally refers to a solvent that does not chemically react with the organocopper complex.
- the polar group in the organocopper complex is one or more of a hydroxyl group, a carboxyl group, an amino group, an ester group, and an amide group.
- the alkyl chain in the organocopper complex may be a saturated alkyl chain or an unsaturated alkyl chain, and the alkyl chain may be a straight chain or a branched chain.
- the organocopper complex is one or more of a substituted copper carboxylate complex, a copper carboxylate derivative, a copper thiophosphate complex, copper quinoline, copper hydroxyquinoline, copper phthalate, thiodiazole copper, copper acetylacetonate, and copper acetoacetate.
- a general formula of the substituted copper carboxylate complex is preferably [RCO 2 ] 2 Cu, where, R is alkyl, alkynyl, cyclo, aryl or heteroaryl; preferably, the substituted copper carboxylate complex is one or more of fatty acid copper having 10 to 22 carbon atoms, copper styrene maleate, copper picolinate, copper 2-pyrazinecarboxylate, copper 2-ethylhexanoate, copper methacrylate, copper thiophene-2-carboxylate, copper methionine, and copper tartrate, and the fatty acid copper having 10 to 22 carbon atoms is preferably one or more of copper oleate, copper linoleate, copper stearate, copper rosinate, copper hexadecanoate, copper palmitate, and copper naphthenate.
- the copper carboxylate derivative is preferably a copper thiocarboxylate derivative [R'CS 2 ] 2 Cu or a copper selenocarboxylate derivative [R'CSe 2 ] 2 Cu, where, R' includes alkyl and alkyl derivatives; and preferably, the copper carboxylate derivative is copper N,N-di-n-butyldithiocarbamate (Cu(SC(S)N(C 4 H 9 ) 2 ) 2 ) and/or copper N,N-din-butyldiselenocarbamate (Cu(SeC(Se)N(C 4 H 9 ) 2 ) 2 ).
- the copper thiophosphate complex is preferably a copper complex of a dialkyldithiophosphate, and a general formula of the copper complex of the dialkyldithiophosphate is (RO) 2 P(S)SHM, where, R is alkyl or aryl, and M includes monovalent copper and divalent copper (CuDDP for short); and preferably, the copper thiophosphate complex is one or more of copper dihexyldithiophosphate, copper dibutyldithiophosphate, copper-containing antioxidant T541, and copper-containing antioxidant T542.
- the copper-containing antioxidant T541 and the copper-containing antioxidant T542 can be purchased from the additive factory of Jinzhou Petrochemical Corporation.
- the grain diameter of the organocopper complex is less than 10 ⁇ m.
- the mass percentage of the organocopper complex in the additive is 20%, 22%, 23%, 25%, 27% or 30%.
- the plasticizer may be a conventional plasticizer in the art, preferably, the plasticizer is a phthalate and/or epoxidized soybean oil, and more preferably, the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate, and epoxidized soybean oil.
- the organocopper complex can be uniformly dispersed on the surface of powder, agglomeration between the organocopper complexes can be prevented, Cu is uniformly distributed at grain boundaries after the organocopper complex is decomposed, the grain boundary Cu concentration is basically equivalent to the intragranular Cu concentration, and the phenomenon of copper depletion at grain boundaries is avoided.
- the mass percentage of the plasticizer in the additive is 0.5%, 0.8% or 1%.
- the organic solvent may be a conventional organic solvent in the art, preferably, the organic solvent is one or more of acetone, toluene, mineral oil, methyl acetate, 120# solvent oil, isooctane, isopropanol, chloroform, and methyl methacrylate, and more preferably, the organic solvent is one or more of 120# solvent oil, toluene, mineral oil, acetone, isooctane, and isopropanol, such as 120# solvent oil, toluene, mineral oil, a mixed solvent of isooctane and isopropanol, and a mixed solvent of acetone and isopropanol.
- the organic solvent is one or more of acetone, toluene, mineral oil, methyl acetate, 120# solvent oil, isooctane, isopropanol, chloroform, and methyl methacrylate
- the organic solvent is one or more of 120# solvent oil, tolu
- the mass percentage of the organic solvent in the additive is 69-79.5%.
- the additive is composed of 20-30% of organocopper complex, 0.5-1% of plasticizer, and 69-79.5% of organic solvent.
- the present invention also provides a preparation method of the above additive, which includes the following step: mixing the organocopper complex, the plasticizer, and the organic solvent.
- the present invention also provides application of the above additive in preparation of a samarium-cobalt magnet.
- the additive has the effects of lubricating and regulating and controlling grain boundaries of samarium-cobalt magnets, can improve the phenomenon of copper depletion at grain boundaries, and improve the remanence, coercivity, and squareness of magnets.
- the present invention also provides a preparation method of a samarium-cobalt 2: 17 type magnet, which includes the following steps: mixing samarium-cobalt magnet alloy powder with the above additive, shaping, sintering, and aging.
- the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder is 0.1-0.2%.
- raw materials of the samarium-cobalt magnet alloy powder include Sm, Cu, Fe, Zr, and Co.
- the mass percentage of Sm in the raw materials of the samarium-cobalt magnet alloy powder is 24-26% such as 24%, 25.5%, and 26%.
- the mass percentage of Cu in the raw materials of the samarium-cobalt magnet alloy powder is 4-6% such as 4%, 5.5%, and 6%.
- the mass percentage of Fe in the raw materials of the samarium-cobalt magnet alloy powder is 10-20% such as 10%, 17%, 19%, and 20%.
- the mass percentage of Zr in the raw materials of the samarium-cobalt magnet alloy powder is 2.0-4% such as 2.0%, 3.5%, and 4%.
- the mass percentage of Co in the raw materials of the samarium-cobalt magnet alloy powder is 45-60% such as 46%, 48%, 51.5%, and 56%.
- the samarium-cobalt magnet alloy powder is composed of 24% of Sm, 4% of Cu, 17% of Fe, 3.5% of Zr, 51.5% of Co.
- the samarium-cobalt magnet alloy powder is composed of 25.5% of Sm, 5.5% of Cu, 19% of Fe, 2% of Zr, and 48% of Co.
- the samarium-cobalt magnet alloy powder is composed of 26% of Sm, 4% of Cu, 10% of Fe, 4% of Zr, and 56% of Co.
- the samarium-cobalt magnet alloy powder is composed of 24% of Sm, 6% of Cu, 20% of Fe, 4% of Zr, and 46% of Co.
- the samarium-cobalt magnet alloy powder is obtained by smelting and crushing the raw materials of the samarium-cobalt magnet alloy powder.
