CN1191211C - 一种由层状前体制备磁性铁氧体的方法 - Google Patents

一种由层状前体制备磁性铁氧体的方法 Download PDF

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CN1191211C
CN1191211C CNB021256853A CN02125685A CN1191211C CN 1191211 C CN1191211 C CN 1191211C CN B021256853 A CNB021256853 A CN B021256853A CN 02125685 A CN02125685 A CN 02125685A CN 1191211 C CN1191211 C CN 1191211C
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ferrite
sodium
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CN1472165A (zh
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段雪
李峰
刘俊杰
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Beijing University of Chemical Technology
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Abstract

本发明介绍了一种由层状前体制备磁性铁氧体的方法，先将Fe2+引入水滑石层板，制备得到Me-Fe2+-Fe3+层状化合物LDH，再利用Fe2+易被氧化的特点，通过对该层状前体进行高温焙烧，使Fe2+氧化成Fe3+制备出晶相单一的两组分或多组分的铁氧体材料。该方法所制备的铁氧体的比饱和磁化强度比传统方法制备的铁氧体的有大幅度提高。由于层状前体中金属元素高度分散、活性高、粒度小(平均粒径40～200nm)，在焙烧前不需要混磨工艺，从而可简化生产工艺，缩短生产周期，节省设备投资，节约生产能耗；同时本制备方法对生产设备无腐蚀作用，无环境污染。

