JP2017210664A - Production method of magnet alloy powder - Google Patents
Production method of magnet alloy powder Download PDFInfo
- Publication number
- JP2017210664A JP2017210664A JP2016105411A JP2016105411A JP2017210664A JP 2017210664 A JP2017210664 A JP 2017210664A JP 2016105411 A JP2016105411 A JP 2016105411A JP 2016105411 A JP2016105411 A JP 2016105411A JP 2017210664 A JP2017210664 A JP 2017210664A
- Authority
- JP
- Japan
- Prior art keywords
- alloy powder
- organic solvent
- magnet alloy
- phosphoric acid
- mol
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 109
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 96
- 239000000956 alloy Substances 0.000 title claims abstract description 96
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000003960 organic solvent Substances 0.000 claims abstract description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 238000010298 pulverizing process Methods 0.000 claims abstract description 18
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 12
- 239000011651 chromium Substances 0.000 claims abstract description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 32
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 239000007800 oxidant agent Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 12
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 9
- 229910001004 magnetic alloy Inorganic materials 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000000593 degrading effect Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 33
- 239000011347 resin Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 16
- 230000007423 decrease Effects 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000009467 reduction Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- -1 rare earth phosphate Chemical class 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- NZEDMAWEJPYWCD-UHFFFAOYSA-N 3-prop-2-enylsulfonylprop-1-ene Chemical compound C=CCS(=O)(=O)CC=C NZEDMAWEJPYWCD-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920003233 aromatic nylon Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- OJKANDGLELGDHV-UHFFFAOYSA-N disilver;dioxido(dioxo)chromium Chemical compound [Ag+].[Ag+].[O-][Cr]([O-])(=O)=O OJKANDGLELGDHV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-N manganese(2+);dihydrate Chemical compound O.O.[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-N 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
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- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- BJRVEOKYZKROCC-UHFFFAOYSA-K samarium(3+);phosphate Chemical compound [Sm+3].[O-]P([O-])([O-])=O BJRVEOKYZKROCC-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
Abstract
Description
本発明は、磁石合金粉の製造方法に関するものであり、より詳しくは、高温に加熱された際の保磁力の低下が少ない磁石合金粉の製造方法に関する。 The present invention relates to a method for producing a magnet alloy powder, and more particularly to a method for producing a magnet alloy powder with little reduction in coercive force when heated to a high temperature.
希土類磁石は、フェライト磁石、アルニコ磁石等と同様に、モーターをはじめとする様々な用途に用いられている磁石材料である。一般に、これらの磁石は焼結により製造されるため、複雑形状への成形が困難である。それに加え、焼結時の収縮が１５％〜２０％ほどあるため、寸法精度の高い製品が得られない。 Rare earth magnets are magnet materials used for various applications including motors, like ferrite magnets and alnico magnets. Generally, since these magnets are manufactured by sintering, it is difficult to form them into complicated shapes. In addition, since the shrinkage during sintering is about 15% to 20%, a product with high dimensional accuracy cannot be obtained.
これらの欠点を解決するため、近年では、ボンド磁石の開発が進められている。ボンド磁石では、ポリアミド樹脂やポリフェニレンサルファイド樹脂をバインダーとして用いることで、磁石粉を固めて成形を行う。しかしながら、希土類元素を含む鉄系磁石粉を用いたボンド磁石では、成形時における加熱による磁気特性の低下が問題となっている。また、ボンド磁石は、その用途に応じて１００℃以上の高温に晒されることがあり、そのような使用時に高温環境に曝されることによる磁気特性の低下も問題となっている。 In recent years, bond magnets have been developed to solve these drawbacks. Bonded magnets are formed by solidifying magnet powder by using polyamide resin or polyphenylene sulfide resin as a binder. However, in a bonded magnet using iron-based magnet powder containing a rare earth element, there is a problem of deterioration of magnetic properties due to heating during molding. Moreover, the bond magnet may be exposed to a high temperature of 100 ° C. or higher depending on its use, and there is also a problem of deterioration of magnetic properties due to exposure to a high temperature environment during such use.
そこで、その磁気特性の低下を改善するために、成形体表面に熱硬化性樹脂等によるコーティングを施すことや、例えば特許文献１に開示されているように、リン酸塩含有塗料によるコーティングを施す方法が提案されているが、保磁力等の観点からすると、十分な特性は得られていない。 Therefore, in order to improve the deterioration of the magnetic properties, the surface of the molded body is coated with a thermosetting resin or the like, for example, as disclosed in Patent Document 1, a coating with a phosphate-containing paint is performed. Although a method has been proposed, sufficient characteristics have not been obtained from the viewpoint of coercive force and the like.
現在のところ、特許文献２に開示されているように、希土類元素を含む鉄系磁石粉を有機溶媒中で粉砕して磁石粉を製造する際に、有機溶剤にリン酸を添加するという方法が、高温に加熱した際の磁気特性の低下を防止するのに有効であるとされている。この方法によれば、磁石粉表面にリン酸鉄を含む皮膜が形成され、加熱条件下での保磁力の低下が抑制された磁石粉を製造することができる。 At present, as disclosed in Patent Document 2, when producing magnet powder by pulverizing iron-based magnet powder containing rare earth elements in an organic solvent, there is a method of adding phosphoric acid to the organic solvent. It is said that it is effective to prevent the deterioration of magnetic properties when heated to a high temperature. According to this method, it is possible to produce magnet powder in which a film containing iron phosphate is formed on the surface of the magnet powder, and the decrease in coercive force under heating conditions is suppressed.
しかしながら、さらなる用途拡大にあたっては、高温環境下において、保磁力の低下をさらに抑制することが求められている。 However, for further application expansion, it is required to further suppress the decrease in coercive force in a high temperature environment.
本発明は、上述した事情に鑑みなされたものであり、ボンド磁石の製造工程あるいはボンド磁石としての使用時に高温に加熱されたとしても、加熱後の室温での保磁力の低下を抑制した磁石合金粉の製造方法を提供することを目的とする。 The present invention has been made in view of the above-described circumstances, and even if heated to a high temperature during the manufacturing process of a bonded magnet or used as a bonded magnet, a magnet alloy that suppresses a decrease in coercive force at room temperature after heating. It aims at providing the manufacturing method of powder.
本発明者は、上述した課題を解決するために鋭意検討を重ねた。その結果、鉄系磁石合金粉を粉砕するに際して、リン酸を含む有機溶媒のｐＨ、リン酸濃度を特定の範囲に調整するとともに、チタン、バナジウム、クロム、マンガン、アルミニウム、シリコン、銅、亜鉛、及びモリブデンからなる群から選ばれる元素を含む化合物のうちの１種以上をその有機溶媒中に特定の割合で添加した状態で粉砕することにより、加熱後の室温での保磁力の低下を抑えることができることを見出し、本発明を完成するに至った。 This inventor repeated earnest examination in order to solve the subject mentioned above. As a result, when pulverizing the iron-based magnet alloy powder, the pH of the organic solvent containing phosphoric acid, the phosphoric acid concentration is adjusted to a specific range, and titanium, vanadium, chromium, manganese, aluminum, silicon, copper, zinc, And reducing the coercive force at room temperature after heating by pulverizing one or more of compounds containing an element selected from the group consisting of molybdenum and added in a specific ratio to the organic solvent. As a result, the present invention has been completed.
（１）本発明の第１の発明は、希土類元素を含む鉄系磁石合金粉を、リン酸を含む有機溶媒中で粉砕して磁石合金粉を製造する方法であって、前記鉄系磁石合金粉を粉砕するに際して、前記リン酸を含む有機溶媒のｐＨを１．５以上８．０以下とし、該有機溶媒中のリン酸濃度を０．１体積％以上２０体積％以下とし、かつ、チタン、バナジウム、クロム、マンガン、アルミニウム、シリコン、銅、亜鉛、及びモリブデンからなる群から選ばれる元素を含む化合物のうちの１種以上を該有機溶媒中の濃度として０．００１ｍｏｌ／Ｌ以上１０ｍｏｌ／Ｌ以下で添加する、磁石合金粉の製造方法である。 (1) A first aspect of the present invention is a method for producing a magnet alloy powder by pulverizing an iron-based magnet alloy powder containing a rare earth element in an organic solvent containing phosphoric acid, the iron-based magnet alloy When pulverizing the powder, the pH of the organic solvent containing phosphoric acid is 1.5 or more and 8.0 or less, the phosphoric acid concentration in the organic solvent is 0.1 vol% or more and 20 vol% or less, and titanium One or more of compounds containing an element selected from the group consisting of vanadium, chromium, manganese, aluminum, silicon, copper, zinc, and molybdenum is 0.001 mol / L or more and 10 mol / L as a concentration in the organic solvent. It is the manufacturing method of the magnet alloy powder added below.