- the smelting is performed by melt-spinning, centrifugal casting or ingot casting.
- the crushing includes coarse crushing, secondary crushing, and fine crushing, wherein the coarse crushing is preferably Jaw crushing, the secondary crushing is preferably disc milling or crushing with an intermediate crusher, and the fine crushing is preferably jet milling or ball milling.
- coarse crushing is preferably Jaw crushing
- secondary crushing is preferably disc milling or crushing with an intermediate crusher
- fine crushing is preferably jet milling or ball milling.
- the grain diameter D50 of the samarium-cobalt magnet alloy powder is 4-6 ⁇ m.
- the samarium-cobalt magnet alloy powder is mixed with the additive, and the mixture is dried to remove most of the solvent, shaped, sintered, and aged.
- the drying is preferably placing the powder in a dryer and drying at 80°C for 5-10 h such as 5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, and 10 h.
- the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder is 0.1%, 0.12%, 0.14%, 0.16%, 0.18% or 0.2%, and an addition amount of the additive is determined by the copper content in a selected substance and the solution concentration.
- the additive is composed of 25% of copper naphthenate, 0.50% of epoxidized soybean oil, and 74.5% of 120# solvent oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 2.5%.
- the additive is composed of 30% of copper oleate, 0.50% of epoxidized soybean oil, and 69.5% of 120# solvent oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.3%.
- the additive is composed of 30% of copper hexadecanoate, 0.50% of dibutyl phthalate, and 69.5% of 120# solvent oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.6%.
- the additive is composed of 27% of copper N,N-di-n-butyldithiocarbamate, 0.50% of dibutyl phthalate, and 72.5% of toluene; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.3%.
- the additive is composed of 25% of copper dihexyldithiophosphate, 0.80% of epoxidized soybean oil, and 74.2% of toluene; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.4%.
- the additive is composed of 22% of copper dibutyldithiophosphate, 0.80% of dioctyl phthalate, and 77.2% of mineral oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 2.4%.
- the additive is composed of 23% of T541, 0.80% of dioctyl phthalate, and 76.2% of mineral oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.5%.
- the additive is composed of 20% of copper acetylacetonate, 1% of epoxidized soybean oil, 40% of isooctane, and 39% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.7%.
- the additive is composed of 23% of copper acetoacetate, 1% of epoxidized soybean oil, 40% of acetone, and 36% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 4.4%.
- the additive is composed of 20% of copper hexadecanoate, 1% of epoxidized soybean oil, 40% of isooctane, and 39% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 8.1%.
- the additive is composed of 23% of copper oleate, 1% of epoxidized soybean oil, 40% of acetone, and 36% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 8.7%.
- the shaping operation and conditions may be conventional in the art, and preferably, the shaping is oriented compression shaping performed in a static magnetic field.
- the magnetic field strength B for shaping is 1.5-2 T.
- the sintering operation and conditions are conventional in the art.
- the sintering is performed in an inert atmosphere.
- the sintering temperature is 1200-1220°C such as 1200°C, 1210°C, 1215°C, and 1220°C.
- the sintering time is 1-5 h such as 1 h, 3 h, 4 h, and 5 h.
- solution treatment is performed after sintering.
- the solution treatment temperature is 1140-1190°C such as 1140°C, 1150°C, 1160°C, and 1190°C.
- the solution treatment time is 5-40 h such as 5 h, 20 h, 35 h, and 40 h.
- the aging operation and conditions are conventional in the art.
- the aging is keeping at 800-900°C (e.g., 810°C, 840°C, 860°C, and 900°C) for 5-20 h (e.g., 5 h, 15 h, and 20 h), cooling to 400°C, and keeping for 5-10 h (e.g., 5 h, 6 h, 7 h, and 10 h).
- 800-900°C e.g., 810°C, 840°C, 860°C, and 900°C
- the cooling is performed at a rate of 0.7°C/min.
- the present invention also provides a samarium-cobalt 2: 17 type magnet, which is prepared by the above preparation method of a samarium-cobalt 2: 17 type magnet.
- the present invention also provides a samarium-cobalt 2: 17 type magnet, in which the grain boundary Cu concentration is basically equivalent to the intragranular Cu concentration.
- the grain boundary Cu concentration in the samarium-cobalt 2: 17 type magnet is 3-5.6%
- the intragranular Cu concentration in the samarium-cobalt 2: 17 type magnet is 3.2-6%
- the percentage is the percentage of atoms
- the intragranular and grain boundary Cu concentrations are distributed uniformly.
- the reagents and materials used in the present invention are all commercially available.
- the present invention has the following positive progressive effects.
- the method of using an additive containing an organocopper complex to regulate and control grain boundaries is easy to operate, does not require extra process procedures, and does not have special requirements for the shape and size of a product, so it is suitable for batch production.
- a finally obtained product has basically equivalent remanence, the coercivity is increased by 5-10 kOe, Hk is increased by 1-4 kOe, and the squareness can reach 60-75%.
- the smelting was performed by melt-spinning, centrifugal casting or ingot casting; the crushing was coarse crushing, secondary crushing, and fine crushing that were performed in sequence, the coarse crushing was Jaw crushing, the secondary crushing was disc milling or crushing with an intermediate crusher; and the fine crushing was jet milling.
- the samarium-cobalt magnet alloy powder obtained at step (1) was mixed with an additive shown in Table 2, and the mixture was dried by using a dryer in a 99.99% N 2 atmosphere at 80°C for a period of time shown in Table 1. Then, the mixture was shaped, sintered, and aged. An addition amount of the additive was determined by a set effective addition amount of Cu (the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder) and the solution concentration, see Table 1.
- the fine crushing was jet milling or ball milling.
- Oriented compression shaping was performed in a static magnetic field.
- the magnetic field strength for shaping, the sintering temperature and time, solution treatment temperature and time, and aging operation are shown in Table 3.
- the cooling in the aging was performed at a rate of 0.7°C/min.
- Samarium-cobalt magnet alloy powder raw materials and additives were prepared according to the formulas shown in Tables 1 and 2, and other process conditions were the same as those in Example 1 in addition to the operation parameters shown in Table 3.
- the additives of Contrasts 1 to 4 contained a lubricant and an organic solvent only; the additives of Contrasts 5 to 7 contained an organocopper complex only; and the additive of Contrast 10 contained an organocopper complex and an organic solvent only.
- the grain boundary Cu concentration is basically equivalent to the intragranular Cu concentration, so that the phenomenon of copper depletion at grain boundaries is avoided.
