CN116986891B - Preparation method of double-ion combined substituted self-bias hexaferrite - Google Patents
Preparation method of double-ion combined substituted self-bias hexaferrite Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 34
- 230000005291 magnetic effect Effects 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 14
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 13
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 abstract description 4
- 239000000696 magnetic material Substances 0.000 abstract description 2
- 230000005415 magnetization Effects 0.000 description 4
- 230000005350 ferromagnetic resonance Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
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Abstract
The invention discloses a preparation method of double-ion combined substituted self-bias hexaferrite, and belongs to the technical field of magnetic materials. The preparation method comprises the following steps: (1) Firstly, preparing BaM ferrite initial powder and spraying divalent Ce in the subsequent high-energy ball milling process 2+ Ce (PFPC) 2 ·3H 2 The 0 rare earth complex is injected into a ball mill tank, and mixed powder is obtained after primary presintering, secondary presintering and secondary ball milling treatment; (2) And finally obtaining the double-ion combined substitution self-bias hexaferrite through a magnetic field orientation forming technology and a strong magnetic field heat treatment technology. The invention is better realized by adding divalent Zn in the preparation process 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 To replace Fe 3+ And the addition of the rare earth complex improves the microstructure and magnetic property of the ferrite.
Description
Technical Field
The invention relates to the technical field of magnetic materials, in particular to a preparation method of double-ion combined substituted self-bias hexaferrite.
Background
Along with the wide application of the active phased array radar in modern electronic countermeasure, a microwave device with characteristics of high frequency, small size, low loss and the like becomes a research focus of microwave and millimeter wave technologies. The microwave circulator is an indispensable important component in a Transmit/Receive (T/R) assembly, and a permanent magnet with a larger size is needed to be built in the traditional circulator to provide a direct current bias field, so that the transceiver system is difficult to realize the miniaturization of the whole machine. The uniaxial hexagonal ferrite has the characteristics of large magnetocrystalline anisotropy, high saturation magnetization and the like, and the microwave circulator prepared based on the uniaxial hexagonal ferrite design has a self-bias field without a permanent magnet, so that the uniaxial hexagonal ferrite has important significance in realizing the miniaturization and planarization of the microwave circulator and even T/R components.
Gyromagnetic materials are widely applied in the field of microwaves, but with the improvement of microwave devices and application technologies, the requirements on gyromagnetic materials are higher and higher, and further improvement of the performances of gyromagnetic materials is urgent, especially materials with good broadband temperature stability and small loss. The patent creatively adds divalent Zn in the preparation process of BaM ferrite 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 To replace Fe 3+ At the same time, the divalent Ce is contained in a spray mode in the ball milling process 2+ Ce (PFPC) 2 ·3H 2 The 0 rare earth complex is injected into a ball milling tank, and grain boundary characteristics of crystal grains are effectively regulated and controlled through a high-energy ball milling technology and a strong magnetic field heat treatment technology, so that the orientation degree is improved, and the microstructure and magnetic characteristics of ferrite are improved.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of double-ion combined substituted self-bias hexaferrite.