Description

一种由层状前体制备磁性铁氧体的方法
技术领域：本发明涉及一种由层状前体制备磁性铁氧体的方法。
技术背景：铁氧体是一种新型的非金属磁性材料，广泛应用于通讯广播、雷达导航、宇宙航行、医学生物等高频或低频领域，从二十世纪四十年代开始进行系统研究和生产以来，得到了极其迅速的发展和广泛的应用。铁氧体是由铁和其他一种或多种金属组成的复合氧化物，如尖晶石型铁氧体的化学分子式为MeFe2O4，其中Me为离子半径与二价铁离子相近的二价金属离子(Mn2+、Zn2+、Cu2+、Ni2+、Mg2+、Co2+等)，因此随着替代金属种类和数量的不同，可以组成各种不同类型的双组份铁氧体或多组份铁氧体。
目前制备铁氧体主要是以各种金属的氧化物、氢氧化物或其它沉淀混合物为原料经焙烧后得到的，由于这些焙烧前体原料的活性较差、混合均匀度和细度不高，因此在制备铁氧体的过程存在反应不易完全、整体均一性差的缺陷，最终影响到铁氧体的磁性能。针对这种状况，人们积极地进行了制备工艺的改进，如文献C.Jovalekic，M.Zdujic，A.Radakovic，and M.Mitic.Mater.Lett.24，365(1995)和文献J.Ding，H.Yang，W.F.Miao，P.G.McCormick，and R.Street.J.Alloys Compd.221，959(1995)通过高能碾磨制备出了阳离子分散性不同于传统法的纳米尖晶石铁氧体，但是由于仍然采用混合物作为焙烧前体的原料，焙烧前体的混合均匀度和细度无法从微观上进行很大程度调整，也很难再进一步提高铁氧体的磁性能。
发明内容：
本发明是为了克服以上方法的缺点，提供一种通过制备整体均一、化学组成和结构在微观上可调变、活性高的单一化合物作为焙烧前体原料来制备铁氧体的方法，从而可得到磁性能好且粒度分布小的铁氧体。
LDHs是一类具有层状结构的新型纳米无机功能材料，其化学组成可以表示为[M2+ 1-XM3+ X(OH)2]X+(An-)X/n·mH2O，其中M2+为Mg2+、Ni2+、Co2+、Zn2+、Cu2+等二价金属阳离子；M3+为Al3+、Cr3+、Fe3+、Sc3+等三价金属阳离子；An-为阴离子，如CO3 2-、NO3 -、Cl-、OH-、SO4 2-、pO4 3-、C6H4(COO)2 2-等无机、有机离子以及络合离子，X值在0.1～0.5之间。在LDHs晶体结构中，由于受晶格能最低效应及其晶格定位效应的影响，使得金属离子在层板上以一定方式均匀分布，即在层板上每一个微小的结构单元中，其化学组成和结构不变。由于LDHs的化学组成和结构在微观上具有可调控性和整体均匀性，本身又是二维纳米材料，这种特殊结构和组成的材料是合成良好磁特性铁氧体的前体材料，因此通过设计可以向其层板引入潜在的磁性物种，制备得到层板组成结构通式为：[MeII (1-Y)(1-X)FeII Y(1-X)FeIII X(OH)2]X+(An-)X/n的LDHs，其中X＝0.2～0.33，X+Y-XY＝2/3，An-为CO3 2-、NO3 -、OH-、SO4 2-；Me为Mn、Zn、Cu、Ni、Mg、Co。以其为前体经高温焙烧得到尖晶石铁氧体。由于LDHs焙烧后能够得到在微观上组成和结构均匀的尖晶石铁氧体，从而使得此磁性产物中整体微观结构单一，磁学性能大幅度提高。这是用传统方法制备铁氧体无法实现的。
本发明通过先将Fe2+引入水滑石层板，制备得到Me-Fe2+-Fe3+LDH化合物，再利用Fe2+易被氧化的特点，通过高温焙烧使Fe2+氧化成Fe3+，制备出晶相单一的两组分或多组分的铁氧体材料。
该铁氧体的制备方法为：
A.按照二价铁离子的摩尔量与三价铁离子的摩尔量之和等于2倍Me2+的摩尔量的比例，配制含有二价金属离子Me2+、二价铁离子和三价铁离子的盐混合溶液，其中各种金属离子的摩尔浓度分别为Me2+：0.1～0.6M，Fe2+：0.1～0.6M，Fe3+：0.1～0.6M；用氢氧化钠和可溶性无机钠盐配制混合碱性溶液，其中氢氧化钠浓度为1.0～2.5M，钠盐浓度为0～1.7M；配制上述溶液所用的溶剂均为通过N2的去离子水；Me2+为离子半径与Fe2+相近的二价金属离子；
B.在N2保护的条件下，将混合碱性溶液缓慢滴加到盐混合溶液中，当体系中的pH值达到7～12时，停止滴加混合碱性溶液，在N2保护的条件下，20～65℃水浴中，晶化5～25h，经过滤，冷却，洗涤，干燥，得到Me2+-Fe2+-Fe3+层状双羟基氢氧化物水滑石(LDH)；
C.将上述LDH置于高温炉中，以2～15℃/min的速率升温至850～1150℃，焙烧2～7h，得到铁氧体MeFe2O4。
步骤A中，盐混合溶液中的的酸根离子可以是Cl-、NO3 -或SO4 2-中的任意一种或几种；其中Me2+可以是Mn2+、Zn2+、Cu2+、Ni2+、Mg2+或Co2+中的任意一种或几种；可溶性钠盐优选碳酸纳、硫酸钠或氯化钠只的任意一种；
步骤B中，洗涤时先用通过N2的去离子冰水洗涤至洗涤液显中性，再用0～10℃的乙醇洗涤2～4次。
本发明具有如下显著效果：1.制备的层状铁氧体前体具有结构均一、组成和结构可调变、活性高的特点，不存在原料混合不均匀、活性低和细度小的缺点；2.制备出的铁氧体的比饱和磁化强度比用传统方法制备的铁氧体大幅度提高(见表1)；3.采用本方法制备出的铁氧体分散均匀、粒度小(平均粒径40～200nm)；4)由于不需要对原料进行混磨工艺，从而可简化生产工艺，缩短生产周期，节省设备投资，大幅度节约生产能耗；5)生产过程对设备无腐蚀作用，无环境污染，适合工业化生产。
表1.几种单组分软磁铁氧体的饱和磁化强度数据对比(常温)
    种类   σ(emu/g)(传统)  σ(emu/g)(本发明)
   MnFe2O4         80         101
   CoFe2O4         80         96
   NiFe2O4         50         66
   CuFe2O4         25         32
   MgFe2O4         27         38
具体实施方式：
实施例1：
用通过N2的去离子水配置Mg(NO3)2、Fe2(NO3)3和FeCl2的混合溶液，使溶液中金属离子的浓度分别Mg2+为0.2M，Fe2+为0.2M，Fe3+为0.2M，将此混合溶液倒入容器中。在N2保护的条件下，缓慢滴加氢氧化钠浓度为1.2M，碳酸钠浓度为0.6M的混合碱溶液，当体系中的pH值达到11.5时，停止滴加碱液。然后在N2保护的条件下，20℃水浴中，晶化8h，然后抽滤，用通过氮气的冰水洗涤，再用0℃的乙醇洗涤2次，干燥，得到Mg2+-Fe2+-Fe3+-CO3 2-型层状双羟基氢氧化物水滑石(LDH)。将LDH放于马弗炉中，以2℃/min的速率升温至950℃，保温4h，自然冷却至室温得到MgFe2O4铁氧体，测得其比饱和磁化强度38emu/g，粒度为58nm。通过Mossbauer(穆斯堡尔谱)测定焙烧前体中的Fe2+被全部氧化成Fe3+。
实施例2：
用Ni(NO3)2、Fe2(NO3)3和FeCl2配制无机盐混合溶液，其中金属离子的摩尔浓度分别Ni2+：为0.4M，Fe2+：0.5M，Fe3+：0.3M；配制钠盐溶液，其中氢氧化钠摩尔浓度为2.4M，碳酸钠摩尔浓度为1.6M，将碱溶液滴加到混合溶液中，当pH值达到9.5时停止滴加，按实施例1的步骤，晶化条件为：在60℃水浴中，晶化25h。焙烧条件为：以10℃/min的速率升温至1150℃，焙烧7h。得到NiFe2O4铁氧体，测得其比饱和磁化强度66emu/g，粒度为102nm。
实施例3：
用Mn(NO3)2、Fe2(SO4)3和FeCl2配制无机盐混合溶液，其中金属离子的摩尔浓度分别为Mn2+：0.25M，Fe2+：0.25M，Fe3+：0.25M；配制钠盐溶液，其中氢氧化钠浓度为2.0M，硫酸钠浓度为1.5M，将碱溶液滴加到混合溶液中，当pH值达到9.5时停止滴加，按实施例1的步骤，晶化条件为：在65℃水浴中，晶化5h。焙烧条件为：以15℃/min的速率升温至850℃，焙烧7h。得到MnFe2O4铁氧体，测得其比饱和磁化强度101emu/g，粒度为180nm。
实施例4：
用Co(NO3)2、Mg(NO3)2、Fe2(NO3)3和FeCl2配制无机盐混合溶液，其中金属离子的摩尔浓度分别为Co2+：0.24M，Mg2+：0.16M，Fe2+：0.4M，Fe3+：0.40M；配制钠盐溶液，其中氢氧化钠摩尔浓度为1.7M，氯化钠摩尔浓度为0.8M，将碱溶液滴加到混合溶液中，当pH值达到9.0时停止滴加，按实施例1的步骤，晶化条件为：在55℃水浴中，晶化20h。焙烧条件为：以15℃/min的速率升温至950℃，保温6h。得到Co0.6Mg0.4Fe2O4铁氧体，测得其比饱和磁化强度76emu/g，粒度为87nm。
实施例5：
用Ni(NO3)2、Cu(NO3)2、Fe2(NO3)3和FeCl2配制无机盐混合溶液，其中金属离子的摩尔浓度分别为Ni2+：0.12M，Cu2+：0.12M，Fe2+：0.24M，Fe3+：0.24M；配制钠盐溶液，其中氢氧化钠摩尔浓度为1.2M，硫酸钠摩尔浓度为0.3M，将碱溶液滴加到混合溶液中，当pH值达到8.0时停止滴加，按实施例1的步骤，晶化条件为：在55℃水浴中，晶化8h。焙烧条件为：以15℃/min的速率升温至1000℃，保温6h。得到Ni0.5Cu0.5Fe2O4铁氧体，测得其比饱和磁化强度54emu/g，粒度为158nm。
实施例6：
用Mn(NO3)2、CoSO4、Fe2(NO3)3和FeSO4配制无机盐混合溶液，其中金属离子的摩尔浓度分别为Co2+：0.2M，Mn2+：0.2M，Fe2+：0.4M，Fe3+：0.4M，；配制钠盐溶液，其中氢氧化钠摩尔浓度为1.5M，氯化钠摩尔浓度为0.5M，将碱溶液滴加到混合溶液中，当pH值达到8.0时停止滴加，然后在N2保护的条件下，28℃水浴中，晶化8h，然后抽滤，用通过氮气的冰水洗涤，再用10℃的乙醇洗涤2次，干燥，得到Mg2+-Fe2+-Fe3+-CO3 2-型层状双羟基氢氧化物水滑石(LDH)。以2℃/min的速率升温至850℃，保温6h。得到Mn0.5Co0.5Fe2O4铁氧体，测得其比饱和磁化强度94emu/g，粒度为78nm。

