CN113990658B - High-remanence-ratio low-porosity hexagonal ferrite thick film and preparation method and application thereof - Google Patents
High-remanence-ratio low-porosity hexagonal ferrite thick film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hexagonal ferrite thick film with high remanence ratio and low porosity, a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing BaM powder with an organic carrier, and grinding to obtain uniformly mixed slurry; (2) Coating the paste on Al by screen printing method 2 O 3 Forming a thick film on the substrate; (3) Placing the thick film and the substrate in a magnetic field, heating, magnetizing and removing glue; (4) And carrying out pressure sintering on the magnetized thick film to obtain the hexagonal ferrite thick film. The invention prepares the hexaferrite thick film with high remanence ratio, low porosity, high density and high saturation magnetization by optimizing the organic carrier, controlling the particle size of BaM powder and improving the film-making process, and can be applied to a self-biased circulator, and the preparation method can realize theThe BaM thick film is prepared in a large scale at low cost, and the industrialization requirement is met.
Description
Technical Field
The invention relates to the technical field of thin film materials, in particular to a hexagonal ferrite thick film with high remanence ratio and low porosity, and a preparation method and application thereof.
Background
M-type hexaferrite (Ba, sr) Fe 12 O 19 (BaM for short) can be applied to microwave high frequency domain (such as K) under the condition of lower bias magnetic field or no bias magnetic field due to higher high uniaxial magnetocrystalline anisotropy and moderate saturation magnetization a Wave band) and millimeter wave band, namely, realizing self-bias application (a higher internal bias magnetic field is still kept after an external field is removed), and further realizing high frequency, miniaturization and integration of the magnetic microwave device.
At present, the preparation technology of barium ferrite films mainly comprises laser pulse deposition (PLD), liquid Phase Epitaxy (LPE), magnetron sputtering, screen printing and other processes. The BaM film with consistent lattice orientation and high quality can be prepared by PLD and magnetron sputtering, but the prepared film has limited thickness (only a few microns), low growth rate, small surface area, low residual magnetization and no potential of self-bias; compared with the film-making methods such as PLD and the like, the LPE has the advantages that the growth rate is high, the film thickness is large, the crystallization quality of the film is high, but the coercive force of the single crystal structure is very low due to the lack of a large number of defects such as crystal boundaries and the like, and the remanence is low, so that the LPE cannot be applied to self-biased devices; compared with the three preparation methods, the BaM thick film is prepared by a screen printing mode, the preparation method is simple, the cost is low, the film is easy to form, the efficiency is high, the film thickness is easy to adjust, and the large-scale industrial production is facilitated, but the performance of the BaM thick film prepared by the screen printing at present needs to be improved, and the problems of low remanence ratio, high porosity, low saturation magnetization and the like exist (Ref.: chen Zhongyan, feng Zekun, xiong Xuan. The research on the barium ferrite thick film [ J ]. Magnetic material and device prepared by the screen printing and the magnetic field orientation, 2010,41 (02): 22-24) 45, huang Zhaolin, zhang Moli, peng Bin. The research on the influence of the organic carrier on the barium ferrite microstructure [ J ]. Functional material and device science report, 5283 (01): 69-73), and the application of the thick film in 5329 self-biasing of the self-zft thick film is limited. Therefore, a method for preparing BaM film with high remanence ratio, low porosity and high saturation magnetization at low cost is needed.
Disclosure of Invention
The invention provides a hexagonal ferrite thick film with high remanence ratio and low porosity, a preparation method and application thereof, and a BaM thick film with high remanence ratio, low porosity and high saturation magnetization is obtained by optimizing the components and proportion of an organic carrier, reducing the particle size of BaM powder and improving the preparation method, so that the performance requirement of a self-biased circulator material is met.
