CN104556997A - NiFe2O4/Bi2Fe4O9 two-phase magnetic composite powder and preparation method thereof - Google Patents
NiFe2O4/Bi2Fe4O9 two-phase magnetic composite powder and preparation method thereof Download PDFInfo
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Abstract
The invention provides a NiFe2O4/Bi2Fe4O9 two-phase magnetic composite powder and a preparation method thereof. The preparation method comprises the following steps: adding Bi(NO3)3.5H2O, Fe(NO3)3.9H2O and Ni(NO3)2.6H2O in water, adding citric acid as a chelating agent, stirring to obtain a sol, drying and grinding the sol, and calcining the ground sol at 700-800 DEG C to obtain the NiFe2O4/Bi2Fe4O9 two-phase magnetic composite powder. According to the NiFe2O4/Bi2Fe4O9 two-phase magnetic composite powder and the preparation method thereof, the chelating agent is added, so that a composite powder with good two-phase combinability can be prepared under a lower calcination temperature; furthermore, the preparation method is simple, the energy is saved, and the mass production is facilitated; due to an exchange coupling function, the saturation magnetization intensity of the composite powder is increased from 1.5 emu/g to 6.8 emu/g along the increasing of the mass percentage of NiFe2O4.
Description
Technical field
The invention belongs to material science, relate to a kind of NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder and preparation method thereof.
Background technology
Along with the high speed development of modern science and technology, people are to the microminiaturization of various device, intelligent, multifunction, integrated, have higher requirement in the aspects such as high-performance, so in the urgent need to developing the advanced material with several functions, ferroelectric, piezoelectricity and ferromagnetic material are with electricity, magnetic, sound, light, mechanics, the detection of the signals such as heat, conversion, transmit, the functions such as Storage and Processing are the material of feature, at unicircuit, automatic control, mechanics of communication, the high-tech areas such as surveying and mapping technology have important and apply widely, very consequence is occupied in national economy and national defense construction.And there is ferroelectricity and ferromagnetic multi-ferroic material is exactly a wherein important class simultaneously, multi-iron material is that one has ferroelectricity, ferromegnetism or ferroelastic material simultaneously, and there is polarization and the magnetoelectric effect that produces of magnetized interaction, a kind ofly have ferroelectric material and ferromagnetic material advantage type material concurrently, at design and research and development novel high-density memory device, spin electric device, the aspects such as magneto-electric coupled senser element all have wide practical use.
Bi
2fe
4o
9a kind of important multiferroic functional materials, Bi
2fe
4o
9the each and magnetic property of crystalline structure, system become the important focus of attention of people.Bi
2fe
4o
9belong to rhombic system, spacer is P4mm.Bi
2fe
4o
9containing octahedral and tetrahedral two kinds of cation coordination configurations on crystalline structure.Bi
2fe
4o
9crystalline structure by Fe-O, octahedra and Bi-O hexahedron connects to form, each structure cell is by four Bi
3+with 8 Fe
3+composition.Tool magnetic iron oxygen face and nonmagnetic bismuth oxygen face form laminate structure, and iron ion occupies tetrahedron and octahedra binding site position, thus causes magnetic behavior.At room temperature, Bi
2fe
4o
9have ferroelectric order and G type antiferromagnetic order, be that minority at room temperature has weak ferromegnetism and ferroelectric substance simultaneously.Now require that magnetoelectric material has coercive field large as far as possible, high saturation magnetization and high magneto-electric coupled coefficient etc. in the industrial production, these seriously limit Bi
2fe
4o
9application in practice.
In order to obtain there is high saturation and magnetic intensity and high coercitive magnetoelectric material, usual people's selection doping vario-property or carry out compound with different materials and realize this purpose.In order to improve Bi
2fe
4o
9ferromegnetism, scholar has done large quantity research.Wherein the people such as Dutta, Dimple P prepares Sc by sonochemistry dispersion method and to adulterate Bi
2fe
4o
9sample, then to adulterate forward and backward ferromegnetism by magnetic strength vibration measurement amount, contrasts show that magnetic property increases from the magnetic hysteresis loop after doping and pure phase magnetic hysteresis loop.Compound is mainly introduced other phases and then is improved its ferroelectricity and magnetic, NiFe
2o
4be a kind of conventional soft magnetic materials, have higher saturation magnetization and low coercive field can be used for electronic industry, because it has high temperature resistant, high rigidity, high strength, the advantage of Heat stability is good, is used as the stupalith of excellent property.Bi
2fe
4o
9niFe is introduced in powder
2o
4bi can be significantly improved
2fe
4o
9saturation magnetization and residual magnetization.Usually the method preparing composite granule first adopts solid phase method to prepare each single-phase powder, then each single-phase powder carried out mechanically mixing.This method, calcining temperature not only required for complex process is high, and the composite granule prepared mixes in grain-size, prepared composite granule two-phase homogeneity, associativity is all poor, cause two-way coupling poor, finally directly have influence on the performance of composite granule, make the performance of composite granule and stripped deviation larger.