Claims (2)

1.一种由层状前体制备磁性铁氧体的方法，其制备步骤如下：
A.按照二价铁离子的摩尔量与三价铁离子的摩尔量之和等于2倍Me2+的摩尔量的比例，配制含有二价金属离子Me2+、二价铁离子和三价铁离子的可溶性盐的混合溶液，其中各种金属离子的摩尔浓度分别为Me2+：0.1～0.6M，Fe2+：0.1～0.6M，Fe3+：0.1～0.6M；用氢氧化钠和可溶性无机钠盐配制混合碱性溶液，其中氢氧化钠浓度为1.0～2.5M，钠盐浓度为0～1.7M；配制上述两种混合溶液所用的溶剂均为通过N2的去离子水；
Me2+是离子半径与Fe2+相近的二价金属离子：Mn2+、Zn2+、Cu2+、Ni2+、Mg2+或Co2+中的任意一种或几种；
B.在N2保护的条件下，将混合碱性溶液缓慢滴加到盐混合溶液中，当体系中的pH值达到7～12时，停止滴加混合碱性溶液，在N2保护的条件下，20～65℃水浴中，晶化5～25h，过滤，冷却，先用通过N2的去离子冰水洗涤至洗涤液显中性，再用0～10℃的乙醇洗涤2～4次，干燥，得到Me2+-Fe2+-Fe3+层状双羟基氢氧化物水滑石(LDH)；
C.将上述LDH置于高温炉中，以2～15℃/min的速率升温至850～1150℃，焙烧2～7h，得到铁氧体MeFe2O4。
2.根据权利要求1所述的由层状前体制备磁性铁氧体的方法，其特征是：
步骤A中Me2+是Mn2+、Co2+、Ni2+、Mg2+中的任意一种或两种；盐混合溶液中的的酸根离子是Cl-、NO3 -或SO4 2-中的任意一种或两种；可溶性无机钠盐是碳酸钠、硫酸钠或氯化钠中的任意一种。
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