In order to solve the above problems, the present invention provides the following technical solutions:
the invention provides a preparation method of a hexaferrite thick film, which comprises the following steps:
(1) Mixing BaM powder with an organic carrier, and grinding to obtain uniformly mixed slurry;
(2) Coating the paste on Al by screen printing method 2 O 3 Forming a thick film on the substrate;
(3) Placing the thick film and the substrate in a magnetic field, heating, magnetizing and removing glue;
(4) And sintering the magnetized thick film, and cooling to obtain the hexagonal ferrite thick film.
Further, the preparation of the BaM powder comprises the following steps:
s1: mixing the mixed raw materials with ball milling beads and absolute alcohol, and then carrying out ball milling;
s2: drying the ball-milled materials;
s3: grinding the dried materials, and placing the ground materials in air or oxygen atmosphere for pre-burning treatment;
s4: grinding the pre-sintered material into powder, and then placing the powder in a flowing oxygen atmosphere for sintering treatment;
s5: and mixing the sintered powder with glass frit, ball milling beads and absolute ethyl alcohol, and performing ball milling and drying treatment to obtain the required BaM powder.
Further, the raw material in S1 comprises BaCO 3 、Fe 2 O 3 。
Further, the raw material in S1 may further contain SrCo 3 。
Further, the molar purity of the components contained in the raw material in S1 was 99.99%.
Further, in S1, the rotation speed of ball milling is preferably 200-300 rpm, and the time of ball milling is preferably 12-24h.
Further, in S2 and S5, the drying temperature is preferably 70-100 ℃, and the drying time is preferably 30-50min.
Further, the pre-firing treatment in S3 specifically includes: the temperature is raised to 1000 ℃ at the heating rate of 2 ℃/min, and the temperature is kept for 4h.
Further, after the pre-sintering, the temperature is reduced at the rate of 1-3 ℃/min.
Further, the sintering treatment in S4 specifically is: heating to 1250 ℃ at the heating rate of 2 ℃/min, and preserving heat for 10h.
Further, the temperature is reduced at the temperature reduction rate of 2-3 ℃/min after sintering.
Further, in S5, the weight ratio of the glass frit to BaM powder is 2% -8%, and the ratio of large, medium and small ball grinding beads in the ball grinding beads is 1:1-3:3-5; wherein the diameter of the large ball grinding bead is 11mm, the diameter of the medium ball grinding bead is 7mm, and the diameter of the small ball grinding bead is 5mm.
Further, in S5, the rotation speed of the ball milling is preferably 200 to 300rpm, and the time of the ball milling is preferably 10 to 80 hours.
Further, in the step (1), the BaM powder has an average particle size of 0.3 to 0.7 μm.
Further, the organic vehicle comprises the following components in percentage by mass: 10-20% of epoxy resin, 40-60% of curing agent, 15-30% of terpineol, 5-10% of tributyl citrate and other components accounting for 1-3% of the total weight of the epoxy resin, the curing agent and the terpineol; the other components are selected from at least three of polydimethylsiloxane, ethylcellulose, castor oil, lecithin, epoxy acrylate and urethane acrylate.
Further, the epoxy resin is preferably a bisphenol a type epoxy resin, and the curing agent is preferably an aliphatic amine resin.
Further, the other components are preferably ethyl cellulose, castor oil, lecithin.
The organic vehicle is prepared by mixing and dispersing powders with glass powder and other solid powders for binding into paste, and printing on ceramic substrate by screen printing method. The organic carrier consists of an organic solvent, a thickening agent, a flatting agent, a dispersing agent and the like, wherein the organic solvent determines the rheological property, the volatility and the bonding property of the organic carrier, and the organic solvent used by the invention consists of epoxy resin, a curing agent, terpineol and tributyl citrate. In addition, the invention is added with components such as epoxy resin, curing agent and the like. The epoxy resin adjusts the rheological property of the organic carrier, so that the viscosity of the organic carrier is kept moderate, and the organic carrier can be fully mixed with the powder. This ensures that the thick film grains are free to rotate and fully oriented during magnetizing. The curing agent improves the adhesive property of the organic vehicle, so that the mixed slurry can be firmly adhered to the substrate. Under the combined action of epoxy resin and curing agent, the thick film can prevent the secondary flow of slurry during heating and magnetizing, and the surface is kept flat and the appearance is complete. In addition, the epoxy resin and the curing agent are added to form the multi-component organic solvent, so that the organic carrier can slowly volatilize in different temperature ranges, the porosity of the thick film is reduced, and the density of the film is improved.
