CN104724684B - 一种InxFe4-xN/Fe3N复合材料制备方法 - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910017389 Fe3N Inorganic materials 0.000 title claims abstract description 10
- 230000005291 magnetic effect Effects 0.000 claims abstract description 23
- 239000011246 composite particle Substances 0.000 claims abstract description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 229910017135 Fe—O Inorganic materials 0.000 claims description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 3
- 238000005915 ammonolysis reaction Methods 0.000 abstract 1
- 230000001419 dependent effect Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 12
- 229910016870 Fe(NO3)3-9H2O Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910001566 austenite Inorganic materials 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- 238000005121 nitriding Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005294 ferromagnetic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明为一种InxFe4?xN/Fe3N复合材料制备方法，本发明属于复合材料技术领域。通过溶胶凝胶与高温氮化相结合的方法制备磁性InxFe4? xN/Fe3N复合颗粒。本发明的InxFe4?xN/Fe3N复合材料的制备方法，其工艺简单；并且该复合磁性材料特性可调，在磁性存储、相关磁性器件设计领域有着重要应用前景。
Description
技术领域
本发明属于复合材料技术领域。特别涉及不同In、Fe组分变化情况下立方In掺杂Fe4N材料与六角Fe3N铁磁材料复合结构的制备方法。
背景技术
最近20年来，铁氮化合物因其卓越的磁学特性引起了人们的广泛关注。在铁氮化合物体系中，六角相的ε-Fe3N和立方相的γ-Fe4N在产业应用上前景则更广阔。ε-Fe3N由六角形Fe原子组成层状排列组成主要结构，同时，在层状结构的八面体空位中，N原子占据其中1/3八面体空位，从而形成了六角ε-Fe3N结构。与ε-Fe3N相比，γ-Fe4N具有更好的热稳定性和化学稳定性。γ-Fe4N具有立方结构，N原子占据体心位置，其余的Fe原子占据顶角和面心位置。同时，Fe4N还具有大的饱和磁化强度和小的矫顽力，这使得它在磁性存储等领域都具有重要应用前景。
作为一个很重要的应用，γ-Fe4N的磁学性质可以通过掺杂进行调制。当γ-Fe4N被掺杂进非磁性金属离子时，该离子会进入立方结构的顶角和面心位置，随着掺杂浓度的不同，从而对其磁性产生明显的影响。尤其重要的是，当掺杂离子的离子大小大于Fe离子时，该离子倾向于进入立方结构的顶角位置。这类离子比如Ga、In、Rh等等，而其中的In离子尤其引人关注。
发明内容
为解决上述技术问题，本发明的目的在于提供一种应用溶胶凝胶与高温氮化相结合的方法制备磁性InxFe4-xN/Fe3N复合颗粒。
为了解决上述技术问题提出的技术方案是：一种InxFe4-xN/Fe3N复合材料制备方法，包括以下步骤：
步骤1、将Fe(NO3)3·9H2O和In(NO3)3·9H2O按5:0.496～2.148的质量比称量，混合并溶于酒精，磁力搅拌器搅拌4小时；
步骤2、加入与步骤1中Fe(NO3)3·9H2O相同质量的柠檬酸，继续搅拌2小时；
步骤3、把上述溶液放入60℃烘箱干燥1周，得到干凝胶；
步骤4、把上述干凝胶放入高温炉，1000℃空气气氛中煅烧4小时，得到In-Fe-O粉末；
步骤5、将步骤4中所得的氧化物粉末放入高温炉，950℃氨气气氛中氮化2小时；
