WO2023093025A1 - 一种高剩磁比、低孔隙率六角铁氧体厚膜及其制备方法与应用 - Google Patents

一种高剩磁比、低孔隙率六角铁氧体厚膜及其制备方法与应用 Download PDF

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WO2023093025A1
WO2023093025A1 PCT/CN2022/100858 CN2022100858W WO2023093025A1 WO 2023093025 A1 WO2023093025 A1 WO 2023093025A1 CN 2022100858 W CN2022100858 W CN 2022100858W WO 2023093025 A1 WO2023093025 A1 WO 2023093025A1
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thick film
hexagonal ferrite
preparation
bam
ball milling
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French (fr)
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汤如俊
彭峰
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苏州大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/16—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates the magnetic material being applied in the form of particles, e.g. by serigraphy, to form thick magnetic films or precursors therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/08—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers
    • H01F10/10—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition
    • H01F10/18—Thin magnetic films, e.g. of one-domain structure characterised by magnetic layers characterised by the composition being compounds
    • H01F10/20—Ferrites
    • H01F10/205—Hexagonal ferrites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F13/00—Apparatus or processes for magnetising or demagnetising
    • H01F13/003—Methods and devices for magnetising permanent magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/22—Heat treatment; Thermal decomposition; Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P1/00—Auxiliary devices
    • H01P1/32—Non-reciprocal transmission devices
    • H01P1/38—Circulators

Definitions

  • 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, a preparation method and application thereof.
  • BaM M-type hexagonal ferrite (Ba,Sr)Fe 12 O 19 (referred to as BaM), because of its high uniaxial magnetocrystalline anisotropy and moderate saturation magnetization, can be realized at a lower bias magnetic field or In the case of no bias magnetic field, it is applied in microwave high-frequency domain (such as K a band) and millimeter wave frequency band, that is, to realize self-bias application (remaining a high internal bias magnetic field after removing the external field), and then realize magnetic microwave devices High frequency, miniaturization and integration.
  • microwave high-frequency domain such as K a band
  • millimeter wave frequency band millimeter wave frequency band
  • barium ferrite film mainly include laser pulse deposition (PLD), liquid phase epitaxy (LPE), magnetron sputtering and screen printing and other processes.
  • PLD laser pulse deposition
  • LPE liquid phase epitaxy
  • magnetron sputtering screen printing and other processes.
  • BaM films with consistent lattice orientation and high quality can be prepared by PLD and magnetron sputtering, but the thickness of the prepared film is limited (only a few microns), the growth rate is low, the surface area is small, and the residual magnetization is low.
  • the advantages of LPE are mainly in the high growth rate, large film thickness and high crystal quality of the film, but it is precisely because of the lack of a large number of defects such as grain boundaries that cause this
  • the coercivity of the quasi-single crystal structure is very low, and the residual magnetism is relatively low and cannot be applied to self-bias devices;
  • the BaM thick film is prepared by screen printing, the preparation method is simple, and the cost is low. And it is easy to form a film, high in efficiency, and easy to adjust the film thickness, which is conducive to large-scale industrial production.
  • the invention provides a high remanence ratio, low porosity hexagonal ferrite thick film and its preparation method and application.
  • a thick BaM film with high remanence ratio, low porosity, and high saturation magnetization is obtained, which meets the performance requirements of self-biased circulator materials.
  • the present invention provides the following technical solutions:
  • the first aspect of the present invention provides a method for preparing a hexagonal ferrite thick film, comprising the following steps:
  • the preparation of the BaM powder comprises the following steps:
  • the raw materials in S1 include BaCO 3 and Fe 2 O 3 .
  • the raw material in S1 may also include SrCo 3 .
  • the molar purity of the components contained in the raw materials in S1 is 99.99%.
  • the rotational speed of the ball mill is preferably 200-300 rpm, and the time of the ball mill is preferably 12-24 hours.
  • the drying temperature is preferably 70-100° C.
  • the drying time is preferably 30-50 minutes.
  • the pre-calcination treatment in S3 specifically includes: raising the temperature to 1000° C. at a heating rate of 2° C./min, and keeping the temperature for 4 hours.
  • the temperature is lowered at a cooling rate of 1-3° C./min after pre-burning.
  • the sintering treatment in S4 specifically includes: raising the temperature to 1250° C. at a heating rate of 2° C./min, and keeping the temperature for 10 hours.
  • the temperature is lowered at a cooling rate of 2-3° C./min.
  • the weight ratio of the glass frit to BaM powder is 2%-8%, and the ratio of large, medium and small ball milling beads in the ball milling beads is 1:1-3:3-5;
  • the diameter of the ball milling beads is 11 mm, the diameter of the medium ball milling beads is 7 mm, and the diameter of the small ball milling beads is 5 mm.