Further, in the step (1), the mass ratio of BaM powder to organic carrier is 2-4:1.
Further, in the step (2), the screen printing operation specifically includes: mixing Al 2 O 3 The substrate is placed in a printing template, and slurry is coated on the substrate from the template through a scraper blade to form a thick film.
Further, in the step (3), the strength of the magnetic field is 8000-10000Oe; the heating and magnetizing temperature is 150-300 ℃, and the heating and magnetizing time is 20-50min.
The magnetization orients the easy magnetization axis (crystal C-axis) of the ferrite particles in the thick film along the external field to obtain high remanence. Wherein the heating in the magnetizing process mainly has the following three functions: the first is that at higher temperatures, the organic vehicle is more mobile to facilitate particle rotation; secondly, the thick film is primarily solidified, and the surface is kept flat; thirdly, the glue can be discharged preliminarily, and a part of the organic carriers can be volatilized. If the heating process is not carried out in the magnetizing process, the thick film paste cannot be completely solidified, and the surface of the thick film paste is uneven. Further, when the slurry is pressure-sintered, the thick film is deformed by squeezing because the slurry is not completely solidified, and thus the slurry cannot be used.
Further, in the step (4), the sintering is preferably pressure sintering.
Further, the specific operation of the pressure sintering is as follows: placing a load on the thick film, placing the thick film in an air atmosphere, heating to a sintering temperature, and sintering for 1-10h; the load pressure is 0.5-3MPa, the heating rate is 2-3 ℃/min, and the sintering temperature is 900-1200 ℃.
The pressure sintering makes BaM thick film promote the combination of powder particles and the densification of material under the combined action of heat energy and stress, and a thick film with higher density is obtained. If only ordinary sintering is performed, the density of the thick film is much lower than that of pressure sintering.
Further, the load is preferably Al 2 O 3 。
Further, in the step (4), the cooling rate is 2-3 ℃/min.
In the sintering process, the heating or cooling speed of the high-temperature area needs to be slowed down, so that BaM is promoted to grow in the high-temperature area to form crystals; on the other hand, the sample can crack when the temperature is increased or decreased too fast at high temperature. The temperature can be rapidly reduced in a low temperature region, and the sintering is accelerated.
In a second aspect, the invention provides a thick hexaferrite film prepared by the preparation method of the first aspect.
Further, the film thickness of the hexaferrite thick film is 0.1-0.4mm, for example: 0.1mm, 0.2mm, 0.3mm, 0.4mm, etc.
In a third aspect, the invention provides a use of the hexaferrite thick film of the second aspect in a self-biased circulator material.
The material requirements for the self-biasing circulator are as follows: remanence ratio (SQ, M) r /M s ) High, preferably SQ ≧ 0.9; the coercive force (Hc) is high, enough coercive force can ensure the working stability of the self-bias field and cannot be easily interfered by the outside, and when Hc is used>3kOe can keep the device stablePerforming fixed operation; high saturation magnetization (4 π Ms), when the 4 π Ms of the material>3kG can be applied to the self-biased circulator; the thick film has a film thickness of not less than 0.1. Mu.m.
Furthermore, the SQ of the hexaferrite thick film is more than or equal to 0.9, the Hc is more than 3kOe, and the 4 pi Ms is more than 3kG, so that the performance requirement of the self-biased circulator material is met.
