CN113897529A - 一种稀土氧化物弥散强化铁钴软磁超细晶合金的制备方法 - Google Patents
一种稀土氧化物弥散强化铁钴软磁超细晶合金的制备方法 Download PDFInfo
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- CN113897529A CN113897529A CN202111096410.7A CN202111096410A CN113897529A CN 113897529 A CN113897529 A CN 113897529A CN 202111096410 A CN202111096410 A CN 202111096410A CN 113897529 A CN113897529 A CN 113897529A
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- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 17
- 239000000956 alloy Substances 0.000 title claims abstract description 17
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 16
- 239000013078 crystal Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- -1 rare earth nitrate Chemical class 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000005728 strengthening Methods 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 10
- 229910017061 Fe Co Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004471 Glycine Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011858 nanopowder Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 1
- XBDUTCVQJHJTQZ-UHFFFAOYSA-L iron(2+) sulfate monohydrate Chemical compound O.[Fe+2].[O-]S([O-])(=O)=O XBDUTCVQJHJTQZ-UHFFFAOYSA-L 0.000 claims 1
- 238000002490 spark plasma sintering Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 229910000531 Co alloy Inorganic materials 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
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- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910020516 Co—V Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical compound [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
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- 238000000137 annealing Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0235—Starting from compounds, e.g. oxides
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
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- 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
- H01F1/12—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 soft-magnetic materials
- H01F1/14—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 soft-magnetic materials metals or alloys