- the samples of the examples have basically equivalent remanence, the coercivity is increased by 5-10 kOe, Hk is increased by 1-4 kOe, and the squareness can reach 60-75%.
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Abstract
Description
- The present invention relates to an additive and application thereof, and a samarium-cobalt 2: 17 type magnet and a preparation method thereof.
- The phenomenon of copper depletion at grain boundaries commonly occurs in Sm2Co17 permanent magnet materials (also referred to as samarium-cobalt 2: 17 type magnets) and has become an obstacle for the improvement of properties, especially the squareness, of the Sm2Co17 permanent magnet materials. The grain boundary structure with copper depletion has a weak domain wall pinning field, which can easily form a reversal magnetization center during demagnetization, thereby reducing the coercivity, squareness, and magnetic energy product of magnets.
- The current practice is to improve the phenomenon of copper depletion at grain boundaries by adding micro or nano copper or copper oxide powder directly to jet-milled powder. For example,
CN111145973A discloses a preparation method of a magnet containing a Cu grain boundary phase, in which CuO powder is mixed with samarium-cobalt powder, and the mixture is pressed and sintered. Although the method can improve the coercivity and squareness to certain extents, the oversize micro powder and introduction of a nonmagnetic grain boundary phase cause the reduction of remanence. Moreover, the micro powder cannot be uniformly dispersed, so that an achieved effect is limited. In addition, a copper diffusion method for regulating and controlling grain boundaries has also been reported, but this diffusion method is only effective for sheet samples only, so its use is limited. - In order to solve the defect that in the prior art, the coercivity and squareness are only improved to limited extents and the remanence may be reduced when overcoming the problem of poor magnetic properties, especially low squareness, of Sm2Co17 permanent magnet materials caused by the phenomenon of copper depletion at grain boundaries, the present invention provides an additive and application thereof, and a samarium-cobalt 2: 17 type magnet and a preparation method thereof. The preparation method of a Sm2Co17 permanent magnet of the present invention can greatly eliminate adverse effects brought by the phenomenon of copper depletion at grain boundaries without reducing the remanence, thereby improving the coercivity, squareness, and magnetic energy product of products.
- The present invention adopts the following technical solutions to solve the above technical problem.
- The present invention provides an additive, which includes the following components by mass percentage: 20-30% of organocopper complex, 0.5-1% of plasticizer, and an organic solvent, and the sum of the mass percentages of the components is 100%,
wherein the organocopper complex is an oil-soluble substance, the mass percentage of Cu in the organocopper complex is greater than 10%, and the organocopper complex contains a polar group and/or an alkyl chain having more than 3 C atoms. - In the present invention, the organocopper complex may be a conventional oil-soluble organocopper complex in the art, for example, may be completely dissolved in an inert solvent such as toluene and mineral oil. The inert solvent generally refers to a solvent that does not chemically react with the organocopper complex.
- Preferably, the polar group in the organocopper complex is one or more of a hydroxyl group, a carboxyl group, an amino group, an ester group, and an amide group.
- The alkyl chain in the organocopper complex may be a saturated alkyl chain or an unsaturated alkyl chain, and the alkyl chain may be a straight chain or a branched chain.
- Preferably, the organocopper complex is one or more of a substituted copper carboxylate complex, a copper carboxylate derivative, a copper thiophosphate complex, copper quinoline, copper hydroxyquinoline, copper phthalate, thiodiazole copper, copper acetylacetonate, and copper acetoacetate.
- A general formula of the substituted copper carboxylate complex is preferably [RCO2]2Cu, where, R is alkyl, alkynyl, cyclo, aryl or heteroaryl; preferably, the substituted copper carboxylate complex is one or more of fatty acid copper having 10 to 22 carbon atoms, copper styrene maleate, copper picolinate, copper 2-pyrazinecarboxylate, copper 2-ethylhexanoate, copper methacrylate, copper thiophene-2-carboxylate, copper methionine, and copper tartrate, and the fatty acid copper having 10 to 22 carbon atoms is preferably one or more of copper oleate, copper linoleate, copper stearate, copper rosinate, copper hexadecanoate, copper palmitate, and copper naphthenate.
- The copper carboxylate derivative is preferably a copper thiocarboxylate derivative [R'CS2]2Cu or a copper selenocarboxylate derivative [R'CSe2]2Cu, where, R' includes alkyl and alkyl derivatives; and preferably, the copper carboxylate derivative is copper N,N-di-n-butyldithiocarbamate (Cu(SC(S)N(C4H9)2)2) and/or copper N,N-din-butyldiselenocarbamate (Cu(SeC(Se)N(C4H9)2)2).
- The copper thiophosphate complex is preferably a copper complex of a dialkyldithiophosphate, and a general formula of the copper complex of the dialkyldithiophosphate is (RO)2P(S)SHM, where, R is alkyl or aryl, and M includes monovalent copper and divalent copper (CuDDP for short); and preferably, the copper thiophosphate complex is one or more of copper dihexyldithiophosphate, copper dibutyldithiophosphate, copper-containing antioxidant T541, and copper-containing antioxidant T542. The copper-containing antioxidant T541 and the copper-containing antioxidant T542 can be purchased from the additive factory of Jinzhou Petrochemical Corporation.
- Preferably, the grain diameter of the organocopper complex is less than 10 µm.
- In the present invention, preferably, the mass percentage of the organocopper complex in the additive is 20%, 22%, 23%, 25%, 27% or 30%.
- In the present invention, the plasticizer may be a conventional plasticizer in the art, preferably, the plasticizer is a phthalate and/or epoxidized soybean oil, and more preferably, the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate, and epoxidized soybean oil. Through the cooperation of the usage amount of the plasticizer and other components of the additive, the organocopper complex can be uniformly dispersed on the surface of powder, agglomeration between the organocopper complexes can be prevented, Cu is uniformly distributed at grain boundaries after the organocopper complex is decomposed, the grain boundary Cu concentration is basically equivalent to the intragranular Cu concentration, and the phenomenon of copper depletion at grain boundaries is avoided.
- In the present invention, preferably, the mass percentage of the plasticizer in the additive is 0.5%, 0.8% or 1%.
- In the present invention, the organic solvent may be a conventional organic solvent in the art, preferably, the organic solvent is one or more of acetone, toluene, mineral oil, methyl acetate, 120# solvent oil, isooctane, isopropanol, chloroform, and methyl methacrylate, and more preferably, the organic solvent is one or more of 120# solvent oil, toluene, mineral oil, acetone, isooctane, and isopropanol, such as 120# solvent oil, toluene, mineral oil, a mixed solvent of isooctane and isopropanol, and a mixed solvent of acetone and isopropanol.