The preparation method of the double-ion combined substituted self-bias hexaferrite comprises the following steps:
(1) And (3) batching: in BaCO 3 Divalent Zn 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 、Fe 2 O 3 As raw materials, according to 20-30 mol% BaCO 3 、5~10 mol%ZnO、5~10 mol%SnO 2 、50~70 mol%Fe 2 O 3 "weighing materials according to the proportion, and mixing materials to obtain BaM ferrite initial powder;
(2) Ball milling for the first time: uniformly mixing BaM ferrite initial powder obtained in the step (1) and deionized water according to the mass ratio of 1:1-5 to obtain mixed powder slurry, and uniformly mixing the mixed powder slurry in a high-energy ball millThe high-energy ball milling time is 1-5 h, and the divalent Ce is contained in a spray mode in the ball milling process 2+ Ce (PFPC) 2 ·3H 2 0 rare earth complex is injected into a ball mill pot, wherein Ce (PFPC) 2 ·3H 2 0 rare earth complex accounts for 1-5% of the total weight of the mixed powder slurry to obtain a mixed ball abrasive;
(3) Drying the mixed ball abrasive powder obtained in the step (2), sieving, and then carrying out primary presintering and secondary presintering treatment on the powder to obtain mixed powder;
(4) Secondary ball milling: uniformly mixing the mixed powder obtained in the step (3) with deionized water according to the mass ratio of 1:1-5, and performing ball milling on the mixed powder for 2-8 hours by adopting a planetary ball mill to obtain powder slurry;
(5) And (3) forming: performing magnetic field orientation molding technology on the powder slurry obtained in the step (4) to prepare a pressed compact, wherein the molding magnetic field is 1-2T, and the molding pressure is 50-150 MPa;
(6) Sintering: and (3) carrying out strong magnetic field heat treatment on the pressed compact obtained in the step (5), wherein the magnetic field strength of the strong magnetic field heat treatment is 6-8T, the heat treatment temperature is 600-900 ℃, the heating rate is 5-10 ℃/min, the heat preservation time is 1-3 h, and then quenching to room temperature, so that the double-ion combined substitution self-bias hexagonal ferrite is finally obtained.
Further, the sintering temperature of the primary presintering in the step (3) is 950-1200 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 3-6 h; the sintering temperature of the secondary presintering is 700-950 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 2-4 h.
Compared with the prior art, the invention has the following advantages and beneficial effects: the patent creatively adds divalent Zn in the preparation process of BaM ferrite 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 To replace Fe 3+ At the same time, the divalent Ce is contained in a spray mode in the ball milling process 2+ Ce (PFPC) 2 ·3H 2 The 0 rare earth complex is injected into a ball milling tank, and the grain boundary characteristics of crystal grains are effectively regulated and controlled through a high-energy ball milling technology and a strong magnetic field heat treatment technology, so that the orientation degree is improved, and the micro-structure of ferrite is improvedStructure and magnetic properties.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the following examples.
Example 1
(1) And (3) batching: in BaCO 3 Divalent Zn 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 、Fe 2 O 3 As a raw material, according to "20 mol% BaCO 3 、5 mol%ZnO、5 mol%SnO 2 、70 mol%Fe 2 O 3 "weighing materials according to the proportion, and mixing materials to obtain BaM ferrite initial powder;
(2) Ball milling for the first time: uniformly mixing BaM ferrite initial powder obtained in the step (1) and deionized water according to the mass ratio of 1:1 to obtain mixed powder slurry, uniformly mixing the mixed powder slurry in a high-energy ball mill for 1 h, and spraying the mixed powder slurry containing divalent Ce during the ball milling 2+ Ce (PFPC) 2 ·3H 2 0 rare earth complex is injected into a ball mill pot, wherein Ce (PFPC) 2 ·3H 2 0 rare earth complex accounts for 1% of the total weight of the mixed powder slurry to obtain mixed ball abrasive;
(3) Drying and sieving the mixed ball abrasive powder obtained in the step (2), and then carrying out primary presintering and secondary presintering treatment on the powder to obtain mixed powder, wherein the sintering temperature of the primary presintering is 950 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 6 h; the sintering temperature of the secondary presintering is 950 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 4 h;
(4) Secondary ball milling: uniformly mixing the mixed powder obtained in the step (3) with deionized water according to the mass ratio of 1:1, and performing ball milling on the mixed powder by adopting a planetary ball mill for 8 h to obtain powder slurry;
(5) And (3) forming: performing magnetic field orientation molding technology on the powder slurry obtained in the step (4) to prepare a pressed compact, wherein the molding magnetic field is 1T, and the molding pressure is 150 MPa;
(6) Sintering: and (3) carrying out strong magnetic field heat treatment on the pressed compact obtained in the step (5), wherein the magnetic field strength is 6T, the heat treatment temperature is 900 ℃, the heating rate is 10 ℃/min, the heat preservation time is 1 h, and then quenching to room temperature, so that the double-ion combined substitution self-bias hexaferrite is finally obtained.