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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Abstract
一种稀土氧化物弥散强化铁钴超细晶合金的制备方法，属于复合材料制备技术领域。工艺为：(1)将铁源、钴源、燃料、稀土硝酸盐按照一定比例配成溶液；(2)加热并搅拌，溶液挥发、浓缩后分解，得到前驱体粉末；(3)将前驱体粉末于300～600℃温度范围内，保护气氛下反应1～3小时。(4)将复合粉末进行放电等离子烧结，烧结温度为750～900℃，烧结压力为40～50MPa，烧结时间为3～5分钟；或进行热等静压直接成型，烧结压力为150‑200MPa，烧结温度800～1200℃，烧结时间为1～3小时，最终得到氧化物弥散强化铁钴超细晶合金。本发明所用原料廉价易得，制作过程简便、快捷，工艺能耗少、成本低，得到的复合材料，氧化物颗粒分布均匀，合金力学性能有所提升。
Description
技术领域
本发明属于复合材料制备技术领域，具体涉及一种稀土氧化物弥散强化铁钴超细晶合金的制备方法。
背景技术
纳米微粒的粒径小、比表面积大，基于此产生的表面效应、小尺寸效应、量子尺寸效应和宏观量子隧道效应等使得纳米材料表现出独特的光、电、磁性质和化学性质。纳米金属粉末在由于其在高磁性记录密度材料、磁性液体材料、催化材料、电导体及电磁吸收材料、生物医学载体和耐腐蚀涂料等材料科学领域应用日益广泛。其中，等原子比Fe-Co软磁合金自20世纪被发现具有良好的磁性能以来，到目前已成为实际应用中饱和磁化强度最高的软磁材料，其饱和磁感应强度可达2.4T，居里温度高达980℃，兼具高磁导率和低矫顽力的特点，主要用于变压器、电动机、电话机膜片、高速打印机嵌铁、接收机线圈、开关和储存铁芯等。高的居里温度使得其可以在其他软磁合金失效的高温环境下正常服役，具有良好的高温磁稳定性，在航空航天动力系统及核工业等国防军工领域也有广阔的应用潜力。目前，限制其在高温服役条件下应用的限制主要包括两方面，其一为昂贵的价格和复杂的制造加工工艺；另外，等原子比Fe-Co软磁合金在730℃左右会发生有序-无序转变，形成的有序相具有极大的脆性而难以加工，材料的屈服强度和延伸率显著下降，机械性能急剧恶化，从而发生失效行为，使其在需要一定电磁功能特性的结构件上的应用受限。稀土元素具有细化细化晶粒、固溶强化、形成新强化相以及净化组织等作用，在Fe-Co软磁合金中添加稀土氧化物可以有效的改善由于相变而引起的合金力学性能恶化，稀土氧化物分布于晶界处，可有效地防止杂质元素在晶界处的偏析；同时也能抑制高温下发生的有序-无序转变，提高材料的热塑性；通过弥散强化阻碍位错在晶界间的传播，抑制合金晶粒的长大，起到细化晶粒的效果，提高材料的强度和韧性，使其在高温下仍然保持良好的力学性能。
目前，制作Fe-Co磁性纳米材料的方法有热分解法、射频等离子炬法、机械研磨法、磁控溅射沉积法、电化学沉积法等。Fenineche N E(Mater Lett,2003,57)以平均粒径分别为20nm和50nm的铁粉和钴粉作为原料，以一定比例在氩气气氛下进行充分混合在球磨机研磨24h，球和样品的质量比为14，后得到粒径为7nm到14nm单磁畴的Fe-Co固溶体，此方法简单易行，但球磨过程中可能引入其他杂质元素，产品质量难以保证。王炫东等人(金属热处理，2020，45(2))将一定比例的铁、钴、钒、铌金属粉末在氩气气氛下进行感应熔炼得到参杂铌的Fe-Co-V合金铸锭，在进行热轧、冷轧制成带材，之后在850℃进行2h退火热处理并进行测试表明铌的加入对Fe-Co-V延伸率有一定的提高效用，但会导致磁导率的降低。
发明内容
本发明提供了一种低成本、高效率制备稀土氧化物弥散强化铁钴合金的制备方法。
本发明提供的生产复合材料的方法，其特征在于包括如下步骤：
a、将铁源、钴源、燃料和稀土硝酸盐按照一定比例溶于去离子水中，其中燃料与铁源、钴源总和的比例按摩尔比为(4～6):1，稀土硝酸盐的含量以占据复合材料整体质量的5％～15％添加；
b、将步骤a形成的溶液进行充分地搅拌，静置一段时间而无沉淀产生后对其进行加热，使溶液挥发、浓缩、分解，得到前驱体粉末；
c、将步骤b得到的前驱体粉末于300～600℃温度范围内，在一定保护性气氛下反应1～3小时，得到稀土氧化物弥散强化铁钴磁性纳米粉末。
d、将步骤c中得到的合金粉末进行放电等离子烧结，也可进行热等静压直接成型得到氧化钇/铁钴超细晶合金。
进一步地，a步骤中加入的铁源为九水合硝酸铁、水合硫酸铁、六水合氯化铁等可溶性的铁盐；其中钴源为六水合硝酸钴、四水合乙酸钴和六水合二氯化钴等可溶性钴盐；铁源为九水硝酸铁时，燃料为甘氨酸、尿素、葡萄糖和柠檬酸等氧化剂，燃料与铁源、钴源总和的比例按摩尔比为(4～6):1；其中稀土硝酸盐为六水合硝酸钇、六水合硝酸镧等可溶性的稀土盐。
进一步地，c步骤中的一定气氛为氢气、一氧化碳等还原性气氛。最佳反应温度为400～500℃；最佳反应时间为1.5～2.5小时。
进一步地，d步骤所述放电等离子烧结，烧结温度为750～900℃，烧结压力为40～50MPa，烧结时间为3～5分钟；所述热等静压直接成型，烧结压力为150-200MPa，烧结温度800～1200℃，烧结时间为1～3小时，得到氧化钇/铁钴超细晶合金。