  • the rotational speed of the ball mill is preferably 200-300 rpm, and the time of the ball mill is preferably 10-80 h.
  • the average particle size of the BaM powder is 0.3-0.7 ⁇ m.
  • the organic vehicle comprises the following components by mass percentage: 10-20% epoxy resin, 40-60% curing agent, 15-30% terpineol, 5-10% tricitrate Butyl ester and other components each accounting for 1-3%; said other components are selected from polydimethylsiloxane, ethyl cellulose, castor oil, lecithin, epoxy acrylate and polyurethane acrylate At least three.
  • the epoxy resin is preferably a bisphenol A epoxy resin
  • the curing agent is preferably an aliphatic amine resin.
  • the other components are preferably ethyl cellulose, castor oil, lecithin.
  • the organic carrier is to mix and disperse the powder with glass powder for bonding and other solid powders to form a paste slurry, so that it can be printed on the ceramic substrate by screen printing.
  • Organic vehicle is made up of organic solvent, thickener, leveling agent, dispersant etc., wherein, organic solvent determines the rheology, volatility, bonding performance of organic vehicle, and the organic solvent used in the present invention is made of epoxy resin, solidified agent, terpineol, tributyl citrate composition.
  • the present invention adds components such as epoxy resin and curing agent.
  • the epoxy resin adjusts the rheology of the organic vehicle so that the viscosity of the organic vehicle remains moderate and can be thoroughly mixed with the powder.
  • the curing agent improves the bonding performance of the organic vehicle, so that the mixed slurry can be firmly adhered to the substrate.
  • the thick film Under the joint action of epoxy resin and curing agent, the thick film can prevent the secondary flow of the slurry during heating and magnetization, and keep the surface smooth and the shape complete.
  • the addition of epoxy resin and curing agent to form a multi-component organic solvent can slowly volatilize the organic carrier in different temperature ranges to reduce the porosity of the thick film and increase the density of the film.
  • step (1) the mass ratio of the BaM powder to the organic vehicle is 2-4:1.
  • the screen printing operation specifically includes: putting the Al 2 O 3 substrate into a printing template, and applying the slurry from the template to the substrate by a scraper to form a thick film.
  • step (3) the strength of the magnetic field is 8000-10000 Oe; the heating and magnetizing temperature is 150-300° C., and the heating and magnetizing time is 20-50 min.
  • 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.
  • the heating during the magnetization process mainly has the following three functions: the first is that at higher temperatures, the fluidity of the organic carrier is stronger to facilitate the rotation of the particles; the second is to initially solidify the thick film and keep the surface smooth; the third is to Preliminary degumming can be used to volatilize part of the organic carrier. If the heating process is not carried out during the magnetization process, the thick film slurry cannot be completely solidified, and the surface will be uneven. And when carrying out pressure sintering, because the slurry is not completely solidified, the thick film will be squeezed and deformed, and cannot be used.
  • the sintering is preferably pressure sintering.
  • the specific operation of the pressure sintering is: place a load on the thick film and place it in an air atmosphere, raise the temperature to the sintering temperature, and sinter for 1-10 hours; the pressure of the load is 0.5-3 MPa, and the heated The rate is 2-3°C/min, and the sintering temperature is 900-1200°C.
  • Pressure sintering makes the BaM thick film under the joint action of thermal energy and stress, promote the combination of powder particles and the densification of the material, and obtain a thicker film with higher density. If only ordinary sintering is performed, the density of the thick film will be much lower than that of pressure sintering.
  • the loading is preferably Al 2 O 3 .
  • step (4) the cooling rate is 2-3°C/min.
  • the high-temperature zone needs to slow down the heating or cooling rate, on the one hand, it promotes the growth of BaM in the high-temperature zone, allowing the crystal to form; on the other hand, heating or cooling too fast at high temperature will cause the sample to crack.
  • the temperature In the low temperature zone, the temperature can be quickly lowered and the sintering can be accelerated.
  • the second aspect of the present invention provides a hexagonal ferrite thick film prepared by the preparation method described in the first aspect.
  • the thickness of the hexagonal ferrite thick film is 0.1-0.4mm, for example: 0.1mm, 0.2mm, 0.3mm, 0.4mm and so on.
  • the third aspect of the present invention provides the application of the hexagonal ferrite thick film described in the second aspect in the self-biased circulator material.
  • the material requirements for self-biased circulators are as follows: high remanence ratio (SQ, M r /M s ), preferably SQ ⁇ 0.9; high coercive force (Hc), sufficient coercive force can ensure self-bias The working stability of the setting field will not be easily disturbed by the outside world.
  • Hc>3kOe the device can maintain stable operation; high saturation magnetization (4 ⁇ Ms), when the material’s 4 ⁇ Ms>3kG can be applied to self-biased circulators; thick The film thickness of the film is not less than 0.1 ⁇ m.