（２）本発明の第２の発明は、第１の発明において、前記リン酸を含む有機溶媒のｐＨを４．０以上５．０以下とする、磁石合金粉の製造方法である。 (2) The second invention of the present invention is the method for producing magnet alloy powder according to the first invention, wherein the pH of the organic solvent containing phosphoric acid is 4.0 or more and 5.0 or less.
（３）本発明の第３の発明は、第１又は第２の発明において、前記クロムを含む化合物である酸化クロム（ＶＩ）、前記マンガンを含む化合物であるマンガンアセチルアセトナート、及び前記アルミニウムを含む化合物であるアルミニウムアセチルアセトナートのうちのいずれか１種以上を添加する、磁石合金粉の製造方法である。 (3) According to a third aspect of the present invention, in the first or second aspect, the chromium (VI) oxide which is a compound containing chromium, the manganese acetylacetonate which is a compound containing manganese, and the aluminum It is a manufacturing method of magnet alloy powder which adds any 1 or more types of aluminum acetylacetonate which is a compound to contain.
（４）本発明の第４の発明は、第１乃至第３のいずれかの発明において、前記有機溶媒に、酸化剤を該有機溶媒中の濃度として０．０００１ｍｏｌ／Ｌ以上１．０ｍｏｌ／Ｌ以下で添加する、磁石合金粉の製造方法である。 (4) According to a fourth aspect of the present invention, in any one of the first to third aspects, the organic solvent has an oxidizing agent in a concentration of 0.0001 mol / L to 1.0 mol / L in the organic solvent. It is the manufacturing method of the magnet alloy powder added below.
（５）本発明の第５の発明は、第４の発明において、前記酸化剤として、硝酸を添加する、磁石合金粉の製造方法である。 (5) The fifth invention of the present invention is the method for producing magnet alloy powder according to the fourth invention, wherein nitric acid is added as the oxidizing agent.
（６）本発明の第６の発明は、第１乃至第５のいずれかの発明において、前記有機溶媒として、分子量１００以下の有機化合物を用いる、磁石合金粉の製造方法である。 (6) A sixth invention of the present invention is the method for producing a magnet alloy powder in any one of the first to fifth inventions, wherein an organic compound having a molecular weight of 100 or less is used as the organic solvent.
（７）本発明の第７の発明は、第６の発明において、前記有機溶媒として、比誘電率が１０以上５０以下である有機溶媒を用いる、磁石合金粉の製造方法である。 (7) The seventh invention of the present invention is the method for producing magnet alloy powder according to the sixth invention, wherein an organic solvent having a relative dielectric constant of 10 or more and 50 or less is used as the organic solvent.
（８）本発明の第８の発明は、第７の発明において、前記有機溶媒として、２−プロパノール又は１−メチル−２−ピロリドン、もしくはそれらの混合物を用いる、磁石合金粉の製造方法である。 (8) The eighth invention of the present invention is the method for producing magnetic alloy powder in the seventh invention, wherein 2-propanol, 1-methyl-2-pyrrolidone, or a mixture thereof is used as the organic solvent. .
（９）本発明の第９の発明は、第８の発明において、前記リン酸を含む有機溶媒として、１−メチル−２−ピロリドンに、リン酸を１０体積％以上１４体積％以下の割合で含有するものを用いる、磁石合金粉の製造方法である。 (9) According to a ninth aspect of the present invention, in the eighth aspect, as the organic solvent containing phosphoric acid, 1-methyl-2-pyrrolidone is added with phosphoric acid at a ratio of 10% by volume to 14% by volume. It is a manufacturing method of magnet alloy powder using what is contained.
本発明によれば、高温環境に曝されることによる、室温での保磁力の低下を効果的に抑制した磁石合金粉を製造することができる。 ADVANTAGE OF THE INVENTION According to this invention, the magnet alloy powder which suppressed effectively the fall of the coercive force at room temperature by being exposed to a high temperature environment can be manufactured.
以下、本発明の具体的な実施形態（以下、「本実施の形態」という）について詳細に説明する。なお、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲で種々の変更が可能である。また、本明細書において、「Ｘ〜Ｙ」（Ｘ、Ｙは任意の数値）との表記は、「Ｘ以上Ｙ以下」の意味である。 Hereinafter, a specific embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, A various change is possible in the range which does not change the summary of this invention. In this specification, the notation “X to Y” (X and Y are arbitrary numerical values) means “X or more and Y or less”.
≪１．磁石合金粉の製造方法≫
本実施の形態に係る磁石合金粉の製造方法は、希土類元素を含む鉄系磁石合金粉を、リン酸を含む有機溶媒中で粉砕して磁石合金粉を製造する方法である。
<< 1. Manufacturing method of magnet alloy powder >>
The method for producing a magnet alloy powder according to the present embodiment is a method for producing a magnet alloy powder by pulverizing an iron-based magnet alloy powder containing a rare earth element in an organic solvent containing phosphoric acid.
ここで、希土類元素を含む鉄系磁石合金粉としては、例えば、Ｔｈ２Ｚｎ１７型、Ｔｈ２Ｎｉ１７型、又はＴｂＣｕ７型結晶構造を有する。これらは、菱面体晶系、六方晶系の結晶構造を持つ金属間化合物であり、Ｔｈ２Ｚｎ１７型の合金粉末としては、例えば、Ｓｍ２Ｆｅ１７Ｎ３合金、Ｎｄ２Ｆｅ１７Ｎ３等が挙げられる。また、Ｔｈ２Ｎｉ１７型の合金粉末としては、例えば、Ｇｄ２Ｆｅ１７Ｎ３等が挙げられる。 Here, the iron-based magnet alloy powder containing a rare earth element has, for example, a Th 2 Zn 17 type, Th 2 Ni 17 type, or TbCu 7 type crystal structure. These are intermetallic compounds having rhombohedral and hexagonal crystal structures. Examples of the Th 2 Zn 17 type alloy powder include Sm 2 Fe 17 N 3 alloy and Nd 2 Fe 17 N 3. Is mentioned. Examples of the Th 2 Ni 17 type alloy powder include Gd 2 Fe 17 N 3 and the like.
また、希土類元素としては、Ｓｍ、Ｎｄ、Ｐｒ、Ｙ、Ｌａ、Ｃｅ、Ｇｄ等が挙げられ、これらは単独でも、混合物でもよいが、Ｓｍが特に好ましい。また、この鉄系磁石合金粉は、遷移金属元素としては、鉄（Ｆｅ）を必須成分として含むものであり、この一部がＣｏで置換されたものであってもよい。具体的に、Ｆｅの２０質量％以下の割合をＣｏで置換することにより、微粉末のキュリー温度や耐食性を向上させることができる。 Examples of rare earth elements include Sm, Nd, Pr, Y, La, Ce, and Gd. These may be used alone or as a mixture, but Sm is particularly preferable. Further, the iron-based magnet alloy powder contains iron (Fe) as an essential component as a transition metal element, and a part thereof may be substituted with Co. Specifically, the Curie temperature and corrosion resistance of the fine powder can be improved by substituting 20% by mass or less of Fe with Co.
また、この鉄系磁石合金粉は、Ｃ、Ａｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｚｒ、Ｎｂ、Ｍｏ、Ａｇ、Ｉｎ、Ｓｎ、Ｈｆ、Ｔａ、Ｗ、Ｒｅ、Ｏｓ、Ｉｒ、Ｐｔ、Ａｕ等が含まれていてもよい。鉄系磁石合金粉において、これら成分が、例えば３質量％以下、好ましくは０．０５質量％〜０．５質量％の割合で含まれていることにより、この鉄系磁石合金粉の粉砕物である磁石合金粉を用いて作製したボンド磁石の耐候性や耐熱性を高めることができる。 In addition, this iron-based magnet alloy powder includes C, Al, Si, Ca, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, In, Sn, Hf, Ta, W, Re, Os, Ir, Pt, Au, or the like may be included. In the iron-based magnet alloy powder, these components are contained in a proportion of, for example, 3% by mass or less, preferably 0.05% by mass to 0.5% by mass. The weather resistance and heat resistance of the bonded magnet produced using a certain magnet alloy powder can be improved.