The invention has the beneficial effects that:
1. according to the invention, the bonding performance of the organic carrier is improved by reducing the particle size of the powder and optimizing the formula of the organic solvent in the organic carrier, and meanwhile, the composition of the organic carrier is enriched, so that the surface flatness of the BaM thick film is improved, the porosity of the film is reduced, and the overall density of the thick film is further improved.
2. The invention provides a preparation process of a screen printing thick film for preparing a self-bias device material, which can be used for preparing a BaM thick film in a large scale at low cost, and can be used for preparing a flat, compact and crack-free BaM thick film by improving the processes such as heating magnetization, pressure sintering, sintering rise and temperature reduction rate control and the like.
3. The BaM thick film with high remanence ratio, low porosity, high density and high saturation magnetization is prepared by selecting materials and improving the preparation process, and the performance requirement of the material of the self-biased circulator is met.
Drawings
FIG. 1 is a schematic illustration of screen printing to produce thick films;
FIG. 2 is a room temperature XRD test pattern of the example and comparative example samples;
FIG. 3 is a room temperature SEM test image of example and comparative example samples;
fig. 4 is a hysteresis loop image of the example and comparative example.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used therein are commercially available without otherwise specified.
The BaM powders of the examples and comparative examples were prepared by the following method of preparation:
(1) Raw material BaCO with the molar purity of 99.99 percent 3 、Fe 2 O 3 The powder medicine is prepared according to the following steps of 1: mixing according to the molar ratio of 12;
(2) And placing the mixed powder into a ball milling tank, placing ball milling beads, adding absolute alcohol to the position with two thirds height of the ball milling tank, placing the ball milling tank into a ball mill, and carrying out ball milling for 18 hours at the rotating speed of 250 r/min.
(3) And taking out the powder subjected to the first ball milling, placing the powder into a mortar, placing the mortar into a dryer for drying, and drying the powder for 40 minutes at 80 ℃.
(4) Grinding the dried medicine, placing the ground medicine into a crucible, placing the crucible into a tube furnace, and pre-burning the medicine in the atmosphere of air or flowing oxygen. Heating according to a certain temperature rate, wherein the heating rate is 2 ℃/min; presintering temperature is 1000 ℃, and presintering time is 4 hours; the cooling rate is 1 to 3 ℃/min.
(5) After the pre-sintering is finished, taking out the sample, and manually grinding the sample in a cleaned mortar for 30 minutes; and putting the ground powder into a clean crucible, and putting the crucible into a tube furnace to perform sintering treatment in a flowing oxygen atmosphere. Heating according to a certain temperature gradient, wherein the heating rate is 2 ℃/min; the sintering temperature is 1250 ℃, and the sintering time is 10 hours; the cooling rate is 2 ℃/min to 3 ℃/min.
(6) Mixing the BaM powder after sintering with a certain proportion of glass frit, wherein the weight ratio of the glass frit to BaM is 4%; then placed in a ball mill jar and placed in a 1:2:4, wherein the large-size ball grinding bead is 11mm, the medium-size ball grinding bead is 7mm, and the small-size ball grinding bead is 5mm; and adding absolute alcohol to the position of two thirds of the height of the ball milling tank, putting the ball milling tank into a ball mill, and performing ball milling for a certain time at the rotating speed of 250 r/min.
(7) And taking out the sample subjected to the second ball milling, placing the sample into a mortar, placing the mortar into a dryer for drying, and drying at 80 ℃ for 40 minutes to obtain the required BaM powder, wherein the particle size of the powder is related to the ball milling time.
Example 1
Mixing BaM powder which is ball-milled for the second time for 80 hours and has an average particle size of 0.4 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 19 weight percent of bisphenol A epoxy resin, 58 weight percent of fatty amine resin, 16 weight percent of terpineol, 9 weight percent of tributyl citrate, 2 weight percent of ethyl cellulose, 1 weight percent of lecithin and 1 weight percent of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and heating for 50min in a 8000Oe magnetic field at 200 deg.C; and loading the magnetized thick film with 1MPa pressure and sintering at 1100 ℃ for 4h to prepare the BaM thick film.