- In the present invention, preferably, the mass percentage of the organic solvent in the additive is 69-79.5%.
- In the present invention, preferably, the additive is composed of 20-30% of organocopper complex, 0.5-1% of plasticizer, and 69-79.5% of organic solvent.
- The present invention also provides a preparation method of the above additive, which includes the following step:
mixing the organocopper complex, the plasticizer, and the organic solvent. - The present invention also provides application of the above additive in preparation of a samarium-cobalt magnet. The additive has the effects of lubricating and regulating and controlling grain boundaries of samarium-cobalt magnets, can improve the phenomenon of copper depletion at grain boundaries, and improve the remanence, coercivity, and squareness of magnets.
- The present invention also provides a preparation method of a samarium-cobalt 2: 17 type magnet, which includes the following steps: mixing samarium-cobalt magnet alloy powder with the above additive, shaping, sintering, and aging.
- The mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder is 0.1-0.2%.
- In the present invention, preferably, raw materials of the samarium-cobalt magnet alloy powder include Sm, Cu, Fe, Zr, and Co.
- Preferably, the mass percentage of Sm in the raw materials of the samarium-cobalt magnet alloy powder is 24-26% such as 24%, 25.5%, and 26%.
- Preferably, the mass percentage of Cu in the raw materials of the samarium-cobalt magnet alloy powder is 4-6% such as 4%, 5.5%, and 6%.
- Preferably, the mass percentage of Fe in the raw materials of the samarium-cobalt magnet alloy powder is 10-20% such as 10%, 17%, 19%, and 20%.
- Preferably, the mass percentage of Zr in the raw materials of the samarium-cobalt magnet alloy powder is 2.0-4% such as 2.0%, 3.5%, and 4%.
- Preferably, the mass percentage of Co in the raw materials of the samarium-cobalt magnet alloy powder is 45-60% such as 46%, 48%, 51.5%, and 56%.
- In a preferred embodiment of the present invention, the samarium-cobalt magnet alloy powder is composed of 24% of Sm, 4% of Cu, 17% of Fe, 3.5% of Zr, 51.5% of Co.
- In a preferred embodiment of the present invention, the samarium-cobalt magnet alloy powder is composed of 25.5% of Sm, 5.5% of Cu, 19% of Fe, 2% of Zr, and 48% of Co.
- In a preferred embodiment of the present invention, the samarium-cobalt magnet alloy powder is composed of 26% of Sm, 4% of Cu, 10% of Fe, 4% of Zr, and 56% of Co.
- In a preferred embodiment of the present invention, the samarium-cobalt magnet alloy powder is composed of 24% of Sm, 6% of Cu, 20% of Fe, 4% of Zr, and 46% of Co.
- Preferably, the samarium-cobalt magnet alloy powder is obtained by smelting and crushing the raw materials of the samarium-cobalt magnet alloy powder.
- Preferably, the smelting is performed by melt-spinning, centrifugal casting or ingot casting.
- Preferably, the crushing includes coarse crushing, secondary crushing, and fine crushing, wherein the coarse crushing is preferably Jaw crushing, the secondary crushing is preferably disc milling or crushing with an intermediate crusher, and the fine crushing is preferably jet milling or ball milling.
- Preferably, the grain diameter D50 of the samarium-cobalt magnet alloy powder is 4-6 µm.
- Preferably, the samarium-cobalt magnet alloy powder is mixed with the additive, and the mixture is dried to remove most of the solvent, shaped, sintered, and aged. The drying is preferably placing the powder in a dryer and drying at 80°C for 5-10 h such as 5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, and 10 h.
- In the present invention, preferably, the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder is 0.1%, 0.12%, 0.14%, 0.16%, 0.18% or 0.2%, and an addition amount of the additive is determined by the copper content in a selected substance and the solution concentration.
- In a preferred embodiment of the present invention, the additive is composed of 25% of copper naphthenate, 0.50% of epoxidized soybean oil, and 74.5% of 120# solvent oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 2.5%.
- In a preferred embodiment of the present invention, the additive is composed of 30% of copper oleate, 0.50% of epoxidized soybean oil, and 69.5% of 120# solvent oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.3%.
- In a preferred embodiment of the present invention, the additive is composed of 30% of copper hexadecanoate, 0.50% of dibutyl phthalate, and 69.5% of 120# solvent oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.6%.
- In a preferred embodiment of the present invention, the additive is composed of 27% of copper N,N-di-n-butyldithiocarbamate, 0.50% of dibutyl phthalate, and 72.5% of toluene; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.3%.
- In a preferred embodiment of the present invention, the additive is composed of 25% of copper dihexyldithiophosphate, 0.80% of epoxidized soybean oil, and 74.2% of toluene; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.4%.
- In a preferred embodiment of the present invention, the additive is composed of 22% of copper dibutyldithiophosphate, 0.80% of dioctyl phthalate, and 77.2% of mineral oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 2.4%.
- In a preferred embodiment of the present invention, the additive is composed of 23% of T541, 0.80% of dioctyl phthalate, and 76.2% of mineral oil; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.5%.
- In a preferred embodiment of the present invention, the additive is composed of 20% of copper acetylacetonate, 1% of epoxidized soybean oil, 40% of isooctane, and 39% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.7%.
- In a preferred embodiment of the present invention, the additive is composed of 23% of copper acetoacetate, 1% of epoxidized soybean oil, 40% of acetone, and 36% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 4.4%.
- In a preferred embodiment of the present invention, the additive is composed of 20% of copper hexadecanoate, 1% of epoxidized soybean oil, 40% of isooctane, and 39% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 8.1%.
- In a preferred embodiment of the present invention, the additive is composed of 23% of copper oleate, 1% of epoxidized soybean oil, 40% of acetone, and 36% of isopropanol; and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 8.7%.
- In the present invention, the shaping operation and conditions may be conventional in the art, and preferably, the shaping is oriented compression shaping performed in a static magnetic field.
- Preferably, the magnetic field strength B for shaping is 1.5-2 T.
- In the present invention, the sintering operation and conditions are conventional in the art.
- Preferably, the sintering is performed in an inert atmosphere.
- Preferably, the sintering temperature is 1200-1220°C such as 1200°C, 1210°C, 1215°C, and 1220°C.
- Preferably, the sintering time is 1-5 h such as 1 h, 3 h, 4 h, and 5 h.
- In the present invention, preferably, solution treatment is performed after sintering.
- Preferably, the solution treatment temperature is 1140-1190°C such as 1140°C, 1150°C, 1160°C, and 1190°C.