Summary of the invention
The object of the present invention is to provide a kind of NiFe
2o
4/ Bi
2fe
4o
9magnetic composite powder and preparation method thereof, in preparation, calcining temperature is lower, and along with NiFe in composite granule
2o
4content increases, and saturation magnetization is increased to 6.8emu/g by 1.5emu/g.
For achieving the above object, the present invention adopts following technical scheme:
A kind of NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder, the chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 10%≤x≤40%.
The chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 20%≤x≤40%.
The chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 30%≤x≤40%.
The chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=40%.
A kind of NiFe
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder, by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 10%≤x≤40%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, stirs and obtain colloidal sol, colloidal sol is carried out drying and obtains chocolate xerogel, calcines 2-4h and obtain NiFe after being ground by xerogel at 700 ~ 800 DEG C
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, iron ion three kinds of total amount of substances of ion 3-4 doubly.
Described stirring at room temperature adopts magnetic agitation to realize, and the time of stirring is 2-3h.
Described drying is carried out in vacuum drying oven.
The temperature of described drying is 150-200 DEG C, and time of drying is 2-3h.
Compared with prior art, the beneficial effect that has of the present invention: the present invention is by by Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and then adds the citric acid as sequestrant, after stirring, obtains colloidal sol, calcines, can obtain NiFe by after colloidal sol drying, grinding at 700 ~ 800 DEG C
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder, the present invention is owing to adding sequestrant, can, under lower calcining temperature, the good composite granule of two-phase associativity can be prepared, and preparation method be simple, save the energy, be convenient to scale operation, overcome in prior art when adopting the method for mechanically mixing to prepare, need higher calcining temperature, and it is uneven to prepare composite granule two-phase, the problem of poor-performing.
In magnetic composite powder prepared by the present invention, only containing Bi
2fe
4o
9and NiFe
2o
4two-phase, exist without other dephasign, purity is higher, and Bi in composite granule
2fe
4o
9the size of crystal grain is approximately 300 ~ 350nm, NiFe
2o
4the size of crystal grain is approximately 50nm, and the dispersiveness of two-phase is better, and due to exchange-coupling interaction, composite granule is along with NiFe
2o
4mass percentage increases, and saturation magnetization is increased to 6.8emu/g by 1.5emu/g.
Accompanying drawing explanation
Fig. 1 is for work as NiFe
2o
4molar percentage be 10%, Bi
2fe
4o
9the XRD figure of composite granule under 700 DEG C of calcinings when molar percentage is 90%.
Fig. 2 is for work as NiFe
2o
4molar percentage be 20%, Bi
2fe
4o
9the XRD figure of composite granule under 730 DEG C of calcinings when molar percentage is 80%.
Fig. 3 is for work as NiFe
2o
4molar percentage be 30%, Bi
2fe
4o
9the XRD figure of composite granule under 770 DEG C of calcinings when molar percentage is 70%.
Fig. 4 is for work as NiFe
2o
4molar percentage be 40%, Bi
2fe
4o
9the XRD figure of composite granule under 800 DEG C of calcinings when molar percentage is 60%.
Fig. 5 is for work as NiFe
2o
4molar percentage be 10%, Bi
2fe
4o
9the SEM figure of composite granule powder after 700 DEG C of calcinings when molar percentage is 90%.
Fig. 6 is for work as NiFe
2o
4molar percentage be 20%, Bi
2fe
4o
9the SEM figure of matrix material powder after 730 DEG C of calcinings when molar percentage is 80%.
Fig. 7 is for work as NiFe
2o
4molar percentage be 30%, Bi
2fe
4o
9the SEM figure of matrix material powder after 770 DEG C of calcinings when molar percentage is 70%.
Fig. 8 is for work as NiFe
2o
4molar percentage be 40%, Bi
2fe
4o
9the SEM figure of matrix material powder after 800 DEG C of calcinings when molar percentage is 60%.