Example 2
Mixing BaM powder which is ball-milled for the second time for 80 hours and has an average particle size of 0.4 μm and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 11wt% of bisphenol A type epoxy resin, 58wt% of fatty amine resin, 27wt% of terpineol, 9wt% of tributyl citrate, 2wt% of ethyl cellulose, 1wt% of lecithin and 1wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and heating for 50min in a 8000Oe magnetic field at 200 deg.C; and loading the magnetized thick film with 1MPa pressure and sintering at 1100 ℃ for 4h to prepare the BaM thick film.
Example 3
Mixing BaM powder which is ball-milled for the second time for 50 hours and has an average particle size of 0.5 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 16wt% of bisphenol A type epoxy resin and 50wt% of fatty amineResin, 23wt% of terpineol, 7wt% of tributyl citrate, 2wt% of ethyl cellulose, 1wt% of lecithin and 1wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and heating for 50min under the conditions of 8000Oe magnetic field and 200 ℃; and loading the magnetized thick film with 1MPa pressure and sintering at 1000 ℃ for 4h to prepare the BaM thick film.
Comparative example 1
Mixing BaM powder which is ball-milled for the second time for 50 hours and has an average particle size of 0.5 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 75wt% of terpineol, 12wt% of tributyl citrate, 5wt% of ethyl cellulose, 4wt% of lecithin and 4wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and heating for 50min under the conditions of 8000Oe magnetic field and 200 ℃; and loading the magnetized thick film with 1MPa pressure and sintering at 1100 ℃ for 4h to prepare the BaM thick film.
Comparative example 2
Mixing BaM powder which is subjected to ball milling for 6 hours for the second time and has an average particle size of 0.8 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 16wt% of bisphenol A type epoxy resin, 50wt% of fatty amine resin, 23wt% of terpineol, 7wt% of tributyl citrate, 2wt% of ethyl cellulose, 1wt% of lecithin and 1wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and heating for 50min in a 8000Oe magnetic field at 200 deg.C; and loading the magnetized thick film with 1MPa pressure and sintering at 1100 ℃ for 4h to prepare the BaM thick film.
Comparative example 3
Mixing BaM powder which is subjected to ball milling for 6 hours for the second time and has an average particle size of 0.8 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 75wt% of terpineol, 12wt% of tributyl citrate, 5wt% of ethyl cellulose, 4wt% of lecithin and 4wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, placing in a magnetic field of 8000Oe,Heating at 200 deg.C for 50min; and loading the magnetized thick film with 1MPa pressure and sintering at 1100 ℃ for 4h to prepare the BaM thick film.
Comparative example 4
Mixing BaM powder which is ball-milled for the second time for 50 hours and has an average particle size of 0.5 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 16wt% of bisphenol A type epoxy resin, 50wt% of fatty amine resin, 23wt% of terpineol, 7wt% of tributyl citrate, 2wt% of ethyl cellulose, 1wt% of lecithin and 1wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and heating for 50min in a 8000Oe magnetic field at 200 deg.C; and sintering the magnetized thick film at 1100 ℃ for 4h without pressure to prepare the BaM thick film.
Comparative example 5
Mixing BaM powder which is ball-milled for the second time for 50 hours and has an average particle size of 0.5 mu m and an organic carrier in a mass ratio of 3:1, mixing to obtain mixed slurry, wherein the organic carrier consists of the following components: 16wt% of bisphenol A type epoxy resin, 50wt% of fatty amine resin, 23wt% of terpineol, 7wt% of tributyl citrate, 2wt% of ethyl cellulose, 1wt% of lecithin and 1wt% of castor oil; on Al by screen printing 2 O 3 Forming a thick film on the substrate, and standing for 50min at normal temperature in a 8000Oe magnetic field; and sintering the magnetized thick film at 1100 ℃ for 4h without pressure to prepare the BaM thick film.
