CN106365205B - 一种锰锌铁氧体纳米粉体的制备方法 - Google Patents
一种锰锌铁氧体纳米粉体的制备方法 Download PDFInfo
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- 239000011858 nanopowder Substances 0.000 title claims abstract description 37
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 33
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011701 zinc Substances 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 24
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 230000001376 precipitating effect Effects 0.000 claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229960002163 hydrogen peroxide Drugs 0.000 claims abstract description 7
- 238000009835 boiling Methods 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000000908 ammonium hydroxide Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000008118 PEG 6000 Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229920002560 Polyethylene Glycol 3000 Polymers 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910001868 water Inorganic materials 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- 230000005415 magnetization Effects 0.000 abstract description 15
- 239000002245 particle Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 8
- 238000005303 weighing Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 13
- 229910000859 α-Fe Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002122 magnetic nanoparticle Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 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 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910017163 MnFe2O4 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005308 ferrimagnetism Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/60—Particles characterised by their size
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
本发明为一种锰锌铁氧体纳米粉体的制备方法。该方法包括如下步骤:(1)将亚铁盐溶于去离子水,然后向亚铁盐溶液中滴加沉淀剂,得到悬浊液;(2)向所得悬浊液滴加过氧化氢溶液;(3)按Mn1‑x‑yZnyFe2+(2/3)xO4中Mn、Zn、Fe摩尔比,称取锰盐、锌盐先后溶于去离子水制成溶液,然后加入到步骤(2)得到的悬浊液中,再滴加沉淀剂;(4)再加入PEG表面活性剂;(5)溶液沸腾回流反应6‑10h;(6)在500‑800℃热处理4‑10h,得到最终产物锰锌铁氧体纳米粉体。本发明的锰锌铁氧体纳米粉体中粒子直径细小(约30nm),具有高的饱和磁化强度(≥100emu/g)。
Description
技术领域:
本发明属于磁性纳米技术领域,涉及一种磁性材料的制备方法,尤其涉及一种锰锌铁氧体纳米粉体的制备方法。
背景技术:
磁性纳米粒子因其独特的物理、化学以及磁学性质受到人们的广泛关注,其应用范围相当广泛,包括磁存储介质、磁流体、催化、生物医药/生物技术、分子影像、环境污染治理等众多领域。近年来,随着纳米技术与生物医学结合的日益深入,磁性纳米粒子在生物标记与分离、磁共振成象、药物载体以及疾病诊断与治疗等方面也逐渐显示出广泛的应用前景。
本发明要制备的锰锌铁氧体是由锰、锌、铁组成的具有尖晶石结构的非金属复合氧化物,是国民经济发展中一种非常重要的基础功能材料。与同类金属磁性材料以及同为尖晶石结构的Fe3O4和MnFe2O4铁氧体相比,它在高频下具有高磁导率、低矫顽力和低损耗等物理化学性能。锰锌铁氧体作为软磁铁氧体的一种,属于亚铁磁性物质,磁性来源于两种没有抵消的反向磁矩。但当纳米锰锌铁氧体颗粒小到一定程度(约数十纳米或更小),尺度就可以和亚畴状态相比拟,其磁化矢量自发磁化至饱和,磁矩呈任意取向,呈现出超顺磁性(当去掉外磁场后剩磁很快消失),从而使其在多个领域具有好的应用前景。
对于纳米锰锌铁氧体粒子,目前的主要研究工作是寻求适当的制备方法以获得分散度高、磁性能好的材料。Xuan等人利用FeSO4、MnSO4、ZnSO4与氨水反应采用水热法在高压釜中制备了磁性能和居里点可调节的锰锌铁氧体(J.Magn.Magn.Mater.2007,312:464-469)。这种方法原料易得,产物结晶度较好,无需煅烧,从而减少了粒子的团聚和结构缺陷。但是,该法在相对较高的温度和压力下进行,设备投资大,生产成本相对较高,难以大批量生产。另外,反应在高压釜中进行,人们无法检测反应过程。CN102503390A公开了一种锰锌铁氧体磁性纳米粒子的制备方法,该方法采用高温分解法,使金属前驱体在还原剂和两亲表面活性剂的作用下发生热分解,从而获得单分散的锰锌铁氧体磁性纳米粒子。由于反应在油相中进行,所得纳米粒子无需表面改性即有单分散特性,避免了纳米粒子的团聚和长大。但由于该方法所采用原料全部都是金属的乙酰丙酮盐,成本高应是其主要缺点。CN101481243A公开的纳米锰锌铁氧体颗粒制备方法则是采用Mn、Zn、Fe的硝酸盐在柠檬酸络合剂的作用下形成溶胶乃至凝胶后,继续加热使其自燃获得的纳米材料。这种方法得到的产物纯度较高,但是自燃过程中由于体系升温较快,粒子容易聚集长大以及尺寸分布不均可能是其主要存在的问题。CN101276668A和CN102731079A是前些年我们申请的专利,虽然它们都采用化学共沉淀技术制备了锰锌铁氧体纳米粉末,但前者所用沉淀剂为碱性很强的NaOH,其中的Na+离子残留难以避免,而且会对材料的性能造成不利影响;后者所用沉淀剂改用碱性较弱且易挥发的碳酸氢铵和氨水,但是由于所制备的锰锌铁氧体纳米粒子细小,团聚以及粒子尺寸不均匀会影响其实际应用。
人们发现,铁氧体纳米粒子尺寸减小时,一方面由于表面能的增大导致其容易团聚成大尺寸的二次粒子。另一方面,纳米粒子的饱和磁化强度和居里点也都随着粒子尺度的减小而降低(J.P.Chen,et al,Phys.Rev.,1996,54:1288),而且其中的阳离子在尖晶石结构中A、B位置的分布处于介稳状态,环境温度的变化会导致阳离子分布产生不可逆的变化,从而影响到材料的性能。如何在获得细小锰锌铁氧体纳米粒子的前提下,保持好的分散性、热稳定性以及高的饱和磁化强度是突破其应用的关键问题。
发明内容:
本发明的目的是针对当前技术中存在的缺陷,提供一种锰锌铁氧体纳米粉体的制备方法。本发明采用化学共沉淀法制备锰锌铁氧体纳米粉体,通过在反应过程中加入PEG表面活性剂,充分利用其空间位阻效应阻止纳米粒子的聚集长大,从而获得分散性好的细小纳米晶颗粒(粒径约30nm)。此外,结合随后的热处理能够充分稳定金属阳离子的分布状态,从而使所制备的纳米粉体不仅具有好的热稳定性,而且具有高的饱和磁化强度(室温Ms≥100emu/g)。
本发明的技术方案为:
一种锰锌铁氧体纳米粉体的制备方法,包括如下步骤:
(1)将亚铁盐溶于去离子水,然后向亚铁盐溶液中滴加沉淀剂,将溶液pH值调至6.5-8.5,得到悬浊液;其中的物料比为每150mL去离子水加入0.08-0.12mol亚铁盐;
(2)向步骤(1)所得悬浊液滴加过氧化氢溶液,然后反应0.5-1h直至悬浊液从浅绿色完全转变为红褐色;加入量为每步骤(1)中的150mL去离子水加入3-7mL过氧化氢溶液;
(3)按Mn1-x-y,ZnyFe2+(2/3)xO4中Mn、Zn、Fe摩尔比,称取锰盐、锌盐先后溶于去离子水制成溶液,然后加入到步骤(2)得到的红褐色悬浊液中,再滴加沉淀剂调节溶液pH值为6.5-8.5;其中,本步骤中的去离子水用量为步骤(1)中去离子水的40%;x=0-0.15,y=0.30-0.50;
(4)将步骤(3)液体移至反应器中,然后在搅拌下,将PEG表面活性剂加入到上述溶液中;其中,每升步骤(3)液体加0.002-0.10molPEG表面活性剂;
(5)在搅拌下,将所得溶液沸腾回流反应6-10h,然后将产物经过过滤,沉淀物经去离子水洗涤、烘干;
(6)惰性气氛下将上步所得沉淀产物在500-800℃热处理4-10h,得到最终产物锰锌铁氧体纳米粉体。
所述的惰性气氛为氮气、氩气或二氧化碳。
所述的表面活性剂具体为PEG300、PEG3000、PEG6000或PEG10000。
所述的沉淀剂为碳酸氢铵溶液和氨水组成的混合溶液,体积比为碳酸氢铵溶液∶氨水=1∶1-4∶1,其中碳酸氢铵浓度为:0.1-1mol/L;氨水浓度为5wt%。
所述的步骤(1)和(3)中沉淀剂的滴加速度为:在1.0-1.5h时间内使溶液pH值达到6.5-8.5。
所述的过氧化氢溶液的浓度优选为质量百分浓度30%。
所述亚铁盐为硫酸亚铁或氯化亚铁。
所述锰盐为硫酸锰或氯化锰。
所述锌盐为硫酸锌或氯化锌。
本发明中,所述的锰锌铁氧体(Mn1-x-yZnyFe2+(2/3)xO4)纳米粉体是由Mn、Zn、Fe三种金属离子按比例组成的具有尖晶石结构的复合氧化物,三种金属离子的比例可由制备时的投料比调控,其中,x=0-0.15,y=0.15-0.50。
本发明的有益效果为:
1、纳米粉体材料,尤其是磁性纳米粒子,在尺寸很小时极易团聚成尺寸较大的二次颗粒而影响其使用,为了抑制这一现象的发生,人们常在纳米粒子的表面加入表面活性剂,但带来的问题是材料饱和磁化强度的降低(曹雪等人,精细石油化工,2010,27(4)53-56)。本发明在锰锌铁氧体纳米粉体制备过程中引入PEG表面活性剂,充分利用其空间位阻效应,达到抑制锰锌铁氧体纳米粉体中粒子团聚的目的,并使锰锌铁氧体纳米粒子具有细小粒径(约30nm)。
2、PEG表面活性剂在纳米粒子表面的存在,阻止了其在受热过程中的快速不均匀长大,故能保持其细小的尺寸和好的分散性。
3、适当温度的热处理能够充分稳定金属阳离子的分布状态,从而能显著提高材料的热稳定性,并使其具有高的饱和磁化强度(≥100emu/g)。这一数值比粒径相近的Co掺杂锰锌铁氧体粒子(~25.2nm)的饱和磁化强度(73emu/g,Zhang et al,Physica B,2009,404:2327-2331)提高了约40%,约是曹雪等人报道的PEG6000包覆的锰锌铁氧体纳米粒子饱和磁化强度的2.5倍。尽管Maryam等人(J.Mag.Mag.Mater.,2015,393:429-436)报道的锰锌铁氧体纳米粉体在粒径为7nm时,具有103emu/g很高的饱和磁化强度,但这是在5K条件下获得的结果。当温度升高至室温时,这一指标迅速降至52.6emu/g,远远低于我们的结果。Song等人(Hydrometallurgy,2015,153:66-73)以废弃的Zn-Mn电池为原料、NaOH为沉淀剂,采用生物萃取、化学共沉淀和沸腾回流等多个过程制备的锰锌铁氧体纳米粒子在粒径为48.24nm时获得了102emu/g,但当粒子尺寸减小至23.73nm时,饱和磁化强度却只有84.43emu/g。
附图说明:
图1为实施例1添加PEG300后制备的Mn1-x-yZnyFe2+(2/3)xO4纳米粉体的红外光谱。
图2为实施例3添加PEG6000后制备的Mn1-x-yZnyFe2+(2/3)xO4纳米粉体的红外光谱。
图3为本发明添加PEG制备的Mn1-x-yZnyFe2+(2/3)xO4纳米粉体的TEM照片,其中,(a)为添加PEG300的纳米粉体;(b)为添加PEG6000的纳米粉体。
图4为本发明添加不同PEG制备的Mn1-x-yZnyFe2+(2/3)xO4纳米粉体的XRD谱。
图5为本发明添加不同PEG制备的Mn1-x-yZnyFe2+(2/3)xO4纳米粉体的磁滞回线。
具体实施方式:
以下结合具体实施例对上述方案做进一步说明。应理解这些实施例是用于说明本发明而不限于限制本发明的范围。实施例中采用的实施条件可以根据厂家的条件做进一步调整,未注明的实施条件通常为常规试验中的条件。
实施例1
本实施例的具体步骤如下:
步骤一,称取27.802g硫酸亚铁(FeSO4·7H2O)(0.1mol铁)溶于150mL去离子水,置于500mL烧杯中搅拌均匀。称取100mL碳酸氢铵(浓度为0.5mol/L)与100mL氨水(浓度为5wt%)倒入分液漏斗内混合均匀,然后向硫酸亚铁溶液中缓慢滴加(滴加时间为1.5h)进行亚铁离子的沉淀,此时硫酸亚铁溶液的pH值调至7.2,亚铁离子完全沉淀,得到悬浊液。
步骤二,称取4.0mL H2O2溶液(质量百分浓度为30%的H2O2溶液),加入步骤一得到的悬浊液中,反应持续0.5h使液体颜色从浅绿色完全转化为红褐色。
步骤三,称取5.493g硫酸锰(MnSO4·H2O)(0.0325mol锰)与5.0323g硫酸锌(ZnSO4·7H2O)(0.0175mol锌)(按照制得的锰锌铁氧体纳米粉体的名义化学式为Mn0.65Zn0.35Fe2O4,相应的x=0,y=0.35。),分别溶于60mL去离子水制成溶液,加入到步骤二悬浊液中,再缓慢滴加(用时1.5h)体积比为1∶1的碳酸氢铵(浓度为0.5mol/L)与氨水(浓度为5wt%)配制成的混合溶液沉淀剂,调节溶液pH值至8.0。
步骤四,将步骤三的溶液转移至500mL烧瓶中,在持续搅拌的条件下,加入PEG300表面活性剂,加入量为每升步骤三的液体加0.04molPEG300,然后继续在搅拌下,沸腾回流反应6h。产物经过滤,去离子水洗涤3次,80℃烘干8h。所得产物的红外光谱分析结果如图1所示,归属纯PEG300的2875cm-1和1105cm-1两个强峰在未添加PEG的产物中没有出现,但在添加PEG300的产物中分别在2861.8cm-1和1084.4cm-1两个位置观察到相应的峰,它们分别对应PEG300分子中CH2基团和C-O-C基团的伸缩振动峰。尽管其强度较弱,但它表明PEG300表面活性剂确实存在于样品表面。
步骤五,将步骤四的烘干产物于500℃氮气气氛中热处理10h制得Mn0.65Zn0.35Fe2O4纳米粉体,粉体的TEM微观形貌如图3a)所示。它们呈尺寸细小、分散性好的球形颗粒,粒径约30nm。图4的XRD谱表明添加PEG300表面活性剂后,与未添加的材料(有少量杂相衍射峰,图中箭头所示)相比,所形成的化合物为纯的锰锌铁氧体纳米粉体。利用LakeShore-7400振动样品磁强计,在20KOe的最大磁场强度下,测定的产物磁滞回线如图5所示。由此,可确定该材料在298K下的饱和磁化强度Ms=105.2emu/g。
实施例2
其他步骤同实例1,变化之处在于:
一是制得的锰锌铁氧体纳米粉体的名义化学式为Mn0.7Zn0.15Fe2.1O4(0.1mol铁,0.0333mol锰,0.0071mol锌;此时,对应的x=0.15,y=0.15);
二是所加H2O2溶液改为5mL;
三是配制成的混合溶液沉淀剂中碳酸氢铵与氨水体积比为2∶1,调节溶液的pH值为7.3-7.5;
四是添加的表面活性剂改为PEG3000,加入量为每升步骤三的液体加0.008molPEG3000;
五是所得沉淀产物于600℃氩气气氛中热处理8h。根据图4的XRD谱可知,所得产物为纯的锰锌铁氧体纳米粉体,而且图5的磁滞回线测试结果表明添加PEG3000后所得锰锌铁氧体纳米粉体的室温饱和磁化强度Ms=102.5emu/g。
实施例3
其他步骤同实例1,变化之处在于:
一是所用原料分别为氯化亚铁(FeCl2·4H2O),氯化锰(MnCl2·4H2O)和氯化锌(ZnCl2)。制得的锰锌铁氧体纳米粉体的名义化学式为Mn0.585Zn0.4Fe2.01O4(0.1mol铁,0.0291mol锰,0.0199mol锌;此时,对应的x=0.015,y=0.4);
二是所加H2O2溶液改为6mL;
三是配制成的混合溶液沉淀剂中碳酸氢铵与氨水体积比为3∶1,调节溶液的pH值为6.5-7.8;
四是添加的表面活性剂改为PEG6000,加入量为每升步骤三的液体加0.006molPEG6000。对烘干后的沉淀产物进行红外光谱分析的结果(图2)表明,归属纯PEG6000的2875.3cm-1和1105cm-1两个强峰在未添加PEG的产物中没有出现,而添加PEG6000的产物分别在2858cm-1和1075.3cm-1两个位置产生了峰。尽管其强度较弱,但它们分别对应PEG6000分子中CH2基团和C-O-C基团的伸缩振动峰,表明PEG6000表面活性剂确实存在于样品表面;
五是所得沉淀产物于700℃二氧化碳气氛中热处理6h。图3b)为所得粉体的TEM微观形貌,同样地,它们也是细小均匀的球状纳米颗粒,粒子尺寸约30nm,并且分散性也较好。图4的XRD谱证实所得产物并未发现其它杂相的衍射峰,说明其为纯的锰锌铁氧体纳米粉体。由图5的磁滞回线可知,添加PEG6000后所得锰锌铁氧体纳米粉体的室温饱和磁化强度Ms=110.5emu/g。
实施例4
其他步骤同实例3,变化之处在于:
一是制得的锰锌铁氧体纳米粉体的名义化学式为Mn0.575Zn0.35Fe2.05O4(0.1mol铁,0.02805mol锰,0.01707mol锌;此时,对应的x=0.075,y=0.35);
二是所加H2O2溶液改为7mL;
三是配制成的混合溶液沉淀剂中碳酸氢铵与氨水体积比为4∶1,调节溶液的pH值为7.0-8.0;
四是添加的表面活性剂改为PEG10000,加入量为每升步骤三的液体加0.004molPEG10000;
五是所得沉淀产物于600℃氩气气氛中热处理5h。图4的XRD谱表明所得产物为纯的锰锌铁氧体纳米粉体,而且图5的磁滞回线测试结果表明添加PEG10000后所得锰锌铁氧体纳米粉体的室温饱和磁化强度Ms=100.5emu/g。
本发明未尽事宜为公知技术。
Claims (1)
1.一种锰锌铁氧体纳米粉体的制备方法,其特征为包括如下步骤:
(1)将亚铁盐溶于去离子水,然后向亚铁盐溶液中滴加沉淀剂,将溶液pH值调至6.5-8.5,得到悬浊液;其中的物料比为每150mL去离子水加入0.08-0.12mol铁盐;
(2)向步骤(1)所得悬浊液滴加过氧化氢溶液,然后反应0.5-1h直至悬浊液从浅绿色完全转变为红褐色;加入量为每步骤(1)中的150mL去离子水加入3-7mL过氧化氢溶液;
(3)按Mn1-x-yZnyFe2+(2/3)xO4中Mn、Zn、Fe摩尔比,称取锰盐、锌盐先后溶于去离子水制成溶液,然后加入到步骤(2)得到的红褐色悬浊液中,再滴加沉淀剂调节溶液pH值为6.5-8.5;其中,本步骤中的去离子水用量为步骤(1)中去离子水的40%;x=0-0.15,y=0.30-0.50;
(4)将步骤(3)液体移至反应器中,然后在搅拌下,将PEG表面活性剂加入到上述溶液中;其中,每升步骤(3)液体加0.002-0.10molPEG表面活性剂;
(5)在搅拌下,将所得溶液沸腾回流反应6-10h,然后将产物经过过滤,沉淀物经去离子水洗涤、烘干;
(6)惰性气氛下将上步所得沉淀产物在500-800℃热处理4-10h,得到最终产物锰锌铁氧体纳米粉体;
所述的惰性气氛为氮气、氩气或二氧化碳;
所述的表面活性剂具体为PEG300、PEG3000、PEG6000或PEG10000;
所述的沉淀剂为碳酸氢铵溶液和氨水组成的混合溶液,体积比为碳酸氢铵溶液:氨水=1:1-4:1,其中碳酸氢铵浓度为:0.1-1mol/L;氨水浓度为5wt%;
所述的步骤(1)和(3)中沉淀剂的滴加速度为:在1.0-1.5h时间内使溶液pH值达到6.5-8.5;
所述的过氧化氢溶液的浓度为质量百分浓度30%;
所述亚铁盐为硫酸亚铁或氯化亚铁;所述锰盐为硫酸锰或氯化锰;所述锌盐为硫酸锌或氯化锌。
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