なお、鉄系磁石合金粉は、例えば、還元拡散法や液体急冷法、ＨＤＤＲ（Hydrogenation Decomposition Desorption Recombination）法によって得られた合金粉末を、窒化熱処理することによって製造することができる。 The iron-based magnet alloy powder can be produced, for example, by subjecting an alloy powder obtained by a reduction diffusion method, a liquid quenching method, or a HDDR (Hydrogen Decomposition Desorption Recombination) method to a nitriding heat treatment.
本実施の形態に係る磁石合金粉の製造方法では、鉄系磁石合金粉を有機溶媒中で粉砕するに際して、リン酸を含む有機溶媒のｐＨを１．５以上８．０以下とし、有機溶媒中のリン酸濃度を０．１体積％以上２０体積％以下とし、さらに、チタン、バナジウム、クロム、マンガン、アルミニウム、シリコン、銅、亜鉛、及びモリブデンからなる群から選ばれる元素を含む化合物のうちの１種以上を有機溶媒中の濃度として０．００１ｍｏｌ／Ｌ以上１０ｍｏｌ／Ｌ以下で添加した状態で行う。 In the method for producing a magnet alloy powder according to the present embodiment, when the iron-based magnet alloy powder is pulverized in an organic solvent, the pH of the organic solvent containing phosphoric acid is 1.5 or more and 8.0 or less, Among the compounds containing an element selected from the group consisting of titanium, vanadium, chromium, manganese, aluminum, silicon, copper, zinc, and molybdenum. One or more kinds are added in a concentration of 0.001 mol / L to 10 mol / L in the organic solvent.
このような製造方法によれば、ボンド磁石の製造工程あるいはボンド磁石としての使用時に高温に加熱されたとしても、加熱後の室温での保磁力の低下を抑制した磁石合金粉を得ることができる。 According to such a manufacturing method, even when heated to a high temperature during the manufacturing process of the bonded magnet or when used as a bonded magnet, it is possible to obtain a magnet alloy powder that suppresses a decrease in coercive force at room temperature after heating. .
［リン酸を含む有機溶媒中での粉砕］
はじめに、有機溶媒へのリン酸添加による皮膜形成について説明する。本実施の形態に係る磁石合金粉の製造方法では、上述したように、希土類元素を含む鉄系磁石合金粉を、リン酸を含む有機溶媒中で粉砕することによって、磁石合金粉を製造する。
[Crushing in an organic solvent containing phosphoric acid]
First, film formation by adding phosphoric acid to an organic solvent will be described. In the method for producing magnet alloy powder according to the present embodiment, as described above, magnet alloy powder is produced by pulverizing iron-based magnet alloy powder containing rare earth elements in an organic solvent containing phosphoric acid.
このように、希土類元素を含む鉄系磁石合金粉を有機溶媒中で粉砕することにより、その鉄系磁石粉の表面に皮膜を形成させる。有機溶媒中での鉄系磁石合金粉の粉砕によれば、その粉砕によって、鉄系磁石合金粉の表面に常に新生面が現れるという状況となるため、その新生面上に随時皮膜が形成される。 Thus, the iron-based magnet alloy powder containing rare earth elements is pulverized in an organic solvent to form a film on the surface of the iron-based magnet powder. According to the pulverization of the iron-based magnet alloy powder in the organic solvent, the pulverization always causes a new surface to appear on the surface of the iron-based magnet alloy powder, so that a film is formed on the new surface as needed.
そして、このような皮膜形成において、ボンド磁石の作製や焼結による磁石作製のため高温環境においても保磁力が低下しないようにするには、リン酸塩（リン酸鉄及び／又はリン酸サマリウム等の希土類リン酸塩）の皮膜を形成させることが重要となり、有機溶媒中にリン酸の添加し、リン酸を含む有機溶媒中で粉砕することが必須となる。 In order to prevent the coercive force from being lowered even in a high temperature environment due to the production of a bonded magnet or the production of a magnet by sintering in such a film formation, a phosphate (such as iron phosphate and / or samarium phosphate) It is important to form a film of a rare earth phosphate), and it is essential to add phosphoric acid to an organic solvent and to grind in an organic solvent containing phosphoric acid.
有機溶媒に添加するリン酸としては、特に限定されず、無水物である必要もない。例えば、通常市販されている、水（Ｈ２Ｏ）を約１５質量％含む試薬一級や試薬特級等の試薬リン酸を用いることができる。 It does not specifically limit as phosphoric acid added to an organic solvent, It is not necessary to be an anhydride. For example, a commercially available reagent phosphoric acid such as a first grade reagent or a special grade reagent containing about 15% by mass of water (H 2 O) can be used.
ここで、有機溶媒としては、特に限定されず、希土類元素を含む鉄系磁石合金粉が過度に溶解や損耗しない有機化合物を主成分とする溶媒であればよい。 Here, it does not specifically limit as an organic solvent, What is necessary is just a solvent which has as a main component the organic compound which the iron-type magnet alloy powder containing rare earth elements does not melt | dissolve or wear excessively.
その中でも、高温に曝されることによる室温での保磁力低下を抑制する観点や、粉砕処理後の有機溶媒の揮発除去等を容易にして製造コストを低減する観点からすると、分子量１００以下の有機化合物を用いることが好ましい。さらに、比誘電率が１０以上５０以下の有機溶媒を用いることによって、粉砕処理における磁石合金粉の溶解を抑えることができ、良好な皮膜を形成して磁気特性に優れる磁石合金粉を得ることができる。 Among them, from the viewpoint of suppressing the decrease in coercive force at room temperature due to exposure to high temperatures, and from the viewpoint of facilitating volatilization and removal of the organic solvent after pulverization and reducing manufacturing costs, an organic compound having a molecular weight of 100 or less. It is preferable to use a compound. Further, by using an organic solvent having a relative dielectric constant of 10 or more and 50 or less, dissolution of the magnet alloy powder in the pulverization treatment can be suppressed, and a magnetic film having excellent magnetic properties can be obtained by forming a good film. it can.
具体的に、そのような有機溶媒の例としては、メタノール、エタノール、１−ブタノール、２−ブタノール、１−プロパノール、２−プロパノール、アセトニトリル、プロピオニトリル、ブチロニトリル、ｉ−ブチロニトリル、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、１−メチル−２−ピロリドン、ジメチルスルホキシドを挙げることができる。 Specifically, examples of such organic solvents include methanol, ethanol, 1-butanol, 2-butanol, 1-propanol, 2-propanol, acetonitrile, propionitrile, butyronitrile, i-butyronitrile, N-methylformamide. , N, N-dimethylformamide, 1-methyl-2-pyrrolidone, and dimethyl sulfoxide.
これらの中でも、２−プロパノール、もしくは水よりも電位領域が広い有機溶媒を用いることがより好ましい。水よりも電位領域が広い有機溶媒としては、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、１−メチル−２−ピロリドン、ジメチルスルホキシド等が挙げられる。そして、特に、２−プロパノール又は１−メチル−２−ピロリドン、もしくはそれらの混合物を用いることによって、高温での保磁力低下をより効果的に軽減することができる。 Among these, it is more preferable to use 2-propanol or an organic solvent having a wider potential region than water. Examples of the organic solvent having a wider potential region than water include acetonitrile, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, dimethyl sulfoxide and the like. In particular, by using 2-propanol, 1-methyl-2-pyrrolidone, or a mixture thereof, it is possible to more effectively reduce the decrease in coercive force at high temperatures.
具体的に、リン酸を含む有機溶媒として、１−メチル−２−ピロリドンに、リン酸を１０体積％以上１４体積％以下の割合で含有するものを用いることが好ましく、これにより、高温環境に曝された場合でも、高い磁気特性を安定的に維持することができる。 Specifically, as the organic solvent containing phosphoric acid, it is preferable to use 1-methyl-2-pyrrolidone containing phosphoric acid in a proportion of 10% by volume or more and 14% by volume or less. Even when exposed, high magnetic properties can be stably maintained.