Performance test
The thick BaM films of examples 1-3 and comparative examples 1-5 were characterized by XRD, SEM and hysteresis loop tests.
XRD test results: as shown in FIG. 2, in which FIGS. 2a to 2C are XRD patterns of BaM thick films prepared in examples 1 to 3, respectively, and FIGS. 2d to 2h are XRDs of BaM thick films prepared in comparative examples 1 to 5, respectively, it can be seen from FIGS. 2a to 2C that the thick films prepared in pressure-sintered examples 1 to 3 have a sharp peak at (0, 2l) and only a hetero peak of (1,0,7) having a small intensity, which indicates that the thick films prepared in examples 1 to 3 have a strong C-axis orientation; comparative example 1 changed the organic vehicle (no epoxy resin and curing agent contained in the organic solvent) compared to example 1, the orientation of the thick film became random, and it can be seen from fig. 2d that there are hetero peaks (1,0,7), (1,1,4), (2,0, 11) in addition to the main peak (0, 2l); in comparison with example 1, the BaM powder of comparative example 2 has a shorter powder secondary ball milling time and a larger particle size, and under otherwise identical conditions, as can be seen from fig. 2e, the thick film prepared in comparative example 2 has many hetero peaks at (1,0,5), (1,0,7), (1,1,4), (2,0,6) and a more disordered crystal orientation, although the peaks at (0,0,2l) are still dominant; comparative example 3 the organic vehicle (no epoxy resin and curing agent contained in the organic solvent) was replaced on the basis of comparative example 2. As shown in FIG. 2f, the thick film prepared in comparative example 3 had the strongest diffraction peak intensity at (1,0,5), and the intensities of other miscellaneous peaks were enhanced correspondingly, while the intensities of diffraction peaks corresponding to (0, 2l) were all reduced; comparative example 4 differs from example 1 only in the sintering process, comparative example 4 in which the thick film was not subjected to a press treatment during sintering, and it can be seen from fig. 2g that the unpressurized BaM thick film, although the peak at (0, 2l) was very pronounced, the thick film had strong C-axis orientation, but the hetero-peaks occurred at (1,0,5), (1,0,7), (1,1,4); FIG. 2h shows the XRD pattern of comparative example 5, the difference between the BaM thick film prepared in comparative example 5 and comparative example 4, the process only during magnetization, comparative example 5 without heating during magnetization, the orientation of the prepared thick film is not complete enough, the peak at (0, 2l) is weak, the number of hetero peaks is large and the strength is high.
SEM test results: as shown in fig. 3, in which fig. 3a to 3c are SEM images of BaM thick films prepared in examples 1 to 3, respectively, and fig. 3d to 3h are SEM images of BaM thick films prepared in comparative examples 1 to 5, respectively; as can be seen from fig. 3a to 3c, the surfaces of the thick films prepared in examples 1 to 3 are more dense and relatively flat, which also illustrates that the crystal grains of the thick films are tightly compressed together through the material optimization and the improvement of the preparation process, further reducing the crystal porosity and increasing the density of the thin films; FIG. 3d is a SEM image of a thick film prepared in comparative example 1, in comparison with example 1, in which the modification of the organic vehicle causes the thick film to have some porosity while generating some cracks upon sintering; FIGS. 3e and 3f are SEM topographies of thick films prepared according to comparative examples 2 and 3, respectively, having a larger particle size of BaM powder, and BaM powder having a particle size too large to allow the film to have more porosity; as can be seen from fig. 3g, the grains of the thick film prepared in comparative example 4 exhibited a distinct out-of-plane orientation, the grain growth was perfect, and the inter-grain pores were small and small; the larger difference in grain size and the presence of more voids in the thick film prepared in comparative example 5 (as shown in fig. 3 h) is presumed to be due to the lack of heating during magnetization, the organic vehicle is not primarily excluded, and excessive void generation occurs during sintering.