- Preferably, the solution treatment time is 5-40 h such as 5 h, 20 h, 35 h, and 40 h.
- In the present invention, the aging operation and conditions are conventional in the art.
- Preferably, the aging is keeping at 800-900°C (e.g., 810°C, 840°C, 860°C, and 900°C) for 5-20 h (e.g., 5 h, 15 h, and 20 h), cooling to 400°C, and keeping for 5-10 h (e.g., 5 h, 6 h, 7 h, and 10 h).
- Preferably, the cooling is performed at a rate of 0.7°C/min.
- The present invention also provides a samarium-cobalt 2: 17 type magnet, which is prepared by the above preparation method of a samarium-cobalt 2: 17 type magnet.
- The present invention also provides a samarium-cobalt 2: 17 type magnet, in which the grain boundary Cu concentration is basically equivalent to the intragranular Cu concentration.
- In the present invention, preferably, the grain boundary Cu concentration in the samarium-cobalt 2: 17 type magnet is 3-5.6%, the intragranular Cu concentration in the samarium-cobalt 2: 17 type magnet is 3.2-6%, the percentage is the percentage of atoms, and the intragranular and grain boundary Cu concentrations are distributed uniformly.
- On the basis of conforming to common knowledge in the art, the above preferred conditions can be combined arbitrarily to obtain preferred embodiments of the present invention.
- The reagents and materials used in the present invention are all commercially available.
- The present invention has the following positive progressive effects.
- The method of using an additive containing an organocopper complex to regulate and control grain boundaries is easy to operate, does not require extra process procedures, and does not have special requirements for the shape and size of a product, so it is suitable for batch production. Compared to a product prepared by the conventional method, a finally obtained product has basically equivalent remanence, the coercivity is increased by 5-10 kOe, Hk is increased by 1-4 kOe, and the squareness can reach 60-75%.
-
-
Fig. 1 is a comparison curve diagram of magnetic properties of samples of Example 4 andContrast 4; -
Fig. 2 is a scanning image of a distributive area of Cu at grain boundaries of the sample ofContrast 4; -
Fig. 3 is a scanning image of a distributive area of Cu at grain boundaries of the sample of Example 4; -
Fig. 4 is a line scanning image of the grain boundary Cu concentration in the sample ofContrast 4; and -
Fig. 5 is a line scanning image of the grain boundary Cu concentration in the sample of Example 4. - The present invention will be further described below with reference to examples, but the present invention is not limited to the range of the examples. Experimental methods that do not indicate specific conditions in the following examples follow conventional methods and conditions or product manuals.
-
- (1) Raw materials of samarium-cobalt magnet alloy powder shown in Table 1 were smelted and crushed to obtain samarium-cobalt magnet alloy powder, and the grain diameter D50 of the samarium-cobalt magnet alloy powder was 4-6 µm.
- The smelting was performed by melt-spinning, centrifugal casting or ingot casting; the crushing was coarse crushing, secondary crushing, and fine crushing that were performed in sequence, the coarse crushing was Jaw crushing, the secondary crushing was disc milling or crushing with an intermediate crusher; and the fine crushing was jet milling.
- (2) The samarium-cobalt magnet alloy powder obtained at step (1) was mixed with an additive shown in Table 2, and the mixture was dried by using a dryer in a 99.99% N2 atmosphere at 80°C for a period of time shown in Table 1. Then, the mixture was shaped, sintered, and aged. An addition amount of the additive was determined by a set effective addition amount of Cu (the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder) and the solution concentration, see Table 1.
- The fine crushing was jet milling or ball milling. Oriented compression shaping was performed in a static magnetic field. The magnetic field strength for shaping, the sintering temperature and time, solution treatment temperature and time, and aging operation are shown in Table 3. The cooling in the aging was performed at a rate of 0.7°C/min.
Table 1 Raw materials of samarium-cobalt magnet alloy powders of examples and contrasts Samarium-cobalt magnet alloy powder (mass percentage) Mass percentage of additive in samarium-cobalt magnet alloy powder / % Drying time / h Sm Cu Fe Zr Co Example 1 24 4 17 3.5 balance 2.5 5 Example 2 24 4 17 3.5 balance 3.3 6 Example 3 24 4 17 3.5 balance 3.6 7.5 Example 4 25.5 5.5 19 2 balance 3.3 6 Example 5 25.5 5.5 19 2 balance 3.4 6.5 Example 6 25.5 5.5 19 2 balance 2.4 5 Example 7 26 4 10 4 balance 3.5 7 Example 8 26 4 10 4 balance 3.7 8 Example 9 24 6 20 4 balance 4.4 10 Example 10 26 4 10 4 balance 8.1 8 Example 11 24 6 20 4 balance 8.7 10 Contrast 1 24 4 17 3.5 balance 0.4 5 Contrast 2 24 4 17 3.5 balance 0.3 6 Contrast 3 24 4 17 3.5 balance 0.4 7.5 Contrast 4 25.5 5.5 19 2 balance 0.4 6 Contrast 5 25.5 5.5 19 2 balance 0.14 6.5 Contrast 6 25.5 5.5 19 2 balance 0.14 5 Contrast 7 26 4 10 4 balance 0.16 7 Contrast 8 26 4 10 4 balance 1.6 8 Contrast 9 24 6 20 4 balance 11 10 Contrast 10 24 6 20 4 balance 4.4 10 Table 2 Components of additives of examples and contrasts and mass percentages thereof Organocopper complex Plasticizer Solvent Effective addition amount of Cu/% Variety Cu content/% Usage amount/% Variety Usage amount/% Variety Usage amount /% Example 1 Copper naphthenate 15.7 25 Epoxidized soybean oil 0.5 120# solvent oil balance 0.1 Example 2 Copper oleate 10 30 Epoxidized soybean oil 0.5 120# solvent oil balance 0.1 Example 3 Copper hexadecanoate 11.08 30 Dibutyl phthalate 0.5 120# solvent oil balance 0.12 Example 4 Copper N,N-di-n-butyldithiocarbamate 13.5 27 Dibutyl