The double-ion combined substituted self-bias hexaferrite prepared by the invention is tested by a magnetic property and vector network analyzer, and the saturation magnetization intensity is 4 pi M s Is 5050 and Gs, and the remanence ratio M r /M s Is 0.88 of coercivity H c 5300 Oe, ferromagnetic resonance linewidth ΔH 389 Oe, anisotropy field H a 14.37 kOe.
Example 2
(1) And (3) batching: in BaCO 3 Divalent Zn 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 、Fe 2 O 3 As a raw material, according to "25 mol% BaCO 3 、8 mol%ZnO、8 mol%SnO 2 、59 mol%Fe 2 O 3 "weighing materials according to the proportion, and mixing materials to obtain BaM ferrite initial powder;
(2) Ball milling for the first time: uniformly mixing BaM ferrite initial powder obtained in the step (1) and deionized water according to the mass ratio of 1:3 to obtain mixed powder slurry, uniformly mixing the mixed powder slurry in a high-energy ball mill for 3 h, and spraying the mixed powder slurry containing divalent Ce during the ball milling 2+ Ce (PFPC) 2 ·3H 2 0 rare earth complex is injected into a ball mill pot, wherein Ce (PFPC) 2 ·3H 2 0 rare earth complex accounts for 3% of the total weight of the mixed powder slurry to obtain mixed ball abrasive;
(3) Drying and sieving the mixed ball abrasive powder obtained in the step (2), and then carrying out primary presintering and secondary presintering treatment on the powder to obtain mixed powder, wherein the sintering temperature of the primary presintering is 1050 ℃, the heating rate is 8 ℃/min, and the heat preservation time is 5 h; the sintering temperature of the secondary presintering is 800 ℃, the heating rate is 8 ℃/min, and the heat preservation time is 3 h;
(4) Secondary ball milling: uniformly mixing the mixed powder obtained in the step (3) with deionized water according to the mass ratio of 1:3, and performing ball milling on the mixed powder by adopting a planetary ball mill for 5 h to obtain powder slurry;
(5) And (3) forming: performing magnetic field orientation molding technology on the powder slurry obtained in the step (4) to prepare a pressed compact, wherein the molding magnetic field is 1.5T, and the molding pressure is 80 MPa;
(6) Sintering: and (3) carrying out strong magnetic field heat treatment on the pressed compact obtained in the step (5), wherein the magnetic field strength is 7 and T, the heat treatment temperature is 800 ℃, the heating rate is 7 ℃/min, the heat preservation time is 2 and h, and then quenching to room temperature, so as to finally obtain the double-ion combined substitution self-bias hexaferrite.
The double-ion combined substituted self-bias hexaferrite prepared by the invention is tested by a magnetic property and vector network analyzer, and the saturation magnetization intensity is 4 pi M s 5350 and Gs, remanence ratio M r /M s Is 0.90 and has coercive force H c 5459 Oe, ferromagnetic resonance linewidth ΔH 375 Oe, anisotropy field H a 15.21 kOe.