步骤6、NH3气氛下降温至室温，得到InxFe4-xN/Fe3N复合颗粒，x＝0.125～0.5。
优选的，步骤1中Fe(NO3)3·9H2O和In(NO3)3·9H2O的纯度达到99.99％。
优选的，步骤1中，将Fe(NO3)3·9H2O和In(NO3)3·9H2O按5:1.019的质量比称量混合，得到In0.25Fe3.75N/Fe3N的复合颗粒。
本发明的有益效果是：
通过非磁性In离子掺杂，制备InxFe4-xN，对铁磁性Fe4N材料进行磁性调控，具体对其饱和磁化强度、矫顽力、居里温度等特性进行调控；同时InxFe4-xN/Fe3N复合材料可通过调节二者的配比，对其磁性进行调控，进而在磁电子学领域具有重要应用。
本发明的InxFe4-xN/Fe3N复合材料的制备方法，其工艺简单；并且该复合磁性材料特性可调，在磁性存储、相关磁性器件设计领域有着重要应用前景。
附图说明
图1.实施例1-3的三个典型InxFe4-xN/Fe3N复合材料元素EDX谱图。
图2.实施例1-3的三个典型InxFe4-xN/Fe3N复合材料的SEM图。
图3.实施例1-3的三个典型InxFe4-xN/Fe3N复合材料的XRD衍射图谱。
图4.实施例1-3的三个典型InxFe4-xN/Fe3N复合材料的磁滞洄线。
具体实施方式
实施例1
一种InxFe4-xN/Fe3N复合材料制备方法，包括以下步骤：
(1)称取5gFe(NO3)3·9H2O(99.99％)以及0.496g In(NO3)3·9H2O(99.99％)，并溶于10ml酒精，磁力搅拌器搅拌4小时；
(2)加入5g柠檬酸，继续搅拌2小时；
(3)把上述溶液放入60℃烘箱干燥1周，得到干凝胶；
(4)把上述干凝胶放入高温炉，1000℃空气气氛中煅烧4小时，得到In-Fe-O粉末；
(5)把上述氧化物粉末放入高温炉，950℃氨气气氛中氮化2小时；
(6)NH3气氛下降温至室温，得到In0.125Fe3.875N/Fe3N复合颗粒。
本实施例制备的In0.125Fe3.875N/Fe3N复合颗粒，其特性如附图1-4所示。表1中1#是本实施例样品In离子的名义浓度以及实际浓度，名义浓度为制备前设计的理论浓度，实际浓度为通过电子能谱(EDS)测得的实际值，实例1#的EDS能谱如附图1所示。从表1可以看出，1#的名义浓度分别为3.125％，实际浓度则对应为2.15％，与设计浓度相差并不是很大。
表1 In离子的名义浓度与实际浓度
附图2是实施例1#的扫描电镜(SEM)图，从图中可以看到，对于实例1#，可以看到多为大颗粒，其颗粒中的孔径较小。附图3为实例1#的X射线衍射(XRD)谱，从图中可以看出，只观察到了Fe3N六角结构和In0.125Fe3.875N立方结构相对应的衍射峰，其相对应的晶面族如图 所示。附图4是实例1#的磁滞洄线谱图，从图中可以看出，在外加磁场为7500G时1#接近饱和，同时，从附图3的插图中也可看到，实例1#有明显的矫顽力。这主要是由于In0.125Fe3.875N与FeN都为铁磁性所导致。
实施例2
一种InxFe4-xN/Fe3N复合材料制备方法，包括以下步骤：
(1)称取5gFe(NO3)3·9H2O(99.99％)以及1.019g In(NO3)3·9H2O(99.99％)，并溶于10ml酒精，磁力搅拌器搅拌4小时；
(2)加入一定量的柠檬酸，继续搅拌2小时；
(3)把上述溶液放入60℃烘箱干燥1周，得到干凝胶；
(4)把上述干凝胶放入高温炉，1000℃空气气氛中煅烧4小时，得到In-Fe-O粉末；
(5)把上述氧化物粉末放入高温炉，950℃氨气气氛中氮化2小时；
(6)NH3气氛下降温至室温，得到In0.25Fe3.75N/Fe3N复合颗粒。
对于实施例2涉及的样品In0.25Fe3.75N/Fe3N复合颗粒，其特性如附图1-4所示。表1中2#是本实例样品中In离子的名义浓度以及实际浓度，实例2#的EDS能谱如附图1所示。从表1可以看出，2#的名义浓度分别为6.25％，实际浓度则对应为5.5％，与设计浓度相差并不是很大。
附图2是实例2#的扫描电镜(SEM)图，从图中可以看到，对于实例2#，颗粒中的孔空隙增大，颗粒被分割成若干小尺寸颗粒；附图3为实例2#的X射线衍射(XRD)谱，从图中可以看出，只观察到了Fe3N六角结构和In0.25Fe3.75N立方结构以及少量InN相对应的衍射峰，其相对应的晶面族如图所示，与实例2#相比，随着In组分增加，立方相InxFe4-xN的衍射峰增强，六角相Fe3N的衍射峰减弱。附图4是实例2#的磁滞洄线谱图，从图中可以看出，在外加磁场为7500G时2#接近饱和，与实例2#性质类似。
实施例3
一种InxFe4-xN/Fe3N复合材料制备方法，包括以下步骤：