phthalate 0.5 Toluene balance 0.12 Example 5 Copper dihexyldithiophosphate 16.5 25 Epoxidized soybean oil 0.8 Toluene balance 0.14 Example 6 Copper dibutyldithiophosphate 26.2 22 Dioctyl phthalate 0.8 Mineral oil balance 0.14 Example 7 T541 about 20 23 Dioctyl phthalate 0.8 Mineral oil balance 0.16 Example 8 Copper acetylacetonate 24.3 20 Epoxidized soybean oil 1 Isooctane 40% 0.18 Isopropanol balance Example 9 Copper acetoacetate 19.7 23 Epoxidized soybean oil 1 Acetone 40% 0.2 Isopropanol balance Example 10 Copper hexadecanoate 11.08 20 Epoxidized soybean oil 1 Isooctane 40% 0.18 Isopropanol balance Example 11 Copper oleate 10 23 Epoxidized soybean oil 1 Acetone 40% 0.2 Isopropanol balance Contrast 1 conventional lubricant (butyl oleate) 0 25 / / 120# solvent oil balance 0 Contrast 2 conventional lubricant (butyl oleate) 0 30 / / 120# solvent oil balance 0 Contrast 3 conventional lubricant (methyl decanoate) 0 30 / / 120# solvent oil balance 0 Contrast 4 conventional lubricant (poly(α-olefin)) 0 27 / / Toluene balance 0 Contrast 5 Copper dihexyldithiophosphate 16.5 / / / / / 0.14 Contrast 6 Copper dibutyldithiophosphate 26.2 / / / / / 0.14 Contrast 7 T541 about 20 / / / / / 0.16 Contrast 8 Copper acetylacetonate 24.3 13 Epoxidized soybean oil 1 Isooctane 40% 0.05 Isopropanol balance Contrast 9 Copper acetoacetate 19.7 23 Epoxidized soybean oil 1 Acetone 40% 0.5 Isopropa nol balan ce Contrast 10 Copper acetoacetate 19.7 23 / / Acetone 40% 0.2 Isopropanol balance Table 3 Parameters of shaping, sintering, solution treatment, and aging of examples and contrasts Magnetic field strength for shaping Sintering Solution Treatment Aging Temperature Time Temperature Time Example 1 1.5T 1210 3 1160 20 keep at 840°C for 20 h, cool to 400°C, and keep for 6 h Example 2 1.5T 1210 3 1160 20 keep at 840°C for 20 h, cool to 400°C, and keep for 6 h Example 3 1.5T 1210 3 1160 20 keep at 840°C for 20 h, cool to 400°C, and keep for 6 h Example 4 1.5T 1215 4 1150 35 keep at 860°C for 15 h, cool to 400°C, and keep for 7 h Example 5 1.5T 1215 4 1150 35 keep at 860°C for 15 h, cool to 400°C, and keep for 7 h Example 6 1.5T 1215 4 1150 35 keep at 860°C for 15 h, cool to 400°C, and keep for 7 h Example 7 2.0T 1200 1 1190 5 keep at 810°C for 20 h, cool to 400°C, and keep for 10 h Example 8 2.0T 1200 1 1190 5 keep at 810°C for 20 h, cool to 400°C, and keep for 10 h Example 9 2.0T 1220 5 1140 40 keep at 900°C for 5 h, cool to 400°C, and keep for 5 h Example 10 2.0T 1200 1 1190 5 keep at 810°C for 20 h, cool to 400°C, and keep for 10 h Example 11 2.0T 1220 5 1140 40 keep at 900°C for 5 h, cool to 400°C, and keep for 5 h Contrast 1 1.5T 1210 3 1160 20 keep at 840°C for 20 h, cool to 400°C, and keep for 6 h Contrast 2 1.5T 1210 3 1160 20 keep at 840°C for 20 h, cool to 400°C, and keep for 6 h Contrast 3 1.5T 1210 3 1160 20 keep at 840°C for 20 h, cool to 400°C, and keep for 6 h Contrast 4 1.5T 1215 4 1150 35 keep at 860°C for 15 h, cool to 400°C, and keep for 7 h Contrast 5 1.5T 1215 4 1150 35 keep at 860°C for 15 h, cool to 400°C, and keep for 7 h Contrast 6 1.5T 1215 4 1150 35 keep at 860°C for 15 h, cool to 400°C, and keep for 7 h Contrast 7 2.0T 1200 1 1190 5 keep at 810°C for 20 h, cool to 400°C, and keep for 10 h Contrast 8 2.0T 1200 1 1190 5 keep at 810°C for 20 h, cool to 400°C, and keep for 10 h Contrast 9 2.0T 1220 5 1140 40 keep at 900°C for 5 h, cool to 400°C, and keep for 5 h Contrast 10 2.0T 1220 5 1140 40 keep at 900°C for 5 h, cool to 400°C, and keep for 5 h - Samarium-cobalt magnet alloy powder raw materials and additives were prepared according to the formulas shown in Tables 1 and 2, and other process conditions were the same as those in Example 1 in addition to the operation parameters shown in Table 3.
- The additives of
Contrasts 1 to 4 contained a lubricant and an organic solvent only; the additives ofContrasts 5 to 7 contained an organocopper complex only; and the additive ofContrast 10 contained an organocopper complex and an organic solvent only. - Magnetic properties, i.e., the remanence Br, the intrinsic coercivity Hcj, a knee point Hk, the squareness Hk/Hcj, and the maximum magnetic energy product (BH)max, of the examples and the contrasts of the present invention were detected by using a pulse magnetic field meter (PFM). Results are shown in Table 4.
Table 4 Data of magnetic properties of examples and contrasts Br (kGs) Hcj (kOe) Hk (kOe) Hk/Hcj (%) BHmax (MGOe) Example 1 11.52 32.44 19.47 60.00 32.88 Example 2 11.53 33.01 19.89 60.25 32.92 Example 3 11.60 34.56 21.55 62.36 33.02 Example 4 11.94 26.23 16.98 64.74 33.14 Example 5 11.93 26.85 17.79 66.26 33.25 Example 6 11.93 27.88 18.56 66.57 33.52 Example 7 10.04 29.88 21.51 72 24.55 Example 8 10.05 32.25 23.86 74 25.24 Example 9 12.16 27.53 20.65 75 34.71 Example 10 10.02 30.25 20.82 68.8 24.84 Example 11 12.11 25.93 18.75 72.3 34.33 Contrast 111.48 23.88 14.52 60.80 31.52 Contrast 211.49 23.91 14.66 61.31 31.61 Contrast 3 11.52 24.62 14.63 59.42 31.58 Contrast 411.93 22.56 12.20 54.08 33.02 Contrast 511.86 24.21 12.18 50.31 32.84 Contrast 6 11.87 24.56 12.14 49.43 32.86 Contrast 7 9.98 21.89 12.24 55.92 24.01 Contrast 89.84 24.15 13.32 55.16 23.71 Contrast 9 12.01 11.52 3.01 26.1 27.94 Contrast 1012.03 21.36 11.75 55 33.21 - As shown in
Fig. 1 to Fig. 5 , in the sample of Example 4, Cu is distributed uniformly at grain boundaries, and the grain boundary Cu concentration is basically equivalent to the intragranular Cu concentration, so that the phenomenon of copper depletion at grain boundaries is avoided. With regard to product performance, compared to the samples prepared by the conventional method, the samples of the examples have basically equivalent remanence, the coercivity is increased by 5-10 kOe, Hk is increased by 1-4 kOe, and the squareness can reach 60-75%.