  • the SQ ⁇ 0.9, Hc>3kOe, and 4 ⁇ Ms>3kG of the hexagonal ferrite thick film meet the performance requirements of the self-biased circulator material.
  • the present invention improves the bonding performance of the organic carrier by reducing the particle size of the powder and optimizing the formulation of the organic solvent in the organic carrier, and enriches the composition of the organic carrier at the same time, which is beneficial to improving the surface smoothness of the BaM thick film and reducing the thickness of the film. porosity, thereby increasing the overall density of the thick film.
  • the present invention provides a screen printing thick film preparation process for preparing self-biased device materials.
  • the above preparation process can prepare BaM thick films at low cost and on a large scale, and the temperature can be raised and lowered by heating, magnetizing, pressurized sintering and sintering Through the improvement of process such as speed control, a flat, dense, and crack-free BaM thick film is prepared.
  • the present invention prepares a BaM thick film with high remanence ratio, low porosity, high density and high saturation magnetization through the improvement of material selection and preparation process, which meets the performance requirements of self-biased circulator materials.
  • Fig. 1 is the schematic diagram that screen printing prepares thick film
  • Fig. 2 is the room temperature XRD test pattern of embodiment and comparative example sample
  • Fig. 3 is the room temperature SEM test image of embodiment and comparative example sample
  • Fig. 4 is the hysteresis loop images of the samples of the examples and the comparative examples.
  • the heating rate is 2°C/min; the pre-burning temperature is 1000°C, and the pre-burning time is 4 hours; the cooling rate is 1°C/min to 3°C/min.
  • the heating rate is 2°C/min; the sintering temperature is 1250°C, and the sintering time is 10 hours; the cooling rate is 2°C/min to 3°C/min.
  • the organic vehicle is composed of the following components: 19 wt% bisphenol A ring Oxygen resin, 58wt% fatty amine resin, 16wt% terpineol, 9wt% tributyl citrate, 2wt% ethyl cellulose, 1wt% lecithin and 1wt% castor oil; by screen printing A thick film is formed on an Al 2 O 3 substrate, placed in a magnetic field of 8000Oe and heated at 200°C for 50min; the thick film after magnetization is loaded with a pressure of 1MPa and sintered at 1100°C for 4h to prepare a BaM thick film.
  • the BaM powder with an average particle size of 0.4 ⁇ m after the second ball milling for 80 hours and the organic vehicle at a mass ratio of 3:1 to obtain a mixed slurry, wherein the organic vehicle is composed of the following components: 11wt% bisphenol A ring Oxygen resin, 58wt% fatty amine resin, 27wt% terpineol, 9wt% tributyl citrate, 2wt% ethyl cellulose, 1wt% lecithin and 1wt% castor oil; by screen printing A thick film is formed on an Al 2 O 3 substrate, placed in a magnetic field of 8000Oe and heated at 200°C for 50min; the thick film after magnetization is loaded with a pressure of 1MPa and sintered at 1100°C for 4h to prepare a BaM thick film.
  • the organic vehicle is composed of the following components: 11wt% bisphenol A ring Oxygen resin, 58wt% fatty amine resin, 27wt% terpineol,
  • the BaM powder with an average particle size of 0.5 ⁇ m after the second ball milling for 50 hours and an organic vehicle at a mass ratio of 3:1 to obtain a mixed slurry, wherein the organic vehicle consists of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7wt% tributyl citrate, 2wt% ethyl cellulose, 1wt% lecithin and 1wt% castor oil; by screen printing A thick film is formed on an Al 2 O 3 substrate, placed in a magnetic field of 8000Oe and heated at 200°C for 50min; the magnetized thick film is loaded with a pressure of 1MPa and sintered at 1000°C for 4h to prepare a BaM thick film.
  • the organic vehicle consists of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7w
  • the BaM powder with an average particle size of 0.5 ⁇ m after the second ball milling for 50 hours and an organic vehicle at a mass ratio of 3:1 to obtain a mixed slurry, wherein the organic vehicle consists of the following components: 75wt% terpineol, 12wt% % tributyl citrate, 5wt% ethyl cellulose, 4wt% lecithin and 4wt% castor oil; form a thick film on an Al 2 O 3 substrate by screen printing, and place it in a 8000Oe magnetic field at 200°C Under the condition of heating for 50min; the magnetized thick film is loaded with 1MPa pressure and sintered at 1100°C for 4h to prepare a BaM thick film.