(1)称取5gFe(NO3)3·9H2O(99.99％)以及2.148g In(NO3)3·9H2O(99.99％)，并溶于10ml酒精，磁力搅拌器搅拌4小时；
(2)加入一定量的柠檬酸，继续搅拌2小时；
(3)把上述溶液放入60℃烘箱干燥1周，得到干凝胶；
(4)把上述干凝胶放入高温炉，1000℃空气气氛中煅烧4小时，得到In-Fe-O粉末；
(5)把上述氧化物粉末放入高温炉，950℃氨气气氛中氮化2小时；
(6)NH3气氛下降温至室温，得到In0.5Fe3.5N/Fe3N复合颗粒。
对于实施例3涉及的样品In0.5Fe3.5N/Fe3N复合颗粒，其特性如附图1-4所示。表1中3#是本实施例样品中In离子的名义浓度以及实际浓度，实例3#的EDS能谱如附图1所示。从表1可以看出，2#的名义浓度分别为12.5％，实际浓度则对应为15.26％。附图2是实例3#的扫描电镜(SEM)图，从图中可以看到，对于实施例3#，其形貌更为特别，只观察到即微小的颗粒分布；附图3为实例3#的X射线衍射(XRD)谱，从图中只观察到了Fe3N六角结构和In0.5Fe3.5N立方结构以及少量InN相对应的衍射峰，与实例2#、1#相比，随着In组分增加，立方相InxFe4-xN的衍射峰明显增强，六角相Fe3N的衍射峰减弱。附图4是实施例3#的磁滞洄线谱图，在外加磁场为7500G时3#接近饱和，与实例2#、1#性质类似，但更为重要的是，实例1#、2#、3#的饱和磁化强度逐渐增加。
本发明的不局限于上述实施例所述的具体技术方案，凡采用等同替换形成的技术方案均为本发明要求的保护范围。
Claims (3)
1.一种InxFe4-xN/Fe3N复合材料制备方法，其特征在于，包括以下步骤：
步骤1、将Fe(NO3)3·9H2O和In(NO3)3·9H2O按5:0.496～2.148的质量比称量，混合并溶于酒精，磁力搅拌器搅拌4小时；
步骤2、加入与步骤1中Fe(NO3)3·9H2O相同质量的柠檬酸，继续搅拌2小时；
步骤3、把上述溶液放入60℃烘箱干燥1周，得到干凝胶；
步骤4、把上述干凝胶放入高温炉，1000℃空气气氛中煅烧4小时，得到In-Fe-O粉末；
步骤5、将步骤4中所得的氧化物粉末放入高温炉，950℃氨气气氛中氮化2小时；
步骤6、NH3气氛下降温至室温，得到InxFe4-xN/Fe3N复合颗粒，x＝0.125～0.5。
2.根据权利要求1所述的InxFe4-xN/Fe3N复合材料制备方法，其特征在于，步骤1中Fe(NO3)3·9H2O和In(NO3)3·9H2O的纯度达到99.99％。
3.根据权利要求1所述的InxFe4-xN/Fe3N复合材料制备方法，其特征在于，步骤1中，将Fe(NO3)3·9H2O和In(NO3)3·9H2O按5:1.019的质量比称量混合，得到In0.25Fe3.75N/Fe3N的复合颗粒。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0565603A (ja) * | 1990-10-05 | 1993-03-19 | Hitachi Metals Ltd | 鉄−希土類系永久磁石材料およびその製造方法 |
| CN103130202A (zh) * | 2013-02-03 | 2013-06-05 | 北京工业大学 | 一种制备高纯度Fe4-xMxN(M=Ni,Co)软磁粉体的方法 |
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| JPH0565603A (ja) * | 1990-10-05 | 1993-03-19 | Hitachi Metals Ltd | 鉄−希土類系永久磁石材料およびその製造方法 |
| CN103130202A (zh) * | 2013-02-03 | 2013-06-05 | 北京工业大学 | 一种制备高纯度Fe4-xMxN(M=Ni,Co)软磁粉体的方法 |
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| Title |
|---|
| The Ternary Nitrides GaFe(3)N and AlFe(3)N: Improved Synthesis and Magnetic Properties;Andreas Houben et al.;《CHEMISTRY OF MATERIALS》;20090826;第21卷(第18期);第4332-4338页 * |
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