本发明技术关键点在于：
1、本发明以溶液燃烧合成法为基，通过液液混合的形式将稀土氧化物均匀分散于铁钴复合材料的基体中，得到氧化物弥散分布的铁钴氧化物前驱体，再根据一定条件下组分中各物质的还原性不同，将铁钴氧化物还原为等原子比铁钴合金而稀土氧化物维持原状，得到氧化物弥散分布的铁钴复合粉末，利用其粒径小、比表面积大的特性对其进行烧结致密化，制得稀土氧化物弥散强化铁钴复合材料，有效的抑制了铁钴合金高温下的无序相变，改善了其力学性能。
2、本发明通过严格控制铁源、钴源、燃料和稀土硝酸盐的比例，制定合理的烧结温度和烧结压力，有效的保证了产品的性能。该方法反应时间短、成本低、能耗少、效率高、产品性能优良，为铁钴磁性复合材料提供了更加广阔的应用空间。
该方法具有以下优点：(1)反应在液相中进行，可实现各组分原子级别的均匀混合，颗粒在基体中可实现均匀弥散分布；(2)反应放出的热量可以使反应自维持，能耗低；(3)反应过程中产生的气体可以起到分散产物的作用，可有效防止粉末颗粒的团聚；(4)所制备的前驱物反应活性高，可降低后续反应温度，提高反应速度。(5)粉末颗粒细小、比表面积大、烧结活性高，有利于后续烧结致密化。(6)原料廉价易得，制作过程简便、快捷，工艺能耗少、成本低，可实现规模化生产。
附图说明
图1为本发明氧化钇/铁钴超细晶合金X射线衍射图。
图2为本发明氧化钇/铁钴超细晶合金微观组织形貌。
图3为本发明氧化钇/铁钴超细晶合金微观组织能谱图。
具体实施方式
下面结合实施例对本发明作进一步的阐述，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后本领域技术人员可以对本发明做各种改动或修改，这些等价同样落于本申请所附权利要求书所限定的范围。
实施例1：
称取硝酸铁0.1mol、硝酸钴0.095mol、甘氨酸0.8mol、硝酸钇0.008mol，将各种原料溶于去离子水中，配制成混合溶液，将溶液置于可控温电炉上进行加热。溶液在经历挥发、浓缩、分解等一系列反应后，得到前驱体粉末，将前驱体粉末在400℃、氢气气氛的条件下反应2小时，得到铁-钴/氧化钇复合粉末。将复合粉末包套处理，进行热等静压烧结，烧结压力200MPa，在800℃下烧结2h进行致密化，得到氧化钇/铁钴合金。
实施例2：
称取氯化铁0.1mol、氯化钴0.095mol、甘氨酸0.9mol、硝酸钇0.009mol，将各种原料溶于去离子水中，配制成混合溶液，将溶液置于可控温电炉上进行加热。溶液在经历挥发、浓缩、分解等一系列反应后，得到前驱体粉末，将前驱体粉末在500℃、一氧化碳气氛的条件下反应1.5小时，得到铁-钴/氧化钇复合粉末。将复合粉末包套处理，进行热等静压烧结，烧结压力150MPa，在1200℃下烧结1h进行致密化，得到氧化钇/铁钴合金。
实施例3：
称取硫酸铁0.1mol、硝酸钴0.095mol、尿素1.1mol、硝酸镧0.006mol，将各种原料溶于去离子水中，配制成混合溶液，将溶液置于可控温电炉上进行加热。溶液在经历挥发、浓缩、分解等一系列反应后，得到前驱体粉末，将前驱体粉末在600℃、一氧化碳气氛的条件下反应1小时，得到铁-钴/氧化镧复合粉末。将复合粉末装模进行放电等离子烧结，在烧结压力50MPa下，在750℃烧结5分钟，得到氧化钇/铁钴合金。
实施例4：
称取硝酸铁0.1mol、乙酸钴0.095mol、甘氨酸0.9mol、硝酸镧0.01mol，将各种原料溶于去离子水中，配制成混合溶液，将溶液置于可控温电炉上进行加热。溶液在经历挥发、浓缩、分解等一系列反应后，得到前驱体粉末，将前驱体粉末在300℃、氢气气氛的条件下反应3小时，得到铁-钴/氧化镧复合材料。将复合粉末装模进行放电等离子烧结，在烧结压力40MPa下，在900℃烧结3分钟，得到氧化钇/铁钴合金。
实施例5：
称取氯化铁0.1mol、硫酸钴0.1mol、葡萄糖0.4mol、硝酸钇0.012mol，将各种原料溶于去离子水中，配制成混合溶液，将溶液置于可控温电炉上进行加热。溶液在经历挥发、浓缩、分解等一系列反应后，得到前驱体粉末，将前驱体粉末在500℃、氢气气氛的条件下反应2小时，得到铁-钴/氧化钇复合粉末。将复合粉末装模进行放电等离子烧结，在烧结压力50MPa下，在800℃烧结3分钟，得到氧化钇/铁钴合金。
Claims (4)
1.一种稀土氧化物弥散强化铁钴超细晶合金的生产方法，其特征在于包括如下步骤：
a、将铁源、钴源、燃料和稀土硝酸盐按照一定比例溶于去离子水中，其中燃料与铁源、钴源总和的比例按摩尔比为(4～6):1，稀土硝酸盐的含量以占据复合材料整体质量的5％～15％添加；
b、将步骤a形成的溶液进行充分地搅拌，静置一段时间而无沉淀产生后对其进行加热，使溶液挥发、浓缩、分解，得到前驱体粉末；
c、将步骤b得到的前驱体粉末于300～600℃温度范围内，在一定保护性气氛下反应1～3小时，得到稀土氧化物弥散强化铁钴磁性纳米粉末；
d、将步骤c中得到的合金粉末进行放电等离子烧结，或者进行热等静压直接成型，得到氧化钇/铁钴超细晶合金。