［リン酸濃度］
有機溶媒中のリン酸の濃度としては、容積百分率で０．１体積％以上２０体積％以下の割合とする。このような濃度でリン酸を含む有機溶媒を調整し、その有機溶媒中で粉砕してリン酸塩の皮膜を形成することで、ボンド磁石作製等の高温環境においても保磁力が低下することを抑えることができる。有機溶媒中のリン酸濃度が０．１体積％未満であると、良好な特性を有する皮膜の形成させることができず、高温環境に曝されることによる室温での保磁力低下を有効に抑制するのにことができない。一方で、リン酸濃度が２０体積％を超えると、リン酸塩の皮膜自体を効率的に形成することができない。
[Phosphoric acid concentration]
The concentration of phosphoric acid in the organic solvent is 0.1% by volume or more and 20% by volume or less by volume. By adjusting an organic solvent containing phosphoric acid at such a concentration and pulverizing in the organic solvent to form a phosphate film, the coercive force decreases even in a high temperature environment such as bond magnet production. Can be suppressed. When the phosphoric acid concentration in the organic solvent is less than 0.1% by volume, it is impossible to form a film having good characteristics, and effectively suppresses the decrease in coercive force at room temperature due to exposure to a high temperature environment. I can't do it. On the other hand, when the phosphoric acid concentration exceeds 20% by volume, the phosphate film itself cannot be formed efficiently.
また、有機溶媒中のリン酸の濃度としては、２体積％以上２０体積％以下の割合であることが好ましく、これにより、より高い磁気特性を有するものが得られる。さらに、有機溶媒中のリン酸濃度として、１０体積％以上１４体積％以下の割合であることが特に好ましく、これにより、高温環境に曝された場合であっても、高い磁気特性を有するものが得られる。 Further, the concentration of phosphoric acid in the organic solvent is preferably a ratio of 2% by volume or more and 20% by volume or less, thereby obtaining a material having higher magnetic properties. Furthermore, it is particularly preferable that the phosphoric acid concentration in the organic solvent is a ratio of 10% by volume or more and 14% by volume or less, so that even if it is exposed to a high temperature environment, it has high magnetic properties. can get.
［ｐＨ］
有機溶媒中で鉄系磁石合金粉を粉砕するに際しての、リン酸を含む有機溶媒のｐＨとしては、１．５以上８．０以下の範囲とする。ｐＨが１．５未満である場合やｐＨが８．０を超える場合には、得られる磁石合金粉において所定の保磁力が得られない。
[PH]
When the iron-based magnet alloy powder is pulverized in an organic solvent, the pH of the organic solvent containing phosphoric acid is in the range of 1.5 to 8.0. When the pH is less than 1.5 or when the pH exceeds 8.0, a predetermined coercive force cannot be obtained in the obtained magnet alloy powder.
また、そのｐＨ条件としては、４．０以上５．０以下の範囲とすることが好ましく、４．４以上４．６以下の範囲とすることが特に好ましい。これにより、より一層に高い保磁力を得ることができる。なお、このような最適なｐＨ範囲が存在する学術的な理由は明らかではないが、鉄系磁石合金粉の表面での皮膜形成の反応機構が、ｐＨにより変化するためであると推察される。 The pH condition is preferably in the range of 4.0 to 5.0, particularly preferably in the range of 4.4 to 4.6. Thereby, a much higher coercive force can be obtained. In addition, although the academic reason that such an optimal pH range exists is not clear, it is guessed that the reaction mechanism of the film formation on the surface of the iron-based magnet alloy powder changes depending on the pH.
有機溶媒のｐＨの調製方法としては、特に限定されないが、例えば、リン酸、硫酸、硝酸等のいずれか１種、もしくは２種類以上を用いて調整することが好ましい。例えば、まず、リン酸を添加することにより有機溶媒のｐＨを４．５程度にまで下げ、次に、リン酸、硫酸、硝酸のいずれか１種又は２種類以上を使用して所定のｐＨになるまで添加する。なお、例えば、リン酸と硝酸の２種類を用いて所定のｐＨになるまで添加した場合、約８５質量％のリン酸と、６０質量％以上８０質量％以下の硝酸を用いたとすると、その有機溶媒は、１０体積％以下の水を含むことになる。 Although it does not specifically limit as a preparation method of pH of an organic solvent, For example, it is preferable to adjust using any 1 type, or 2 or more types, such as phosphoric acid, a sulfuric acid, nitric acid. For example, by first adding phosphoric acid, the pH of the organic solvent is lowered to about 4.5, and then using one or more of phosphoric acid, sulfuric acid, and nitric acid to a predetermined pH. Add until For example, when two kinds of phosphoric acid and nitric acid are used until they are added to a predetermined pH, when about 85% by mass phosphoric acid and 60% by mass to 80% by mass nitric acid are used, The solvent will contain 10% or less by volume of water.
［金属元素含有化合物］
本実施の形態においては、有機溶剤に特定の金属元素を含有する化合物を所定の割合で添加し、その有機溶剤中で鉄系磁石合金粉を粉砕する。具体的には、チタン、バナジウム、クロム、マンガン、アルミニウム、シリコン、銅、亜鉛、及びモリブデンからなる群から選ばれる元素を含む化合物のうちの１種以上を有機溶媒に添加し、その有機溶媒中で粉砕する。このように有機溶媒に上述した特定の金属元素を含有する化合物を添加し、その金属元素含有化合物を所定の割合で含む有機溶媒中で鉄系磁石合金粉を粉砕することにより、形成される皮膜中にこれらの金属元素が含まれるようになり、このことにより、得られる磁石合金粉の保磁力低下を抑制することができ、磁気特性を向上させることができる。
[Metal element-containing compounds]
In the present embodiment, a compound containing a specific metal element is added to an organic solvent at a predetermined ratio, and the iron-based magnet alloy powder is pulverized in the organic solvent. Specifically, one or more compounds selected from the group consisting of titanium, vanadium, chromium, manganese, aluminum, silicon, copper, zinc, and molybdenum are added to an organic solvent, and the organic solvent Grind with. Thus, the film formed by adding the compound containing the above-mentioned specific metal element to the organic solvent and grinding the iron-based magnet alloy powder in the organic solvent containing the metal element-containing compound in a predetermined ratio These metal elements are contained therein, and this makes it possible to suppress a decrease in coercive force of the obtained magnet alloy powder and to improve magnetic properties.
金属元素含有化合物としては、上述したように、チタン、バナジウム、クロム、マンガン、アルミニウム、シリコン、銅、亜鉛、及びモリブデンからなる群から選ばれる元素を含む化合物であり、それら化合物のうちから１種単独で、又は２種以上を併用する。 As described above, the metal element-containing compound is a compound containing an element selected from the group consisting of titanium, vanadium, chromium, manganese, aluminum, silicon, copper, zinc, and molybdenum. Use alone or in combination of two or more.
例えば、チタンを含む化合物としては、酸化チタンなどの無機チタン化合物、テトラアルキルチタネートなどの有機チタン化合物等が挙げられる。また、また、バナジウムを含む化合物としては、バナジン酸、バナジン酸アンモニウムなどのバナジン酸塩、酸化バナジウム、塩化バナジウム等が挙げられる。また、クロムを含む化合物としては、酸化クロム（ＶＩ）、酸化クロム（ＩＩＩ）、硫酸クロムｎ水和物、二クロム酸カリウム、クロム酸銀、塩化クロム六水和物等が挙げられる。また、マンガンを含む化合物としては、硝酸マンガン、酢酸マンガン、硫酸マンガン、塩化マンガン、炭酸マンガン、マンガンアセチルアセトナート等が挙げられる。また、アルミニウムを含む化合物としては、酢酸アルミニウム、塩化アルミニウム、水酸化アルミニウム、アルミニウムアセチルアセトナート等が挙げられる。また、シリコンを含む化合物としては、酸化シリコン、テトラメトキシシランやテトラエトキキシランなどのテトラアルコキシシラン、メチルトリメトキシシランや３−クロロプロピルトリメトキシシランなどのアルキルアルコキシシラン等が挙げられる。また、銅を含む化合物としては、硝酸銅、硫酸銅、酸化銅、水酸化銅、塩化銅などの無機銅化合物、酢酸銅、銅アセチルアセトナート、銅アルコキシド等が挙げられる。また、亜鉛を含む化合物としては、硫酸亜鉛、硝酸亜鉛、塩化亜鉛、酸化亜鉛、水酸化亜鉛などの無機亜鉛化合物、クエン酸亜鉛、ギ酸亜鉛、乳酸亜鉛などの有機亜鉛化合物等が挙げられる。また、モリブデンを含む化合物としては、モリブデン酸、モリブデン酸アンモニウムなどのモリブデン酸塩、酸化モリブデン、塩化モリブデン等が挙げられる。 For example, examples of the compound containing titanium include inorganic titanium compounds such as titanium oxide and organic titanium compounds such as tetraalkyl titanate. In addition, examples of the compound containing vanadium include vanadate such as vanadic acid and ammonium vanadate, vanadium oxide, and vanadium chloride. Examples of the compound containing chromium include chromium oxide (VI), chromium oxide (III), chromium sulfate n-hydrate, potassium dichromate, silver chromate, and chromium chloride hexahydrate. Examples of the compound containing manganese include manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, manganese carbonate, manganese acetylacetonate, and the like. Examples of the compound containing aluminum include aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum acetylacetonate. Examples of the compound containing silicon include silicon oxide, tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, and alkylalkoxysilanes such as methyltrimethoxysilane and 3-chloropropyltrimethoxysilane. Examples of the compound containing copper include inorganic copper compounds such as copper nitrate, copper sulfate, copper oxide, copper hydroxide, and copper chloride, copper acetate, copper acetylacetonate, and copper alkoxide. Examples of the compound containing zinc include inorganic zinc compounds such as zinc sulfate, zinc nitrate, zinc chloride, zinc oxide and zinc hydroxide, and organic zinc compounds such as zinc citrate, zinc formate and zinc lactate. In addition, examples of the compound containing molybdenum include molybdates such as molybdic acid and ammonium molybdate, molybdenum oxide, molybdenum chloride, and the like.