Example 3
(1) And (3) batching: in BaCO 3 Divalent Zn 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 、Fe 2 O 3 As a raw material, according to "30 mol% BaCO 3 、10 mol%ZnO、10 mol%SnO 2 、50 mol%Fe 2 O 3 "weighing materials according to the proportion, and mixing materials to obtain BaM ferrite initial powder;
(2) Ball milling for the first time: uniformly mixing BaM ferrite initial powder obtained in the step (1) and deionized water according to the mass ratio of 1:5 to obtain mixed powder slurry, uniformly mixing the mixed powder slurry in a high-energy ball mill for 5 h, and spraying the mixed powder slurry containing divalent Ce during the ball milling 2+ Ce (PFPC) 2 ·3H 2 0 rare earth complex is injected into a ball mill pot, wherein Ce (PFPC) 2 ·3H 2 0 rare earth complex accounts for 5% of the total weight of the mixed powder slurry to obtain mixed ball abrasive;
(3) Drying and sieving the mixed ball abrasive powder obtained in the step (2), and then carrying out primary presintering and secondary presintering treatment on the powder to obtain mixed powder, wherein the sintering temperature of the primary presintering is 1200 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 3 h; the sintering temperature of the secondary presintering is 700 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 2 h;
(4) Secondary ball milling: uniformly mixing the mixed powder obtained in the step (3) with deionized water according to the mass ratio of 1:5, and performing ball milling on the mixed powder by adopting a planetary ball mill for 2 h to obtain powder slurry;
(5) And (3) forming: performing magnetic field orientation molding technology on the powder slurry obtained in the step (4) to prepare a pressed compact, wherein the molding magnetic field is 2T, and the molding pressure is 50 MPa;
(6) Sintering: and (3) carrying out strong magnetic field heat treatment on the pressed compact obtained in the step (5), wherein the magnetic field strength is 8T, the heat treatment temperature is 700 ℃, the heating rate is 5 ℃/min, the heat preservation time is 3 h, and then quenching to room temperature, so that the double-ion combined substitution self-bias hexaferrite is finally obtained.
The double-ion combined substituted self-bias hexaferrite prepared by the invention is tested by a magnetic property and vector network analyzer, and the saturation magnetization intensity is 4 pi M s 5598 Gs, remanence ratio M r /M s Is 0.91 of coercivity H c 5726 and Oe, a ferromagnetic resonance linewidth Δh of 364 and Oe, and an anisotropy field H a 15.94 kOe.
Claims (2)
1. The preparation method of the double-ion combined substituted self-bias hexaferrite is characterized by comprising the following steps of:
(1) And (3) batching: in BaCO 3 Divalent Zn 2+ ZnO and tetravalent Sn of (2) 4+ SnO of (C) 2 、Fe 2 O 3 As raw materials, according to 20-30 mol% BaCO 3 、5~10 mol%ZnO、5~10 mol%SnO 2 、50~70 mol%Fe 2 O 3 "weighing materials according to the proportion, and mixing materials to obtain BaM ferrite initial powder;
(2) Ball milling for the first time: uniformly mixing BaM ferrite initial powder obtained in the step (1) and deionized water according to the mass ratio of 1:1-5 to obtain mixed powder slurry, uniformly mixing the mixed powder slurry in a high-energy ball mill for 1-5 h, wherein the high-energy ball milling is carried out in the ball milling processSpray pattern will contain divalent Ce 2+ Ce (PFPC) 2 ·3H 2 Injecting the O rare earth complex into a ball mill tank, wherein Ce (PFPC) 2 ·3H 2 The O rare earth complex accounts for 1-5% of the total weight of the mixed powder slurry to obtain a mixed ball abrasive;
(3) Drying the mixed ball abrasive powder obtained in the step (2), sieving, and then carrying out primary presintering and secondary presintering treatment on the powder to obtain mixed powder;
(4) Secondary ball milling: uniformly mixing the mixed powder obtained in the step (3) with deionized water according to the mass ratio of 1:1-5, and performing ball milling on the mixed powder for 2-8 hours by adopting a planetary ball mill to obtain powder slurry;
(5) And (3) forming: performing magnetic field orientation molding technology on the powder slurry obtained in the step (4) to prepare a pressed compact, wherein the molding magnetic field is 1-2T, and the molding pressure is 50-150 MPa;
(6) Sintering: and (3) carrying out strong magnetic field heat treatment on the pressed compact obtained in the step (5), wherein the magnetic field strength of the strong magnetic field heat treatment is 6-8T, the heat treatment temperature is 600-900 ℃, the heating rate is 5-10 ℃/min, the heat preservation time is 1-3 h, and then quenching to room temperature, so that the double-ion combined substitution self-bias hexagonal ferrite is finally obtained.
2. The method for preparing the double-ion combined substituted self-bias hexaferrite according to claim 1, which is characterized in that: the sintering temperature of the primary presintering in the step (3) is 950-1200 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 3-6 h; the sintering temperature of the secondary presintering is 700-950 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time is 2-4 h.
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