Claims (10)
- An additive, characterized by comprising the following components by mass percentage: 20-30% of organocopper complex, 0.5-1% of plasticizer, and an organic solvent, the sum of the mass percentages of the components being 100%,
the organocopper complex being an oil-soluble substance, the mass percentage of Cu in the organocopper complex being greater than 10%, the organocopper complex containing a polar group and/or an alkyl chain having more than 3 C atoms. - The additive according to claim 1, characterized in that the additive satisfies one or more of the following conditions:(1) the polar group in the organocopper complex is one or more of a hydroxyl group, a carboxyl group, an amino group, an ester group, and an amide group;(2) the organocopper complex is one or more of a substituted copper carboxylate complex, a copper carboxylate derivative, a copper thiophosphate complex, copper quinoline, copper hydroxyquinoline, copper phthalate, thiodiazole copper, copper acetylacetonate, and copper acetoacetate;a general formula of the substituted copper carboxylate complex is preferably [RCO2]2Cu, where, R is alkyl, alkynyl, cyclo, aryl or heteroaryl; preferably, the substituted copper carboxylate complex is one or more of fatty acid copper having 10 to 22 carbon atoms, copper styrene maleate, copper picolinate, copper 2-pyrazinecarboxylate, copper 2-ethylhexanoate, copper methacrylate, copper thiophene-2-carboxylate, copper methionine, and copper tartrate, and the fatty acid copper having 10 to 22 carbon atoms is preferably one or more of copper oleate, copper linoleate, copper stearate, copper rosinate, copper hexadecanoate, copper palmitate, and copper naphthenate;the copper carboxylate derivative is preferably a copper thiocarboxylate derivative [R'CS2]2Cu or a copper selenocarboxylate derivative [R'CSe2]2Cu, where, R' comprises alkyl and alkyl derivatives; and preferably, the copper carboxylate derivative is copper N,N-di-n-butyldithiocarbamate and/or copper N,N-di-n-butyldiselenocarbamate;the copper thiophosphate complex is preferably a copper complex of a dialkyldithiophosphate, and a general formula of the copper complex of the dialkyldithiophosphate is (RO)2P(S)SHM, where, R is alkyl or aryl, and M comprises monovalent copper and divalent copper; and preferably, the copper thiophosphate complex is one or more of copper dihexyldithiophosphate, copper dibutyldithiophosphate, copper-containing antioxidant T541, and copper-containing antioxidant T542;(3) the grain diameter of the organocopper complex is less than 10 µm;(4) the mass percentage of the organocopper complex in the additive is 20%, 22%, 23%, 25%, 27% or 30%;(6) the plasticizer is a phthalate and/or epoxidized soybean oil, and preferably, the plasticizer is one or more of dibutyl phthalate, dioctyl phthalate, and epoxidized soybean oil;(7) the mass percentage of the plasticizer in the additive is 0.5%, 0.8% or 1%;(8) the organic solvent is one or more of acetone, toluene, mineral oil, methyl acetate, 120# solvent oil, isooctane, isopropanol, chloroform, and methyl methacrylate, preferably, the organic solvent is one or more of 120# solvent oil, toluene, mineral oil, acetone, isooctane, and isopropanol, and more preferably, the organic solvent is 120# solvent oil, toluene, mineral oil, a mixed solvent of isooctane and isopropanol, or a mixed solvent of acetone and isopropanol;(9) the mass percentage of the organic solvent in the additive is 69-79.5%; and(10) the additive is composed of 20-30% of organocopper complex, 0.5-1% of plasticizer, and 69-79.5% of organic solvent.
- Application of the additive according to claim 1 or 2 in preparation of a samarium-cobalt magnet.
- A preparation method of a samarium-cobalt 2: 17 type magnet, characterized by comprising: mixing samarium-cobalt magnet alloy powder with the additive according to claim 1 or 2, shaping, sintering, and aging,
the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder being 0.1-0.2%. - The preparation method of a samarium-cobalt 2: 17 type magnet according to claim 4, characterized in that the preparation method of a samarium-cobalt 2: 17 type magnet satisfies one or more of the following conditions:(1) raw materials of the samarium-cobalt magnet alloy powder comprise Sm, Cu, Fe, Zr, and Co;preferably, the mass percentage of Sm in the raw materials of the samarium-cobalt magnet alloy powder is 24-26% such as 24%, 25.5%, and 26%;preferably, the mass percentage of Cu in the raw materials of the samarium-cobalt magnet alloy powder is 4-6% such as 4%, 5.5%, and 6%;preferably, the mass percentage of Fe in the raw materials of the samarium-cobalt magnet alloy powder is 10-20% such as 10%, 17%, 19%, and 20%;preferably, the mass percentage of Zr in the raw materials of the samarium-cobalt magnet alloy powder is 2.0-4% such as 2.0%, 3.5%, and 4%; andpreferably, the mass percentage of Co in the raw materials of the samarium-cobalt magnet alloy powder is 45-60% such as 46%, 48%, 51.5%, and 56%;(2) the samarium-cobalt magnet alloy powder is obtained by melting and crushing the raw materials of the samarium-cobalt magnet alloy powder;(3) the grain diameter D50 of the samarium-cobalt magnet alloy powder is 4-6 µm; and(4) the samarium-cobalt magnet alloy powder is mixed with the additive, and the mixture is dried, shaped, sintered, and aged.
- The preparation method of a samarium-cobalt 2: 17 type magnet according to claim 5, characterized in that the preparation method of a samarium-cobalt 2: 17 type magnet satisfies one or more of the following conditions:(1) the samarium-cobalt magnet alloy powder is composed of 24% of Sm, 4% of Cu, 17% of Fe, 3.5% of Zr, and 51.5% of Co;or, the samarium-cobalt magnet alloy powder is composed of 25.5% of Sm, 5.5% of Cu, 19% of Fe, 2% of Zr, and 48% of Co;or, the samarium-cobalt magnet alloy powder is composed of 26% of Sm, 4% of Cu, 10% of Fe, 4% of Zr, and 56% of Co;or, the samarium-cobalt magnet alloy powder is composed of 24% of Sm, 6% of Cu, 20% of Fe, 4% of Zr, and 46% of Co;(2) the smelting is performed by melt-spinning, centrifugal casting or ingot casting;(3) the crushing comprises coarse crushing, secondary crushing, and fine crushing, the coarse crushing is preferably Jaw crushing, the secondary crushing is preferably disc milling or crushing with an intermediate crusher, and the fine crushing is preferably jet milling or ball milling; and(4) the drying is placing the powder in a dryer and drying at 80°C for 5-10 h, and the drying time is preferably 5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h or 10 h.