その中でも、特に、クロムを含む化合物である酸化クロム（ＶＩ）、マンガンを含む化合物であるとしてはマンガンアセチルアセトナート、アルミニウムを含む化合物であるアルミニウムアセチルアセトナートのうちのいずれか１種以上を用いることが好ましく、これにより、特に高い温度の環境下に曝されるような場合であっても、保磁力の低下をより効果的に抑制することができ、磁気特性を一層に向上させることができる。 Among them, in particular, one or more of chromium (VI) oxide, which is a compound containing chromium, manganese acetylacetonate, which is a compound containing manganese, and aluminum acetylacetonate, which is a compound containing aluminum, are used. It is preferable, and this makes it possible to more effectively suppress the decrease in coercive force even when exposed to a particularly high temperature environment, and to further improve the magnetic characteristics. .
金属元素含有化合物の添加量としては、０．００１ｍｏｌ／Ｌ以上１０ｍｏｌ／Ｌ以下の割合とすることが必要となる。添加量が０．００１ｍｏｌ／Ｌ未満であると、保磁力低下を抑制する効果が得られず、有効に磁気特性を向上させることができない。一方で、添加量が１０ｍｏｌ／Ｌを超えると、再び保磁力低下を抑制する効果が得られなくなる。このため、金属元素含有化合物の添加量としては、０．００１ｍｏｌ／Ｌ以上１０ｍｏｌ／Ｌ以下とし、好ましくは０．０１ｍｏｌ／Ｌ以上８．０ｍｏｌ／Ｌ以下とし、より好ましくは０．１ｍｏｌ／Ｌ以上５．０ｍｏｌ／Ｌ以下とする。 As the addition amount of the metal element-containing compound, it is necessary to set the ratio between 0.001 mol / L and 10 mol / L. If the addition amount is less than 0.001 mol / L, the effect of suppressing the decrease in coercive force cannot be obtained, and the magnetic characteristics cannot be improved effectively. On the other hand, when the addition amount exceeds 10 mol / L, the effect of suppressing the reduction in coercive force cannot be obtained again. Therefore, the amount of the metal element-containing compound added is 0.001 mol / L or more and 10 mol / L or less, preferably 0.01 mol / L or more and 8.0 mol / L or less, more preferably 0.1 mol / L or more. 5.0 mol / L or less.
なお、上述した金属元素含有化合物の添加量は、リン酸を含まない状態の有機溶媒への含有割合（モル濃度）をいうものとする。 In addition, the addition amount of the metal element containing compound mentioned above shall say the content rate (molar concentration) to the organic solvent in the state which does not contain phosphoric acid.
［酸化剤］
また、この磁石合金粉の製造方法においては、さらに有機溶剤に酸化剤を所定の割合で添加し、その有機溶剤中で鉄系磁石合金粉を粉砕することがより好ましい。
[Oxidant]
Moreover, in this method for producing a magnet alloy powder, it is more preferable to add an oxidant to an organic solvent at a predetermined ratio, and pulverize the iron-based magnet alloy powder in the organic solvent.
酸化剤としては、当該物質を０．０１ｍｏｌ／Ｌ〜１．０ｍｏｌ／Ｌのモル濃度で含む水溶液を作製し、これに白金電極（表面は湿式ＳｉＣ紙で１５００番研磨相当の粗さ）を自然浸漬したときの電位が、銀／塩化銀参照電極基準で０．６Ｖ以上のものであることが好ましい。なお、この測定にあたっては、酸化剤を含む水溶液と照合電極との間を、飽和塩化カリウム水溶液と寒天で作製した塩橋で繋いで計測するものとする。 As an oxidizing agent, an aqueous solution containing the substance in a molar concentration of 0.01 mol / L to 1.0 mol / L is prepared, and a platinum electrode (the surface is a wet SiC paper with a roughness equivalent to 1500 polishing) is naturally added thereto. It is preferable that the electric potential when immersed is 0.6 V or more based on a silver / silver chloride reference electrode. In this measurement, the measurement is performed by connecting an aqueous solution containing an oxidant and the reference electrode with a salt bridge made of a saturated aqueous potassium chloride solution and agar.
具体的に、その酸化剤としては、硝酸、過マンガン酸カリウム、二クロム酸カリウム等が挙げられるが、これに限定されない。その中でも、酸化剤として硝酸を用いた場合には、高温環境に曝されることによる室温での磁石合金粉の保磁力の低下をより効果的に抑制することができる。このため、特に高い温度の環境下に曝されるような場合には、酸化剤として硝酸を用いることが好ましい。 Specific examples of the oxidizing agent include, but are not limited to, nitric acid, potassium permanganate, and potassium dichromate. Among these, when nitric acid is used as the oxidizing agent, it is possible to more effectively suppress a decrease in coercive force of the magnet alloy powder at room temperature due to exposure to a high temperature environment. For this reason, it is preferable to use nitric acid as an oxidant when exposed to a particularly high temperature environment.
酸化剤は、有機溶媒の酸化還元電位（ＯＲＰ）を変化させる。このように有機溶媒に酸化剤を添加し、その酸化剤を所定の割合で含む有機溶媒中で鉄系磁石合金粉を粉砕することにより、変化した酸化還元電位が皮膜形成に関与して、得られる磁石合金粉の磁気特性を向上させることができる。 The oxidizing agent changes the redox potential (ORP) of the organic solvent. Thus, by adding an oxidizing agent to an organic solvent and pulverizing the iron-based magnet alloy powder in an organic solvent containing the oxidizing agent in a predetermined ratio, the changed redox potential is involved in the film formation and obtained. The magnetic properties of the magnet alloy powder obtained can be improved.
このとき、酸化剤の添加量としては、０．０００１ｍｏｌ／Ｌ以上１．０ｍｏｌ／Ｌ以下の割合とすることが好ましい。添加量が０．０００１ｍｏｌ／Ｌ未満であると、有機溶媒の酸化還元電位がほとんど変化しないため、保磁力低下を抑制する効果が十分に得られず、有効に磁気特性を向上させることができないことがある。一方で、添加量が１．０ｍｏｌ／Ｌを超えると、逆に磁気特性が低下する可能性がある。このため、酸化剤の添加量としては、０．０００１ｍｏｌ／Ｌ以上１．０ｍｏｌ／Ｌ以下とすることが好ましく、より好ましくは０．００１ｍｏｌ／Ｌ以上０．８ｍｏｌ／Ｌ以下とし、特に好ましくは０．０１ｍｏｌ／Ｌ以上０．５ｍｏｌ／Ｌとする。 At this time, the addition amount of the oxidizing agent is preferably set to a ratio of 0.0001 mol / L to 1.0 mol / L. When the addition amount is less than 0.0001 mol / L, the redox potential of the organic solvent hardly changes, so the effect of suppressing the reduction in coercive force cannot be obtained sufficiently, and the magnetic properties cannot be improved effectively. There is. On the other hand, when the addition amount exceeds 1.0 mol / L, there is a possibility that the magnetic properties are deteriorated. For this reason, the addition amount of the oxidizing agent is preferably 0.0001 mol / L or more and 1.0 mol / L or less, more preferably 0.001 mol / L or more and 0.8 mol / L or less, and particularly preferably 0. .01 mol / L or more and 0.5 mol / L.