Hysteresis loop test results: as shown in fig. 4, in which fig. 4a to 4c are the hysteresis loop test results of BaM thick films prepared in examples 1 to 3, respectively, and fig. 4d to 4h are the hysteresis loop test results of BaM thick films prepared in comparative examples 1 to 5, respectively; the test results and relative densities (i.e., the ratio of the actual density to the theoretical density of the thick film) for each of the above samples are summarized in table 1 below:
TABLE 1 respective Performance parameters of the samples
As can be seen from Table 1, the thick films prepared in examples 1 to 3 have a lower particle size and a higher relative density than the comparative examples, and it can be seen from the results of the hysteresis loop test that the magnetic indexes of the thick films prepared in the examples all satisfy the requirements of the self-bias circulator material.
The characterization and test results are combined to obtain:
(1) comparing example 1 with comparative example 1, it can be seen that when the organic solvent is not in the preferred range, the crystal orientation of the thick film has the appearance of a miscellaneous peak, the micro porosity is increased, the density is reduced, and the SQ value of the prepared thick film is reduced;
(2) as can be seen from comparison of example 1 with comparative example 2, when the powder particle size is out of the preferred range, the crystal orientation of the thick film becomes more disordered, the density decreases due to increased porosity, and the SQ value of the prepared thick film decreases;
(3) comparison of comparative example 2 with comparative example 3 shows that when the organic vehicle is not preferable, the crystal orientation of the thick film is more disordered and the hetero-peak becomes the strongest peak; the porosity is further increased, the relative density is small, in addition, the saturation magnetization is reduced, the residual magnetization is increased, and the SQ is further reduced;
(4) comparing example 1 and comparative example 4, it can be seen that hot press sintering can enhance the crystal orientation of BaM thick film, reduce microscopic porosity, enhance the thick film density, and increase the thick film relative density from 0.78 to 0.92 after hot pressing, but the remanence ratio (SQ) is slightly reduced from 0.94 to 0.91.
(5) In comparison with comparative example 5 and comparative example 4, it can be seen that the thick film becomes more porous and the density decreases without heating during the magnetization, and further, the saturation magnetization, residual magnetization and residual magnetization ratio decrease.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (4)
1. The preparation method of the hexaferrite thick film is characterized by comprising the following steps of:
(1) Mixing BaM powder with an organic carrier, and grinding to obtain uniformly mixed slurry; the BaM powder has an average particle size of 0.3-0.7 μm; the mass ratio of BaM powder to organic carrier is 2-4:1; the organic carrier comprises the following components in percentage by mass: 10-20% of epoxy resin, 40-60% of curing agent, 15-30% of terpineol, 5-10% of tributyl citrate and other components accounting for 1-3% of the total weight of the epoxy resin, the curing agent and the terpineol; the other components are selected from at least three of polydimethylsiloxane, ethyl cellulose, castor oil, lecithin, epoxy acrylate and urethane acrylate; the epoxy resin is bisphenol A type epoxy resin, and the curing agent is aliphatic amine resin;
(2) Passing the slurry through a wireApplication to Al by screen printing 2 O 3 Forming a thick film on the substrate;
(3) Placing the thick film and the substrate in a magnetic field, and heating and magnetizing; the strength of the magnetic field is 8000-10000Oe; the heating and magnetizing temperature is 150-300 ℃, and the heating and magnetizing time is 20-50 min;
(4) Sintering the magnetized thick film, and cooling to obtain the hexagonal ferrite thick film; the sintering is pressure sintering; the specific operation of the pressure sintering is as follows: placing a load on the thick film, then placing the thick film in an air atmosphere, heating to a sintering temperature, and sintering to 1-10h; the load pressure is 0.5-3MPa, the heating rate is 2-3 ℃ per min, and the sintering temperature is 900-1200 ℃;
the method for controlling the particle size of the BaM powder specifically comprises the following steps: mixing the BaM sintered powder with glass frit, adding ball milling beads and absolute ethyl alcohol, and ball milling at the rotating speed of 200-300 rpm for 10-80 h; the weight ratio of the glass frit to BaM powder is 2% -8%, the ratio of the large, medium and small ball grinding beads in the ball grinding beads is 1:1-3:3-5, wherein the diameter of the large ball grinding bead is 11mm, the diameter of the medium ball grinding bead is 7mm, and the diameter of the small ball grinding bead is 5mm.