- The preparation method of a samarium-cobalt 2: 17 type magnet according to claim 4, characterized in that the preparation method of a samarium-cobalt 2: 17 type magnet satisfies one or more of the following conditions:(1) the mass percentage of Cu in the organocopper complex in the samarium-cobalt magnet alloy powder is 0.1%, 0.12%, 0.14%, 0.16%, 0.18% or 0.2%;(2) the additive is composed of 25% of copper naphthenate, 0.50% of epoxidized soybean oil, and 74.5% of 120# solvent oil, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 2.5%;or, the additive is composed of 30% of copper oleate, 0.50% of epoxidized soybean oil, and 69.5% of 120# solvent oil, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.3%;or, the additive is composed of 30% of copper hexadecanoate, 0.50% of dibutyl phthalate, and 69.5% of 120# solvent oil, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.6%;or, the additive is composed of 27% of copper N,N-di-n-butyldithiocarbamate, 0.50% of dibutyl phthalate, and 72.5% of toluene, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.3%;or, the additive is composed of 25% of copper dihexyldithiophosphate, 0.80% of epoxidized soybean oil, and 74.2% of toluene, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.4%;or, the additive is composed of 22% of copper dibutyldithiophosphate, 0.80% of dioctyl phthalate, and 77.2% of mineral oil, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 2.4%;or, the additive is composed of 23% of T541, 0.80% of dioctyl phthalate, and 76.2% of mineral oil, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.5%;or, the additive is composed of 20% of copper acetylacetonate, 1% of epoxidized soybean oil, 40% of isooctane, and 39% of isopropanol, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 3.7%;or, the additive is composed of 23% of copper acetoacetate, 1% of epoxidized soybean oil, 40% of acetone, and 36% of isopropanol, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 4.4%;or, the additive is composed of 20% of copper hexadecanoate, 1% of epoxidized soybean oil, 40% of isooctane, and 39% of isopropanol, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 8.1%;or, the additive is composed of 23% of copper oleate, 1% of epoxidized soybean oil, 40% of acetone, and 36% of isopropanol, and the mass percentage of the additive in the samarium-cobalt magnet alloy powder is preferably 8.7%.
- The preparation method of a samarium-cobalt 2: 17 type magnet according to claim 4, characterized in that the preparation method of a samarium-cobalt 2: 17 type magnet satisfies one or more of the following conditions:(1) the magnetic field strength B for shaping is 1.5-2 T;(2) the sintering is performed in an inert atmosphere;(3) the sintering temperature is 1200-1220°C such as 1200°C, 1210°C, 1215°C, and 1220°C;(4) the sintering time is 1-5 h such as 1 h, 3 h, 4 h, and 5 h;(5) solution treatment is performed after sintering,preferably, the solution treatment temperature is 1140-1190°C such as 1140°C, 1150°C, 1160°C, and 1190°C;preferably, the solution treatment time is 5-40 h such as 5 h, 20 h, 35 h, and 40 h, and(6) the aging is keeping at 800-900°C for 5-20 h, cooling to 400°C, and keeping for 5-10 h,
preferably, the cooling is performed at a rate of 0.7°C/min. - A samarium-cobalt 2: 17 type magnet, characterized by being prepared by the preparation method of a samarium-cobalt 2: 17 type magnet according to any one of claims 4 to 8.
- A samarium-cobalt 2: 17 type magnet, characterized in that the grain boundary Cu concentration in the samarium-cobalt 2: 17 type magnet is basically equivalent to the intragranular Cu concentration, and
preferably, the grain boundary Cu concentration in the samarium-cobalt 2: 17 type magnet is 3-5.6%, the intragranular Cu concentration in the samarium-cobalt 2: 17 type magnet is 3.2-6%, and the percentage is the percentage of atoms.
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CN111145973A (en) | 2018-11-06 | 2020-05-12 | 中国科学院宁波材料技术与工程研究所 | Samarium-cobalt permanent magnet containing grain boundary phase and preparation method thereof |
CN111370191A (en) * | 2020-03-20 | 2020-07-03 | 杭州永磁集团有限公司 | Heavy rare earth element-free samarium-cobalt permanent magnet material with low coercive force temperature coefficient and high temperature and preparation method thereof |
US20200243233A1 (en) * | 2019-01-28 | 2020-07-30 | Baotou Tianhe Magnetics Technology Co., Ltd. | Samarium-Cobalt Magnets And Method For Preparing The Same |
US20200243232A1 (en) * | 2015-10-08 | 2020-07-30 | Kyushu Institute Of Technology | Rare earth-cobalt permanent magnet |
US20210079248A1 (en) * | 2014-06-19 | 2021-03-18 | National Research Council Of Canada | Molecular inks |
CN113593882A (en) * | 2021-07-21 | 2021-11-02 | 福建省长汀卓尔科技股份有限公司 | 2-17 type samarium-cobalt permanent magnet material and preparation method and application thereof |
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US20200243232A1 (en) * | 2015-10-08 | 2020-07-30 | Kyushu Institute Of Technology | Rare earth-cobalt permanent magnet |
CN111145973A (en) | 2018-11-06 | 2020-05-12 | 中国科学院宁波材料技术与工程研究所 | Samarium-cobalt permanent magnet containing grain boundary phase and preparation method thereof |
US20200243233A1 (en) * | 2019-01-28 | 2020-07-30 | Baotou Tianhe Magnetics Technology Co., Ltd. | Samarium-Cobalt Magnets And Method For Preparing The Same |
CN111370191A (en) * | 2020-03-20 | 2020-07-03 | 杭州永磁集团有限公司 | Heavy rare earth element-free samarium-cobalt permanent magnet material with low coercive force temperature coefficient and high temperature and preparation method thereof |
CN113593882A (en) * | 2021-07-21 | 2021-11-02 | 福建省长汀卓尔科技股份有限公司 | 2-17 type samarium-cobalt permanent magnet material and preparation method and application thereof |
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