Fig. 9 is for work as NiFe
2o
4molar percentage is 10%, Bi
2fe
4o
9the magnetic hysteresis loop of molar percentage composite granule powders after 700 DEG C of calcinings when being 90%.
Figure 10 is for work as NiFe
2o
4molar percentage is 20%, Bi
2fe
4o
9the magnetic hysteresis loop of molar percentage composite granule powders after 730 DEG C of calcinings when being 80%.
Figure 11 is for work as NiFe
2o
4molar percentage is 30%, Bi
2fe
4o
9the magnetic hysteresis loop of molar percentage composite granule powders after 770 DEG C of calcinings when being 70%.
Figure 12 is for work as NiFe
2o
4molar percentage be 40%, Bi
2fe
4o
9the magnetic hysteresis loop of molar percentage composite granule powders after 800 DEG C of calcinings when being 60%.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
NiFe
2o
4/ Bi
2fe
4o
9the chemical formula of two-phase magnetic composite powder is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=10%.
Above-mentioned NiFe
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder is: by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=10%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, magnetic agitation 2h is at room temperature adopted to obtain colloidal sol, by colloidal sol in vacuum drying oven at 200 DEG C dry 2h, obtain chocolate xerogel, by xerogel grind after 700 DEG C calcining 4h obtain NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, 4 times of iron ion three kinds of total amount of substances of ion; The quality of water is Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
22 times of O total mass.
As seen from Figure 1, only Bi is contained in composite granule
2fe
4o
9and NiFe
2o
4two-phase, exists without other dephasign.As seen from Figure 5, large grain size (Bi
2fe
4o
9crystal grain) size is approximately 300nm, little crystal grain (NiFe
2o
4crystal grain) size is approximately 50nm, and the favorable dispersity of two-phase.As seen from Figure 9, two-way coupling is better, and saturation magnetization is 1.5emu/g.
Embodiment 2
NiFe
2o
4/ Bi
2fe
4o
9the chemical formula of two-phase magnetic composite powder is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=20%.
Above-mentioned NiFe
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder is: by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=20%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, magnetic agitation 3h is at room temperature adopted to obtain colloidal sol, by colloidal sol in vacuum drying oven at 150 DEG C dry 3h, obtain chocolate xerogel, by xerogel grind after 730 DEG C calcining 3h obtain NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, 4 times of iron ion three kinds of total amount of substances of ion; The quality of water is Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
22 times of O total mass.
As seen from Figure 2, only Bi is contained in composite granule
2fe
4o
9and NiFe
2o
4two-phase, exists without other dephasign.As seen from Figure 6, large grain size (Bi
2fe
4o
9crystal grain) size is approximately 300nm, little crystal grain (NiFe
2o
4crystal grain) size is approximately 50nm, and the favorable dispersity of two-phase.As seen from Figure 10, two-way coupling is better, and saturation magnetization is 2.8emu/g.
Embodiment 3
NiFe
2o
4/ Bi
2fe
4o
9the chemical formula of two-phase magnetic composite powder is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=30%.
Above-mentioned NiFe
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder is: by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=30%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, magnetic agitation 2.5h is at room temperature adopted to obtain colloidal sol, by colloidal sol in vacuum drying oven at 160 DEG C dry 2.5h, obtain chocolate xerogel, by xerogel grind after 770 DEG C calcining 2.5h obtain NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, 3.5 times of iron ion three kinds of total amount of substances of ion; The quality of water is Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
22 times of O total mass.
As seen from Figure 3, only Bi is contained in composite granule
2fe
4o
9and NiFe
2o
4two-phase, exists without other dephasign.As seen from Figure 7, large grain size (Bi
2fe
4o
9crystal grain) size is approximately 350nm, little crystal grain (NiFe
2o
4crystal grain) size is approximately 50nm, and the favorable dispersity of two-phase.As seen from Figure 11, two-way coupling is better, and saturation magnetization is 4.5emu/g.
Embodiment 4
NiFe
2o
4/ Bi
2fe
4o
9the chemical formula of two-phase magnetic composite powder is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=40%.
Above-mentioned NiFe
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder is: by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=40%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, magnetic agitation 3h is at room temperature adopted to obtain colloidal sol, by colloidal sol in vacuum drying oven at 180 DEG C dry 2h, obtain chocolate xerogel, by xerogel grind after 800 DEG C calcining 2h obtain NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, 3 times of iron ion three kinds of total amount of substances of ion; The quality of water is Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
22 times of O total mass.