  • the organic vehicle consists of the following components: 75wt% terpineol, 12wt% % tributyl citrate, 5wt% ethyl cellulose, 4wt% lecithin and 4wt% castor oil; form a thick film
  • the organic vehicle is composed of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7wt% tributyl citrate, 2wt% ethyl cellulose, 1wt% lecithin and 1wt% castor oil; by screen printing A thick film is formed on an Al 2 O 3 substrate, placed in a magnetic field of 8000Oe and heated at 200°C for 50min; the thick film after magnetization is loaded with a pressure of 1MPa and sintered at 1100°C for 4h to prepare a BaM thick film.
  • the BaM powder with an average particle size of 0.8 ⁇ m after the second ball milling for 6 hours and an organic vehicle at a mass ratio of 3:1 to obtain a mixed slurry, wherein the organic vehicle consists of the following components: 75wt% terpineol, 12wt% % tributyl citrate, 5wt% ethyl cellulose, 4wt% lecithin and 4wt% castor oil; form a thick film on an Al 2 O 3 substrate by screen printing, and place it in a 8000Oe magnetic field at 200°C Under the condition of heating for 50min; the magnetized thick film is loaded with 1MPa pressure and sintered at 1100°C for 4h to prepare a BaM thick film.
  • the organic vehicle consists of the following components: 75wt% terpineol, 12wt% % tributyl citrate, 5wt% ethyl cellulose, 4wt% lecithin and 4wt% castor oil; form a thick film
  • the BaM powder with an average particle size of 0.5 ⁇ m after the second ball milling for 50 hours and an organic vehicle at a mass ratio of 3:1 to obtain a mixed slurry, wherein the organic vehicle consists of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7wt% tributyl citrate, 2wt% ethyl cellulose, 1wt% lecithin and 1wt% castor oil; by screen printing Form a thick film on an Al 2 O 3 substrate, place it in a magnetic field of 8000Oe, and heat it at 200°C for 50 minutes; the magnetized thick film is sintered at 1100°C for 4 hours without pressure to prepare a BaM thick film.
  • the organic vehicle consists of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7wt% tribu
  • the BaM powder with an average particle size of 0.5 ⁇ m after the second ball milling for 50 hours and an organic vehicle at a mass ratio of 3:1 to obtain a mixed slurry, wherein the organic vehicle consists of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7wt% tributyl citrate, 2wt% ethyl cellulose, 1wt% lecithin and 1wt% castor oil; by screen printing A thick film was formed on an Al 2 O 3 substrate, and it was left to stand at room temperature for 50 minutes in a magnetic field of 8000 Oe; the thick film after magnetization was sintered at 1100°C for 4 hours without pressure to prepare a BaM thick film.
  • the organic vehicle consists of the following components: 16 wt% bisphenol A ring Oxygen resin, 50wt% fatty amine resin, 23wt% terpineol, 7wt% tribu
  • Comparative Example 3 replaced the organic vehicle on the basis of Comparative Example 2 (the organic solvent does not contain epoxy resin and curing agent), as shown in Figure 2f, Comparative Example 3 was prepared
  • the thick film has the strongest diffraction peak intensity at (1,0,5), and other miscellaneous peak intensities are also enhanced accordingly, and the corresponding diffraction peak intensity of (0,0,2l) all decreases; comparative example 4 and embodiment 1 There is only a difference in the sintering process.
  • the thick film was not subjected to pressure treatment during sintering.
  • FIGS 3e and 3f are the SEM topography images of thick films prepared in comparative examples 2 and 3 with larger particle sizes of BaM powder, respectively, and the excessive particle size of BaM powder makes the films have more pores; as can be seen from Figure 3g, comparative example 4
  • the grains of the prepared thick film show obvious out-of-plane orientation, the grain growth is perfect, and the pores between the grains are few and small; while the thick film prepared in Comparative Example 5 has a large gap between the grains and more pores (As shown in Figure 3h), it is speculated that the organic carrier was not preliminarily excluded due to the lack of heating during magnetization, resulting in the generation of excessive pores during sintering.
  • Hysteresis loop test results as shown in Figure 4, wherein Figures 4a to 4c are the hysteresis loop test results of the BaM thick films prepared in Examples 1 to 3, respectively, and Figures 4d to 4h are Comparative Examples 1 to 5 respectively
  • the hysteresis loop test results of the BaM thick film prepared in the test results and relative density (i.e. the ratio of the actual density and theoretical density of the thick film) of the above-mentioned samples are summarized in the following table 1:
  • Comparative Example 2 Comparative Example 3 Comparing Comparative Example 2 and Comparative Example 3, it can be seen that when the organic carrier is not preferred, the crystal orientation of the thick film is more disordered, and the miscellaneous peak becomes the strongest peak; the porosity is further increased, and the relative density is smaller. In addition, the saturation magnetization decreases, The residual magnetization increases, and the SQ decreases further;
  • Example 1 Comparing Example 1 and Comparative Example 4, it can be seen that compared with ordinary sintering, hot-pressing sintering can enhance the crystal orientation of BaM thick film, reduce microscopic porosity, and enhance the density of thick film. After hot pressing, the relative density of thick film is from 0.78 It increased to 0.92, but the remanence ratio (SQ) decreased slightly, from 0.94 to 0.91.