なお、上述した酸化剤の添加量は、リン酸を含まない状態の有機溶媒への含有割合（モル濃度）をいうものとする。 In addition, the addition amount of the oxidizing agent mentioned above shall mean the content rate (molar concentration) to the organic solvent in the state which does not contain phosphoric acid.
≪２．磁石合金粉末を用いたボンド磁石の製造≫
上述したように、本実施の形態に係る磁石合金粉の製造方法によれば、ボンド磁石の製造工程あるいはボンド磁石としての使用時に高温に加熱された場合であっても、加熱後の室温での保磁力の低下を抑制した磁石合金粉を得ることができる。
≪2. Manufacture of bonded magnets using magnetic alloy powder >>
As described above, according to the method for manufacturing a magnet alloy powder according to the present embodiment, even when heated to a high temperature during the manufacturing process of a bonded magnet or when used as a bonded magnet, Magnet alloy powder that suppresses the decrease in coercive force can be obtained.
具体的に、上述した製造方法により得られた磁石合金粉を用いてボンド磁石を製造する方法としては、特に限定されず、例えば、磁石合金粉を、公知の熱可塑性樹脂や添加剤と混合し、得られたボンド磁石用組成物を、射出成形、圧縮成形、押出成形、圧延成形、トランスファー成形等で成形することによって製造することができる。 Specifically, the method for producing a bonded magnet using the magnet alloy powder obtained by the above-described production method is not particularly limited. For example, the magnet alloy powder is mixed with a known thermoplastic resin or additive. The obtained bonded magnet composition can be produced by molding by injection molding, compression molding, extrusion molding, rolling molding, transfer molding or the like.
熱可塑性樹脂は、磁石合金粉のバインダーとして働くものであり、その種類は特に限定されずに従来公知のものを使用することができる。例えば、６ナイロン、６，６ナイロン、１１ナイロン、１２ナイロン、６，１２ナイロン、芳香族系ナイロン、これらの分子を一部変性した変性ナイロン等のポリアミド樹脂、直鎖型ポリフェニレンサルファイド樹脂、架橋型ポリフェニレンサルファイド樹脂、セミ架橋型ポリフェニレンサルファイド樹脂、低密度ポリエチレン、線状低密度ポリエチレン樹脂、高密度ポリエチレン樹脂、超高分子量ポリエチレン樹脂、ポリプロピレン樹脂、エチレン−酢酸ビニル共重合樹脂、エチレン−エチルアクリレート共重合樹脂、アイオノマー樹脂、ポリメチルペンテン樹脂、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン共重合樹脂、アクリロニトリル−スチレン共重合樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリ酢酸ビニル樹脂、ポリビニルアルコール樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、メタクリル樹脂、ポリフッ化ビニリデン樹脂、ポリ三フッ化塩化エチレン樹脂、四フッ化エチレン−六フッ化プロピレン共重合樹脂、エチレン−四フッ化エチレン共重合樹脂、四フッ化エチレン−パーフルオロアルキルビニルエーテル共重合樹脂、ポリテトラフルオロエチレン樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリフェニレンオキサイド樹脂、ポリアリルエーテルアリルスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリアリレート樹脂、芳香族ポリエステル樹脂、酢酸セルロース樹脂、前出各樹脂系エラストマー等が挙げられ、これらの単重合体や他種モノマーとのランダム共重合体、ブロック共重合体、グラフト共重合体、他の物質での末端基変性品等が挙げられる。 The thermoplastic resin serves as a binder for the magnet alloy powder, and the type thereof is not particularly limited, and conventionally known ones can be used. For example, 6 nylon, 6,6 nylon, 11 nylon, 12 nylon, 6,12 nylon, aromatic nylon, polyamide resin such as modified nylon obtained by partially modifying these molecules, linear polyphenylene sulfide resin, cross-linked type Polyphenylene sulfide resin, semi-crosslinked polyphenylene sulfide resin, low density polyethylene, linear low density polyethylene resin, high density polyethylene resin, ultrahigh molecular weight polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, ethylene-ethyl acrylate copolymer Resin, ionomer resin, polymethylpentene resin, polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, polyvinylidene chloride resin, poly vinegar Vinyl resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl formal resin, methacrylic resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, ethylene-tetrafluoroethylene Copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, polytetrafluoroethylene resin, polycarbonate resin, polyacetal resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyphenylene oxide resin, polyallyl ether allyl sulfone resin, poly Ether sulfone resin, polyether ether ketone resin, polyarylate resin, aromatic polyester resin, cellulose acetate resin, each of the above resin-based elastomers And the like, random copolymers of these homopolymers and other species monomer, block copolymers, graft copolymers, and end groups modified products with other substances.
また、製造した磁石合金粉の性質を損なわない範囲で、パラフィンワックス、流動パラフィンといった脂肪酸類等の滑剤、ヒンダード・アミン系安定剤や、フェノール系、ホスファイト系、チオエーテル系等の抗酸化剤等の安定剤などの。従来公知の添加剤を配合することができる。 In addition, lubricants such as paraffin waxes and liquid paraffins, hindered amine stabilizers, antioxidants such as phenols, phosphites, and thioethers as long as the properties of the magnetic alloy powder produced are not impaired. Such as stabilizers. A conventionally well-known additive can be mix | blended.
磁石合金粉と上述した各成分との混合方法としては、特に限定されず、例えば、リボンブレンダー、タンブラー、ナウターミキサー、ヘンシェルミキサー、スーパーミキサー等の混合機、あるいは、バンバリーミキサー、ニーダー、ロール、ニーダールーダー、単軸押出機、二軸押出機等の混練機を用いて行うことができる。 The mixing method of the magnetic alloy powder and each component described above is not particularly limited, for example, a blender such as a ribbon blender, tumbler, nauter mixer, Henschel mixer, super mixer, or Banbury mixer, kneader, roll, It can be performed using a kneader such as a kneader ruder, a single screw extruder, or a twin screw extruder.
このようにして、各成分を混合することにより、ボンド磁石用組成物を得ることができる。なお、得られるボンド磁石用組成物の形状としては、パウダー状、ビーズ状、ペレット状、あるいはこれらの混合物の形であるが、取扱易さの点で、ペレット状が望ましい。 Thus, the composition for bonded magnets can be obtained by mixing each component. In addition, as a shape of the composition for bonded magnets obtained, it is a powder form, a bead form, a pellet form, or the form of these mixtures, However, The pellet form is desirable from the point of the ease of handling.
次に、上述のようにして得られたボンド磁石用組成物を、熱可塑性樹脂の溶融温度で加熱溶融した後、所望の形状を有する磁石に成形する。成形法としては、例えば、射出成形法、押出成形法、射出圧縮成形法、射出プレス成形法、トランスファー成形法等の各種成形法が挙げられるが、これらの中では、特に射出成形法、押出成形法、射出圧縮成形法、及び射出プレス成形法が好ましい。 Next, the bonded magnet composition obtained as described above is heated and melted at the melting temperature of the thermoplastic resin, and then formed into a magnet having a desired shape. Examples of the molding method include various molding methods such as an injection molding method, an extrusion molding method, an injection compression molding method, an injection press molding method, and a transfer molding method. Among these molding methods, in particular, the injection molding method and the extrusion molding method. Method, injection compression molding, and injection press molding are preferred.
具体的に、ボンド磁石用組成物を用いたボンド磁石の成形に際しては、射出成形により、例えば、成形温度２００℃〜３００℃、金型温度１００〜１５０℃の条件で成形する。 Specifically, when forming a bonded magnet using the bonded magnet composition, it is formed by injection molding under conditions of a molding temperature of 200 ° C. to 300 ° C. and a mold temperature of 100 to 150 ° C., for example.
このように、磁石合金粉は、ボンド磁石の製造過程において高温に曝される。しかしながら、上述した本実施の形態に係る磁石合金粉の製造方法によれば、高温に加熱されたとしても、加熱後の室温での保磁力の低下を抑制することができ、安定的に磁気特性を維持することができる。 Thus, the magnet alloy powder is exposed to a high temperature in the manufacturing process of the bonded magnet. However, according to the above-described method for producing a magnet alloy powder according to the present embodiment, even when heated to a high temperature, a decrease in coercive force at room temperature after heating can be suppressed, and magnetic characteristics can be stably provided. Can be maintained.