As seen from Figure 4, only Bi is contained in composite granule
2fe
4o
9and NiFe
2o
4two-phase, exists without other dephasign.As seen from Figure 8, large grain size (Bi
2fe
4o
9crystal grain) size is approximately 350nm, little crystal grain (NiFe
2o
4crystal grain) size is approximately 50nm, and the favorable dispersity of two-phase.As seen from Figure 12, two-way coupling is better, and saturation magnetization is 6.8emu/g.
Embodiment 5
NiFe
2o
4/ Bi
2fe
4o
9the chemical formula of two-phase magnetic composite powder is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=25%.
Above-mentioned NiFe
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder is: by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=25%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, magnetic agitation 3h is at room temperature adopted to obtain colloidal sol, by colloidal sol in vacuum drying oven at 200 DEG C dry 2h, obtain chocolate xerogel, by xerogel grind after 700 DEG C calcining 4h obtain NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, 3 times of iron ion three kinds of total amount of substances of ion; The quality of water is Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
22 times of O total mass.
Claims (8)
1. a NiFe
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder, is characterized in that, the chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 10%≤x≤40%.
2. NiFe according to claim 1
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder, is characterized in that, the chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 20%≤x≤40%.
3. NiFe according to claim 1
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder, is characterized in that, the chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 30%≤x≤40%.
4. NiFe according to claim 1
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder, is characterized in that, the chemical formula of this two-phase composite granule is xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and x=40%.
5. a kind of NiFe according to claim 1
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder, is characterized in that, by chemical general formula xNiFe
2o
4/ (1-x)/Bi
2fe
4o
9, wherein x is NiFe
2o
4mass percent, and 10%≤x≤40%, by analytically pure Bi (NO
3)
35H
2o, Fe (NO
3)
39H
2o and Ni (NO
3)
26H
2o is added to the water, and is mixed with solution, then in solution, adds citric acid, stirs and obtain colloidal sol, colloidal sol is carried out drying and obtains chocolate xerogel, calcines 2-4h and obtain NiFe after being ground by xerogel at 700 ~ 800 DEG C
2o
4/ Bi
2fe
4o
9two-phase magnetic composite powder; Wherein, the amount of substance of citric acid be nickel ion, bismuth ion, iron ion three kinds of total amount of substances of ion 3-4 doubly.
6. a kind of NiFe according to claim 5
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder, is characterized in that, described stirring at room temperature adopts magnetic agitation to realize, and the time of stirring is 2-3h.
7. a kind of NiFe according to claim 5
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder, is characterized in that, described drying is carried out in vacuum drying oven.
8. a kind of NiFe according to claim 5 or 7
2o
4/ Bi
2fe
4o
9the preparation method of two-phase magnetic composite powder, is characterized in that, the temperature of described drying is 150-200 DEG C, and time of drying is 2-3h.
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CN106277076A (en) * | 2016-08-16 | 2017-01-04 | 贵州省分析测试研究院 | The synthetic method of a kind of spinel type compound and application thereof |
CN110078490A (en) * | 2019-06-05 | 2019-08-02 | 广西师范大学 | A kind of Bi2Fe4O9- MgFe2O4Composite ceramics and preparation method thereof |
CN110787981A (en) * | 2019-12-05 | 2020-02-14 | 广西师范大学 | Preparation method of bismuth titanate-nickel ferrite multiferroic composite film |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105645944A (en) * | 2015-12-30 | 2016-06-08 | 陕西科技大学 | Bi2Fe4O9/BaFe12O19 (bismuth ferrite/barium ferrite) composite ceramic and preparation method thereof |
CN105645944B (en) * | 2015-12-30 | 2018-05-15 | 陕西科技大学 | A kind of Bi2Fe4O9/BaFe12O19Composite ceramics and preparation method thereof |
CN106277076A (en) * | 2016-08-16 | 2017-01-04 | 贵州省分析测试研究院 | The synthetic method of a kind of spinel type compound and application thereof |
CN106277076B (en) * | 2016-08-16 | 2018-02-02 | 贵州省分析测试研究院 | A kind of synthetic method of spinel type compound and its application |
CN110078490A (en) * | 2019-06-05 | 2019-08-02 | 广西师范大学 | A kind of Bi2Fe4O9- MgFe2O4Composite ceramics and preparation method thereof |
CN110787981A (en) * | 2019-12-05 | 2020-02-14 | 广西师范大学 | Preparation method of bismuth titanate-nickel ferrite multiferroic composite film |
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