  • SQ remanence ratio
  • Comparative Example 5 Comparative Example 5 with Comparative Example 4, it can be seen that if there is no heating process during the magnetization process, the porosity of the thick film increases and the density decreases. In addition, the saturation magnetization, residual magnetization and remanence ratio will all decrease.

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Abstract

本发明公开了一种高剩磁比、低孔隙率六角铁氧体厚膜及其制备方法与应用，所述制备方法包括以下步骤：(1)将BaM粉末与有机载体混合、研磨，得到混合均匀的浆料；(2)将浆料通过丝网印刷法涂抹到Al 2O 3基片上，形成厚膜；(3)将上述厚膜与基片放置磁场中，进行加热充磁、排胶；(4)对充磁后的厚膜进行加压烧结，得到所述六角铁氧体厚膜。本发明通过优化有机载体、控制BaM粉末粒径、改进制膜工艺，制备得到高剩磁比、低孔隙率、高密度、高饱和磁化强度的六角铁氧体厚膜，可应用于自偏置环形器，且上述制备方法可实现低成本、大规模制备BaM厚膜，满足产业化需求。

Description

一种高剩磁比、低孔隙率六角铁氧体厚膜及其制备方法与应用 技术领域
本发明涉及薄膜材料技术领域，具体涉及一种高剩磁比、低孔隙率六角铁氧体厚膜及其制备方法与应用。
背景技术
M型六角铁氧体(Ba,Sr)Fe 12O 19(简称BaM)，因具有较高的高单轴磁晶各向异性和适中的饱和磁化强度，可以实现在较低的偏置磁场或无偏置磁场的情况下应用于微波高频域(如K a波段)和毫米波频段，即实现自偏置应用(撤去外场后仍保持较高的内偏置磁场)，进而实现磁性微波器件的高频化、小型化和集成化。
目前，钡铁氧体膜的制备技术主要有激光脉冲沉积(PLD)、液相外延(LPE)和磁控溅射以及丝网印刷等工艺。其中，通过PLD、磁控溅射方式可制备得到晶格取向一致、高质量的BaM薄膜，但制备的薄膜的厚度有限(只有几个微米)、生长速率低、表面积小且剩余磁化强度低，不具备自偏置的潜力；与上述PLD等制膜方法相比，LPE的优势主要在生长速率高、薄膜厚度大以及薄膜的结晶质量高，但正是因为缺少大量晶界等缺陷而致使这类单晶结构的矫顽力非常低，进而剩磁比较低而无法应用于自偏置器件中；较之上述三种制备方法，丝网印刷方式制备BaM厚膜，制备方法简单、成本低，且易成膜、效率高、膜厚易调整，有利于大规模工业生产，但目前通过丝网印刷制备的BaM厚膜的性能还有待提高，存在剩磁比低、孔隙率高、饱和磁化强度低等问题(Ref.：陈中艳,冯则坤,熊炫.丝网印刷及磁场取向制备钡铁氧体厚膜研究[J].磁性材料及器件,2010,41(02):22-24+45；黄照林,张万里,彭斌.有机载体对钡铁氧体厚膜微结构的影响研究[J].功能材料与器件学报,2011,17(01):69-73)，这些问题都限制了 BaM厚膜在自偏置器件中的应用。因此，目前亟需一种低成本可制备高剩磁比、低孔隙率、高饱和磁化强度的BaM膜的制备方法。
发明内容
本发明提供了一种高剩磁比、低孔隙率六角铁氧体厚膜及其制备方法与应用，通过优化有机载体的组分和配比、降低BaM粉末粒径以及制备方法上的改进，得到高剩磁比、低空隙率、高饱和磁化强度的BaM厚膜，满足自偏置环形器材料的性能需求。
为解决上述问题，本发明提供了如下所述的技术方案：
本发明第一方面提供了一种六角铁氧体厚膜的制备方法，包括以下步骤：
(1)将BaM粉末与有机载体混合、研磨，得到混合均匀的浆料；
(2)将浆料通过丝网印刷法涂抹到Al 2O 3基片上，形成厚膜；
(3)将上述厚膜与基片放置磁场中，进行加热充磁、排胶；
(4)对充磁后的厚膜进行烧结，降温得到所述六角铁氧体厚膜。
进一步地，所述BaM粉末的制备包括以下步骤：
S1：将混合后的原料与球磨珠、无水酒精混合后，进行球磨；
S2：对球磨后的物料进行干燥处理；
S3：将干燥后的物料磨碎后置于空气或氧气气氛中进行预烧处理；
S4：将预烧后的物料研磨成粉末状，再置于流动氧气气氛中进行烧结处理；
S5：将烧结后的粉末与玻璃料、球磨珠、无水乙醇混合，进行球磨、干燥处理，得到所需的BaM粉末。