以下に、本発明の実施例を示してより具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
（１）成分
鉄系磁石合金粉 ：Ｓｍ−Ｆｅ−Ｎ系磁石合金粉
（平均粒径２０μｍ、住友金属鉱山株式会社製）
リン酸 ：８５％濃度水溶液
（商品名：りん酸、関東化学株式会社製）
硝酸 ：６９〜７０％濃度水溶液
（商品名：硝酸、関東化学株式会社製）
硫酸 ：９５％硫酸
（商品名：硫酸、関東化学株式会社製）
酸化クロム（ＶＩ） ：酸化クロム（ＶＩ）（無水クロム酸）（商品名）
（和光純薬工業株式会社製）
マンガンアセチルアセトナート：
ビス（２，４−ペンタジオナト）マンガン（ＩＩ）二水和物
（東京化成工業株式会社製）
アルミニウムアセチルアセトナート：
トリス（２，４−ペンタジオナト）アルミニウム（ＩＩＩ）
（東京化成工業株式会社製）
(1) Component Iron-based magnet alloy powder: Sm-Fe-N-based magnet alloy powder
(Average particle size 20 μm, manufactured by Sumitomo Metal Mining Co., Ltd.)
Phosphoric acid: 85% strength aqueous solution
(Product name: phosphoric acid, manufactured by Kanto Chemical Co., Inc.)
Nitric acid: 69-70% strength aqueous solution
(Product name: Nitric acid, manufactured by Kanto Chemical Co., Inc.)
Sulfuric acid: 95% sulfuric acid
(Product name: sulfuric acid, manufactured by Kanto Chemical Co., Inc.)
Chromium oxide (VI): Chromium oxide (VI) (chromic anhydride) (trade name)
(Wako Pure Chemical Industries, Ltd.)
Manganese acetylacetonate:
Bis (2,4-pentadionato) manganese (II) dihydrate
(Tokyo Chemical Industry Co., Ltd.)
Aluminum acetylacetonate:
Tris (2,4-pentadionato) aluminum (III)
(Tokyo Chemical Industry Co., Ltd.)
（２）保磁力評価方法
磁石合金粉の保磁力Ｈｃについては、日本ボンド磁石工業協会ボンド磁石試験方法ガイドブックＢＭＧ−２００２に従って、振動試料型磁力計により常温で測定した。
(2) Coercive force evaluation method The coercive force Hc of the magnet alloy powder was measured at room temperature with a vibrating sample magnetometer in accordance with the Bond Magnet Test Method Guidebook BMG-2002 of the Japan Bond Magnet Industry Association.
［実施例１〜１３、比較例１〜８］
有機溶媒である２−プロパノール（分子量：６０．１、比誘電率：１８）２００ｇに、所定量のリン酸と、ｐＨ調整用に濃度９５％の硫酸を希釈して作製した１質量％硫酸水溶液と、酸化クロム（ＶＩ）とを、それぞれ所定の割合で添加した有機溶媒を、粉砕溶媒として用意した。この粉砕媒体に、希土類元素を含む鉄系磁石合金粉であるＳｍ−Ｆｅ−Ｎ系磁石合金粉１００ｇを投入し、媒体攪拌ミルを用いて、平均粒径が２μｍになるように微粉砕した。
[Examples 1 to 13, Comparative Examples 1 to 8]
A 1% by mass aqueous sulfuric acid solution prepared by diluting a predetermined amount of phosphoric acid and sulfuric acid with a concentration of 95% for pH adjustment into 200 g of organic solvent 2-propanol (molecular weight: 60.1, relative dielectric constant: 18). And an organic solvent to which chromium oxide (VI) was added in a predetermined ratio were prepared as grinding solvents. To this pulverization medium, 100 g of Sm—Fe—N magnet alloy powder, which is an iron-based magnet alloy powder containing a rare earth element, was added and finely pulverized to a mean particle diameter of 2 μm using a medium stirring mill.
粉砕後のスラリーをヌッチェで濾過し、さらにその上から４００ｇの２−プロパノールをかけながら置換して、残留するリン酸を洗い流した。続いて、得られたケーキ状粉砕物をミキサに投入し、真空中１５０℃で２時間乾燥して取り出した。 The pulverized slurry was filtered with Nutsche and further replaced with 400 g of 2-propanol while washing away the remaining phosphoric acid. Subsequently, the obtained cake-like pulverized product was put into a mixer and dried in a vacuum at 150 ° C. for 2 hours and taken out.
下記表１に、鉄系磁石合金粉を粉砕するのに用いた有機溶媒の種類、ｐＨ、リン酸の容量パーセント濃度、酸化クロム（ＶＩ）のモル濃度をまとめて示す。なお、酸化クロム（ＶＩ）のモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。 Table 1 below summarizes the type, pH, volume percent concentration of phosphoric acid, and molar concentration of chromium (VI) oxide used to grind the iron-based magnet alloy powder. In addition, the molar concentration of chromium (VI) oxide indicates a content ratio in an organic solvent not containing phosphoric acid.
また、得られた磁石合金粉の室温での保磁力Ｈｃ１を測定し、次に、その磁石合金粉を電気炉にて真空中２５０℃加熱し、冷却後に回収した磁石合金粉の室温での保磁力Ｈｃ２を測定した。下記表１には、このときの保磁力減少率（１−Ｈｃ２／Ｈｃ１）を示す。 Further, the coercive force H c1 at room temperature of the obtained magnet alloy powder was measured, and then the magnet alloy powder was heated in an electric furnace at 250 ° C. in a vacuum, and the magnet alloy powder recovered after cooling at room temperature. The coercive force Hc2 was measured. Table 1 below shows the coercive force reduction rate (1-H c2 / H c1 ) at this time.
［実施例１４〜２６、比較例９〜１２］
酸化クロム（ＶＩ）に代えて、マンガンアセチルアセトナートを添加したこと以外は、それぞれ、実施例１〜１３、比較例１〜４と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。なお、下記表１に記載のマンガンアセチルアセトナートのモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。
[Examples 14 to 26, Comparative Examples 9 to 12]
Magnet alloy powders were prepared in the same manner as in Examples 1 to 13 and Comparative Examples 1 to 4, respectively, except that manganese acetylacetonate was added instead of chromium oxide (VI), and the coercive force reduction rate was evaluated. did. In addition, the molar concentration of manganese acetylacetonate described in Table 1 below indicates a content ratio in an organic solvent not containing phosphoric acid.
［実施例２７〜３９、比較例１３〜１６］
酸化クロム（ＶＩ）に代えて、アルミニウムアセチルアセトナートを添加したこと以外は、それぞれ、実施例１〜１３、比較例１〜４と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。なお、下記表１に記載のアルミニウムアセチルアセトナートのモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。
[Examples 27 to 39, Comparative Examples 13 to 16]
Magnet alloy powders were produced in the same manner as in Examples 1 to 13 and Comparative Examples 1 to 4 except that aluminum acetylacetonate was added instead of chromium oxide (VI), and the coercive force reduction rate was evaluated. did. In addition, the molar concentration of the aluminum acetylacetonate described in Table 1 below indicates the content ratio in the organic solvent in a state not containing phosphoric acid.
［実施例４０〜５２、比較例１７〜２４］
有機溶媒として１−メチル−２−ピロリドン（分子量：９９．１４、比誘電率：３２）を用いたこと以外は、それぞれ、実施例１〜１３、比較例１〜８と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。
[Examples 40 to 52, Comparative Examples 17 to 24]
Magnet alloy powder as in Examples 1 to 13 and Comparative Examples 1 to 8, respectively, except that 1-methyl-2-pyrrolidone (molecular weight: 99.14, relative dielectric constant: 32) was used as the organic solvent. The coercive force reduction rate was evaluated.
下記表２に、鉄系磁石合金粉を粉砕するのに用いた有機溶媒の種類、ｐＨ、リン酸の容量パーセント濃度、酸化クロム（ＶＩ）のモル濃度をまとめて示す。なお、酸化クロム（ＶＩ）のモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。 Table 2 below summarizes the type, pH, volume percent concentration of phosphoric acid, and molar concentration of chromium (VI) oxide used to grind the iron-based magnet alloy powder. In addition, the molar concentration of chromium (VI) oxide indicates a content ratio in an organic solvent not containing phosphoric acid.