2. The method for preparing the hexaferrite thick film according to claim 1, wherein in the step (4), the temperature reduction rate is 2-3 ℃/min.
3. The hexaferrite thick film prepared by the preparation method of claim 1 or 2, wherein the thickness of the hexaferrite thick film is 0.1-0.4 mm.
4. Use of a hexaferrite thick film of claim 3 in a self-biasing circulator material.
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| PCT/CN2022/100858 WO2023093025A1 (en) | 2021-11-23 | 2022-06-23 | Hexagonal ferrite thick film with high remanence ratio and low porosity, and preparation method therefor and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864412A (en) * | 2014-02-25 | 2014-06-18 | 桂林电子科技大学 | Low-resistance BaM<II><x>Bi<1-x>O3 negative-temperature-coefficient thermosensitive thick-film material and preparation method thereof |
| CN108823531A (en) * | 2018-06-28 | 2018-11-16 | 苏州大学 | Flexible hexad ferrite film and preparation method thereof |
| CN112851325A (en) * | 2021-01-29 | 2021-05-28 | 无锡杰夫电声股份有限公司 | Z-type hexaferrite powder with high saturation magnetization and preparation method thereof |
Family Cites Families (3)
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| US20100173101A1 (en) * | 2006-08-11 | 2010-07-08 | Northeastern University | Method of manufacturing thick-film, low microwave loss, self-biased barium-hexaferrite having perpendicular magnetic anisotropy |
| JP4678783B2 (en) * | 2006-12-06 | 2011-04-27 | Ｎｅｃトーキン株式会社 | Soft magnetic thick film and inductor using the same |
| CN113990658B (en) * | 2021-11-23 | 2023-01-06 | 苏州大学 | High-remanence-ratio low-porosity hexagonal ferrite thick film and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864412A (en) * | 2014-02-25 | 2014-06-18 | 桂林电子科技大学 | Low-resistance BaM<II><x>Bi<1-x>O3 negative-temperature-coefficient thermosensitive thick-film material and preparation method thereof |
| CN108823531A (en) * | 2018-06-28 | 2018-11-16 | 苏州大学 | Flexible hexad ferrite film and preparation method thereof |
| CN112851325A (en) * | 2021-01-29 | 2021-05-28 | 无锡杰夫电声股份有限公司 | Z-type hexaferrite powder with high saturation magnetization and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| BARIUM HEXAFERRITE THICK FILMS BY HOT PRESS SINTERING;H. C. JIANG等;《Modern Physics Letters B》;20100310;第24卷(第6期);第561-566页 * |
| Barium hexaferrite thick films prepared by screen printing for microwave applications;W. L. Zhang等;《Materials Research Innovations》;20160105;S8-537-S8-540 * |
| Effects of sintering temperature on the barium hexaferrite thick films prepared by screen printing method;Zhaolin Huang等;《Functional and Electronic Materials》;20111231;51-54页 * |
| Temperature dependent magnetic properties of conical magnetic structure M-type hexaferrites BaFe10.2Sc1.8O19 and SrFe10.2Sc1.8O19;Weihu Zhang等;《Journal of Alloys and Compounds》;20180326;368-374页 * |
| 丝网印刷钡铁氧体厚膜及其在集成环行器中的应用研究;黄照林;《硕士学位论文全文数据库工程科技Ⅱ辑》;20110715(第07期);21-58页 * |
| 钡铁氧体厚膜的制备工艺研究;谌贵辉等;《电子元件与材料》;20120229;第31卷(第2期);30-32页 * |
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