2.根据权利要求1所述的稀土氧化物弥散强化铁钴纳米复合粉材料的生产方法，其特征在于其中a步骤中加入的铁源为九水合硝酸铁、水合硫酸铁、六水合氯化铁可溶性的铁盐；其中钴源为六水合硝酸钴、四水合乙酸钴和六水合二氯化钴可溶性钴盐；铁源为九水硝酸铁时，燃料为甘氨酸、尿素、葡萄糖和柠檬酸氧化剂，燃料与铁源、钴源总和的比例按摩尔比为(4～6):1；其中稀土硝酸盐为六水合硝酸钇、六水合硝酸镧可溶性的稀土盐，稀土硝酸盐的含量以占据复合材料整体质量的5％～15％添加。
3.根据权利要求1所述的稀土氧化物弥散强化铁钴纳米复合材料的生产方法，其特征在于c步骤中的一定气氛为氢气、一氧化碳还原性保护气氛，反应温度为300～600℃；反应时间为1～3小时。
4.根据权利要求1所述的稀土氧化物弥散强化铁钴超细晶合金的生产方法，其特征在于d步骤中所述的成形方式为放电等离子烧结或热等静压成型；d步骤中放电等离子烧结时，烧结温度为750～900℃，烧结压力为40～50MPa，烧结时间为3～5分钟；热等静压成型时，烧结压力为150-200MPa，烧结温度800～1200℃，烧结时间为1～3小时。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538528A (zh) * | 2022-02-28 | 2022-05-27 | 北京科技大学 | 一种CoFe2O4纳米磁性材料的生产方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5868876A (en) * | 1996-05-17 | 1999-02-09 | The United States Of America As Represented By The United States Department Of Energy | High-strength, creep-resistant molybdenum alloy and process for producing the same |
| US20150093279A1 (en) * | 2013-10-02 | 2015-04-02 | Honywell International Inc. | Methods for forming oxide dispersion-strengthened alloys |
| CN104525962A (zh) * | 2014-12-17 | 2015-04-22 | 北京科技大学 | 一种制备纳米级氧化物弥散强化铁基复合粉末的方法 |
| CN104985194A (zh) * | 2015-06-17 | 2015-10-21 | 北京科技大学 | 一种氧化物弥散强化铁钴纳米复合粉末的制备方法 |
| CN109371308A (zh) * | 2018-12-17 | 2019-02-22 | 湘潭大学 | 制备多主元合金增韧氧化铝基金属陶瓷复合粉末的方法 |
-
2021
- 2021-09-16 CN CN202111096410.7A patent/CN113897529A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5868876A (en) * | 1996-05-17 | 1999-02-09 | The United States Of America As Represented By The United States Department Of Energy | High-strength, creep-resistant molybdenum alloy and process for producing the same |
| US20150093279A1 (en) * | 2013-10-02 | 2015-04-02 | Honywell International Inc. | Methods for forming oxide dispersion-strengthened alloys |
| CN104525962A (zh) * | 2014-12-17 | 2015-04-22 | 北京科技大学 | 一种制备纳米级氧化物弥散强化铁基复合粉末的方法 |
| CN104985194A (zh) * | 2015-06-17 | 2015-10-21 | 北京科技大学 | 一种氧化物弥散强化铁钴纳米复合粉末的制备方法 |
| CN109371308A (zh) * | 2018-12-17 | 2019-02-22 | 湘潭大学 | 制备多主元合金增韧氧化铝基金属陶瓷复合粉末的方法 |
Non-Patent Citations (1)
| Title |
|---|
| 张德印: "氧化物弥散强化铁基材料的制备及性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114538528A (zh) * | 2022-02-28 | 2022-05-27 | 北京科技大学 | 一种CoFe2O4纳米磁性材料的生产方法 |
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