进一步地，S1中所述原料包含BaCO 3、Fe 2O 3。
进一步地，S1中所述原料还可以包含SrCo 3。
进一步地，S1中所述原料中包含的组分的摩尔纯度为99.99％。
进一步地，S1中，球磨的转速优选为200～300rpm，球磨的时间优选为12-24h。
进一步地，S2及S5中，干燥的温度优选为70-100℃，干燥的时间优选为30-50min。
进一步地，S3中所述预烧处理具体为：以2℃/min的升温速率升温至1000℃，保温4h。
进一步地，预烧后以1-3℃/min的降温速率降温。
进一步地，S4中所述烧结处理具体为：以2℃/min的升温速率升温至1250℃，保温10h。
进一步地，烧结后以2-3℃/min的降温速率降温。
进一步地，S5中，所述玻璃料与BaM粉末的重量比为2％-8％，所述球磨珠中大、中、小球磨珠的比例为1:1-3:3-5；其中大球磨珠的直径为11mm，中球磨珠的直径为7mm，小球磨珠的直径为5mm。
进一步地，S5中，所述球磨的转速优选为200～300rpm，球磨的时间优选为10-80h。
进一步地，步骤(1)中，所述BaM粉末的平均粒径为0.3-0.7μm。
进一步地，所述有机载体包含按质量百分比计的以下组分：10-20％的环氧树脂、40-60％的固化剂、15-30％的松油醇、5-10％柠檬酸三丁酯及各占1-3％的其它组分；所述其它组分选自聚二甲基硅氧烷、乙基纤维素、蓖麻油、卵磷脂、环氧丙烯酸酯和聚氨酯丙烯酸酯中的至少三种。
进一步地，所述环氧树脂优选双酚A型环氧树脂，所述固化剂优选脂肪胺树脂。
进一步地，所述其它组分优选乙基纤维素、蓖麻油、卵磷脂。
有机载体是将粉末和作粘合用的玻璃粉及其它固体粉末混合分散成膏状浆料，以便用丝网印刷方法将其印刷在陶瓷基片上。有机载体由有机溶剂、增稠剂、流平剂、分散剂等组成，其中，有机溶剂决定着有机载体的流变性、挥发性、粘结性能，本发明使用的有机溶剂由环氧树脂、固化剂、松油醇、柠檬酸三丁脂组成。此外，本发明添加了环氧树脂、固化剂等成分。环氧树脂调节了有机载体的流变性，使得有机载体的粘度保持适中，可以与粉末充分混合。这可以保证在充磁时，厚膜晶粒自由转动，充分取向。固化剂提升了有机载体的粘结性能，使得混合后的浆料可以与基片牢固的粘附在一起。在环氧树脂和固化剂共同作用下，厚膜在加热充磁中可以防止浆料二次流动，保持表面平整，形貌完整。此外，添加了环氧树脂和固化剂形成多元有机溶剂可以使有机载体在不同温度区间缓慢挥发，以降低厚膜孔隙率，提高膜的致密度。
进一步地，步骤(1)中，所述BaM粉末与有机载体的质量比为2-4:1。
进一步地，步骤(2)中，所述丝网印刷的操作具体为：将Al 2O 3基片放入印刷模板中，通过刮板将浆料从模板上涂抹到基片上，形成厚膜。
进一步地，步骤(3)中，所述磁场的强度为8000-10000Oe；所述加热充磁的温度为150-300℃，加热充磁的时间为20-50min。
充磁使厚膜中铁氧体颗粒的易磁化轴(晶体C轴)沿着外场进行取向，以获得高剩磁。其中充磁过程中加热主要有以下三个作用：第一是在较高温度下，有机载体的流动性更强，以便颗粒转动；第二是使厚膜初步固化，保持表面平整；第三是可以初步排胶，挥发一部分有机载体。若在充磁过程中不进行加热过程，厚膜浆料无法完全凝固，表面会有凹凸不平。而且在进行加压烧结时，由于浆料未完全凝固，厚膜会被挤压变形，无法使用。
进一步地，步骤(4)中，所述烧结优选加压烧结。
进一步地，所述加压烧结的具体操作为：将厚膜上放置负载后置于空气气氛中，升温至烧结温度，烧结1-10h；所述负载的压力为0.5-3MPa，所述升温的速率为2-3℃/min，烧结温度为900-1200℃。
加压烧结使BaM厚膜在热能和应力的共同作用下，促进粉末颗粒的结合和材料的致密化，得到更高密度的厚膜。若仅进行普通烧结，厚膜的密度相对于加压烧结会低很多。
进一步地，所述负载优选为Al 2O 3。
进一步地，步骤(4)中，所述降温的速率为2-3℃/min。
在烧结过程中，高温区需要使升温或降温的速度慢下来，一方面促进BaM在高温区生长，让晶体形成；另一方面高温时升温或者降温过快会使样品开裂。在低温区就可以快速降温，加快烧结。
本发明第二方面提供了一种由第一方面所述制备方法制备得到的六角铁氧体厚膜。
进一步地，所述六角铁氧体厚膜的膜厚为0.1-0.4mm，例如：0.1mm、0.2mm、0.3mm、0.4mm等。
本发明第三方面提供了第二方面所述的一种六角铁氧体厚膜在自偏置环形器材料中的应用。