［実施例５３〜６５、比較例２５〜２８］
有機溶媒として１−メチル−２−ピロリドン（分子量：９９．１４、比誘電率：３２）を用いたこと以外は、それぞれ、実施例１４〜２６、比較例９〜１２と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。なお、下記表２に記載のマンガンアセチルアセトナートのモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。
[Examples 53 to 65, Comparative Examples 25 to 28]
Magnet alloy powder as in Examples 14 to 26 and Comparative Examples 9 to 12, respectively, except that 1-methyl-2-pyrrolidone (molecular weight: 99.14, relative dielectric constant: 32) was used as the organic solvent. The coercive force reduction rate was evaluated. In addition, the molar concentration of manganese acetylacetonate described in Table 2 below indicates a content ratio in an organic solvent not containing phosphoric acid.
［実施例６６〜７８、比較例２９〜３２］
有機溶媒として１−メチル−２−ピロリドン（分子量：９９．１４、比誘電率：３２）を用いたこと以外は、それぞれ、実施例２７〜３９、比較例１３〜１６と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。なお、下記表２に記載のアルミニウムアセチルアセトナートのモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。
[Examples 66 to 78, Comparative Examples 29 to 32]
Magnet alloy powder as in Examples 27 to 39 and Comparative Examples 13 to 16, respectively, except that 1-methyl-2-pyrrolidone (molecular weight: 99.14, relative dielectric constant: 32) was used as the organic solvent. The coercive force reduction rate was evaluated. In addition, the molar concentration of aluminum acetylacetonate described in Table 2 below indicates a content ratio in an organic solvent in a state not containing phosphoric acid.
［実施例７９〜９３］
有機溶媒に、酸化クロム（ＶＩ）、マンガンアセチルアセトナート、アルミニウムアセチルアセトナートをモル濃度が０．５ｍｏｌ／Ｌとなるように添加し、さらに、酸化剤として濃度６９〜７０％の硝酸を希釈して作製した硝酸水溶液を０．０００１〜１ｍｏｌ／Ｌの割合で添加したこと以外は、実施例７９〜８３は実施例２と同様に、実施例８４〜８８は実施例１５と同様に、実施例８９〜９３は実施例１８と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。
[Examples 79 to 93]
Chromium (VI) oxide, manganese acetylacetonate, and aluminum acetylacetonate are added to an organic solvent so that the molar concentration is 0.5 mol / L, and nitric acid with a concentration of 69 to 70% is diluted as an oxidizing agent. Examples 79 to 83 are the same as Example 2 and Examples 84 to 88 are the same as Example 15, except that the nitric acid aqueous solution prepared in the above is added at a rate of 0.0001 to 1 mol / L. 89-93 produced magnet alloy powder like Example 18, and evaluated the coercivity decreasing rate.
下記表３に、鉄系磁石合金粉を粉砕するのに用いた有機溶媒の種類、ｐＨ、リン酸の容量パーセント濃度、酸化クロム（ＶＩ）、マンガンアセチルアセトナート、アルミニウムアセチルアセトナートのモル濃度、硝酸のモル濃度をまとめて示す。なお、酸化クロム（ＶＩ）、マンガンアセチルアセトナート、アルミニウムアセチルアセトナートのモル濃度、硝酸のモル濃度は、リン酸を含まない状態の有機溶媒への含有割合を示す。 In Table 3 below, the type of organic solvent used to pulverize the iron-based magnet alloy powder, pH, volume percent concentration of phosphoric acid, molar concentration of chromium (VI) oxide, manganese acetylacetonate, aluminum acetylacetonate, The molar concentration of nitric acid is shown collectively. In addition, the molar concentration of chromium oxide (VI), manganese acetylacetonate, and aluminum acetylacetonate, and the molar concentration of nitric acid indicate the content ratio in an organic solvent that does not contain phosphoric acid.
［実施例９４〜１０８］
有機溶媒に、酸化クロム（ＶＩ）、マンガンアセチルアセトナート、アルミニウムアセチルアセトナートをモル濃度が０．５ｍｏｌ／Ｌとなるように添加し、さらに、酸化剤として濃度６９〜７０％の硝酸を希釈して作製した硝酸水溶液を０．０００１〜１ｍｏｌ／Ｌの割合で添加したこと以外は、実施例９４〜９８は実施例４１と同様に、実施例９９〜１０３は実施例５４と同様に、実施例１０４〜１０８は実施例６７と同様にして磁石合金粉末を作製し、保磁力減少率を評価した。
[Examples 94 to 108]
Chromium (VI) oxide, manganese acetylacetonate, and aluminum acetylacetonate are added to an organic solvent so that the molar concentration is 0.5 mol / L, and nitric acid with a concentration of 69 to 70% is diluted as an oxidizing agent. Examples 94 to 98 were the same as Example 41, and Examples 99 to 103 were the same as Example 54, except that the nitric acid aqueous solution prepared in the above was added at a rate of 0.0001 to 1 mol / L. In 104 to 108, magnet alloy powders were produced in the same manner as in Example 67, and the coercive force reduction rate was evaluated.
表１〜３に示すように、実施例で得られた磁石合金粉は、比較例の磁石合金粉に比べて、高温環境に曝されることによる室温での保磁力の低下を効果的に抑制できることが分かる。 As shown in Tables 1 to 3, the magnet alloy powder obtained in the examples effectively suppresses the decrease in coercive force at room temperature due to exposure to a high temperature environment compared to the magnet alloy powder of the comparative example. I understand that I can do it.
Claims (9)
前記鉄系磁石合金粉を粉砕するに際して、
前記リン酸を含む有機溶媒のｐＨを１．５以上８．０以下とし、該有機溶媒中のリン酸濃度を０．１体積％以上２０体積％以下とし、かつ、チタン、バナジウム、クロム、マンガン、アルミニウム、シリコン、銅、亜鉛、及びモリブデンからなる群から選ばれる元素を含む化合物のうちの１種以上を該有機溶媒中の濃度として０．００１ｍｏｌ／Ｌ以上１０ｍｏｌ／Ｌ以下で添加する
磁石合金粉の製造方法。 A method for producing a magnet alloy powder by pulverizing an iron-based magnet alloy powder containing a rare earth element in an organic solvent containing phosphoric acid,
When pulverizing the iron-based magnet alloy powder,
The pH of the organic solvent containing phosphoric acid is 1.5 or more and 8.0 or less, the phosphoric acid concentration in the organic solvent is 0.1 vol% or more and 20 vol% or less, and titanium, vanadium, chromium, manganese Magnetic alloy in which one or more of compounds containing an element selected from the group consisting of aluminum, silicon, copper, zinc, and molybdenum are added at a concentration of 0.001 mol / L to 10 mol / L in the organic solvent Powder manufacturing method.
請求項１に記載の磁石合金粉の製造方法。 The manufacturing method of the magnet alloy powder of Claim 1. The pH of the organic solvent containing the said phosphoric acid shall be 4.0 or more and 5.0 or less.
請求項１又は２に記載の磁石合金粉の製造方法。 One or more of chromium oxide (VI), which is a compound containing chromium, manganese acetylacetonate, which is a compound containing manganese, and aluminum acetylacetonate, which is a compound containing aluminum, are added. The manufacturing method of the magnet alloy powder of 1 or 2.
請求項１乃至３のいずれか１項に記載の磁石合金粉の製造方法。 The method for producing a magnet alloy powder according to any one of claims 1 to 3, wherein an oxidizing agent is added to the organic solvent at a concentration of 0.0001 mol / L to 1.0 mol / L in the organic solvent.
請求項４に記載の磁石合金粉の製造方法。 The method for producing magnet alloy powder according to claim 4, wherein nitric acid is added as the oxidizing agent.
請求項１乃至５のいずれか１項に記載の磁石合金粉の製造方法。 The method for producing a magnet alloy powder according to any one of claims 1 to 5, wherein an organic compound having a molecular weight of 100 or less is used as the organic solvent.
請求項６に記載の磁石合金粉の製造方法。 The method for producing a magnet alloy powder according to claim 6, wherein an organic solvent having a relative dielectric constant of 10 to 50 is used as the organic solvent.
請求項７に記載の磁石合金粉の製造方法。 The method for producing magnet alloy powder according to claim 7, wherein 2-propanol, 1-methyl-2-pyrrolidone, or a mixture thereof is used as the organic solvent.
請求項８に記載の磁石合金粉の製造方法。 The method for producing a magnet alloy powder according to claim 8, wherein the organic solvent containing phosphoric acid includes 1-methyl-2-pyrrolidone containing phosphoric acid at a ratio of 10 vol% to 14 vol%.
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