自偏置环形器对材料的要求有以下几点：剩磁比(SQ，M r/M s)高，优选SQ≥0.9；矫顽力(Hc)高，足够的矫顽力可以保障自偏置场的工作稳定性、不会轻易受外界干扰，当Hc>3kOe可使器件保持稳定运行；高饱和磁化强度(4πMs)，当材料的4πMs>3kG就可以应用于自偏置环形器；厚膜的膜厚不小于0.1μm。
进一步地，所述六角铁氧体厚膜的SQ≥0.9、Hc>3kOe、4πMs>3kG，满足 自偏置环形器材料的性能需求。
本发明的有益效果：
1.本发明通过降低粉末粒径、优化有机载体中有机溶剂的配方，提升有机载体的粘结性能，同时丰富了有机载体的组成成分，有利于改善BaM厚膜的表面平整度以及降低膜的孔隙率，进而提高厚膜整体的致密度。
2.本发明提供了一种制备自偏置器件材料的丝网印刷厚膜制备工艺，上述制备工艺可低成本、大规模制备BaM厚膜，通过加热充磁、加压烧结以及烧结升、降温速率的控制等工艺上的改进，制备得到平整、致密、无开裂现象的BaM厚膜。
3.本发明通过对材料的选择、制备工艺的改进制备得到一种高剩磁比、低孔隙率、高密度、高饱和磁化强度的BaM厚膜，满足自偏置环形器材料的性能需求。
附图说明
图1为丝网印刷制备厚膜的示意图；
图2为实施例和对比例样品的室温XRD测试图谱；
图3为实施例和对比例样品的室温SEM测试图像；
图4为实施例和对比例样品的磁滞回线图像。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术 语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例及对比例中的BaM粉末通过以下制备方法制备得到：
(1)将原料摩尔纯度为99.99％的BaCO 3、Fe 2O 3粉末药品按1：12的摩尔比混合；
(2)将混合后粉体置于球磨罐中并放入球磨珠，加入无水酒精至球磨罐三分之二高度处，将球磨罐放入球磨机，在250r/min的转速条件下球磨18小时。
(3)将第一次球磨后的粉体取出并置于研钵内，放入烘干机烘干，在80℃下烘40分钟。
(4)将烘干后的药品磨碎并置于坩埚中，放入管式炉在空气或流动氧气气氛中进行预烧处理。按照一定的温度速率升温，升温速率为2℃/min；预烧温度为1000℃，预烧时间为4小时；降温速率为1℃/min至3℃/min。
(5)预烧完成后，取出样品，并放入清洗过的研钵中手工研磨30分；将研磨后的粉末放入洁净的坩埚中，放入管式炉在流动氧气气氛中进行烧结处理。按照一定的温度梯度升温，升温速率为2℃/min；烧结温度为1250℃，烧结时间为10小时；降温速率为2℃/min至3℃/min。
(6)将烧结完成的BaM粉末和一定比例玻璃料混合，玻璃料与BaM的重量比为4％；然后置于球磨罐中并放入1：2：4的大、中、小球磨珠，其中大号球磨珠为11mm，中号球磨珠为7mm，小号球磨珠为5mm；加入无水酒精至球磨罐三分之二高度处，将球磨罐放入球磨机，在250r/min的转速下球磨一定时间。
(7)将第二次球磨的样品取出并置于研钵内，放入烘干机烘干，在80℃下烘干40分钟，得到所需的BaM粉末，其粒径与球磨时间相关。
实施例1
将第二次球磨80小时、平均粒径为0.4μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：19wt％的双酚A型环氧树脂、58wt％的脂肪胺树脂、16wt％的松油醇、9wt％的柠檬酸三丁脂、2wt％的乙基纤维素、1wt％的卵磷脂及1wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，加载1MPa压力并在1100℃下烧结4h，制备得到BaM厚膜。
实施例2
将第二次球磨80小时、平均粒径为0.4μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：11wt％的双酚A型环氧树脂、58wt％的脂肪胺树脂、27wt％的松油醇、9wt％的柠檬酸三丁脂、2wt％的乙基纤维素、1wt％的卵磷脂及1wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，加载1MPa压力并在1100℃下烧结4h，制备得到BaM厚膜。
实施例3
将第二次球磨50小时、平均粒径为0.5μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：16wt％的双酚A型环氧树脂、50wt％的脂肪胺树脂、23wt％的松油醇、7wt％的柠檬酸三丁脂、2wt％的乙基纤维素、1wt％的卵磷脂及1wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，加载1MPa压力并在1000℃下烧结4h，制备得到BaM厚膜。
对比例1
将第二次球磨50小时、平均粒径为0.5μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：75wt％的松油醇、12wt％的柠檬酸三丁脂、5wt％的乙基纤维素、4wt％的卵磷脂及4wt％的 蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，加载1MPa压力并在1100℃下烧结4h，制备得到BaM厚膜。
对比例2
将第二次球磨6小时、平均粒径为0.8μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：16wt％的双酚A型环氧树脂、50wt％的脂肪胺树脂、23wt％的松油醇、7wt％的柠檬酸三丁脂、2wt％的乙基纤维素、1wt％的卵磷脂及1wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，加载1MPa压力并在1100℃下烧结4h，制备得到BaM厚膜。
对比例3
将第二次球磨6小时、平均粒径为0.8μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：75wt％的松油醇、12wt％的柠檬酸三丁脂、5wt％的乙基纤维素、4wt％的卵磷脂及4wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，加载1MPa压力并在1100℃下烧结4h，制备得到BaM厚膜。
对比例4
将第二次球磨50小时、平均粒径为0.5μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：16wt％的双酚A型环氧树脂、50wt％的脂肪胺树脂、23wt％的松油醇、7wt％的柠檬酸三丁脂、2wt％的乙基纤维素、1wt％的卵磷脂及1wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，置于8000Oe磁场、200℃的条件下加热50min；将充磁后的厚膜，不加压力，在1100℃下烧结4h，制备得到BaM厚膜。
对比例5
将第二次球磨50小时、平均粒径为0.5μm的BaM粉末与有机载体以质量比3：1进行混合得到混合浆料，其中有机载体由以下组分组成：16wt％的双酚A型环氧树脂、50wt％的脂肪胺树脂、23wt％的松油醇、7wt％的柠檬酸三丁脂、2wt％的乙基纤维素、1wt％的卵磷脂及1wt％的蓖麻油；通过丝网印刷在Al 2O 3基片上形成厚膜，在8000Oe磁场中常温下静置50min；将充磁后的厚膜，不加压力，在1100℃下烧结4h，制备得到BaM厚膜。
性能测试
对上述实施例1～3及对比例1～5中的BaM厚膜进行XRD、SEM及磁滞回线测试表征。
XRD测试结果：如图2所示，其中图2a～2c分别为实施例1～3中制备的BaM厚膜的XRD图，图2d～2h分别为对比例1～5中制备的BaM厚膜的XRD，由图2a～2c可知，加压烧结的实施例1～3制备的厚膜，在(0，0，2l)的峰十分明显，且仅有(1，0，7)这一个强度很小的杂峰，该现象说明实施例1～3制备的厚膜有很强的C轴取向；对比例1相较于实施例1改变了有机载体(有机溶剂中不包含环氧树脂和固化剂)，厚膜的取向变的杂乱，从图2d可以发现其主峰(0，0，2l)之外存在了(1，0，7)、(1，1，4)、(2，0，11)等杂峰；较之实施例1，对比例2中的BaM粉末的粉末二次球磨时间短、粒径大，在其它条件均一致的情况下，由图2e可知，对比例2制备的厚膜虽然在(0，0，2l)的峰仍占主导，但在(1，0，5)、(1，0，7)、(1，1，4)、(2，0，6)存在许多杂峰，晶体取向变的更加杂乱；对比例3在对比例2的基础上更换了有机载体(有机溶剂中不包含环氧树脂和固化剂)，如图2f所示，对比例3制备得到的厚膜在(1，0，5)处的衍射峰强度最强，其他杂峰强度也相应的增强，而(0，0，2l)对应的衍射峰强度均降低；对比例4与实施例1仅在烧结处理工艺上存在差异，对比例4中厚膜在烧结时未进行加压处理，从图2g中可发现未加压的BaM厚膜虽然在(0，0，2l)的峰十分明显，厚膜有很强的C轴取向，但在(1，0，5)、(1，0，7)、(1，1，4)处出现杂峰；图2h为对 比例5的XRD图，对比例5制备的BaM厚膜与对比例4的差异，仅在充磁时的工艺，对比例5在充磁时未进行加热，制备得到的厚膜取向不够完全，在(0，0，2l)的峰很弱，而杂峰多且强度高。
SEM测试结果：如图3所示，其中图3a～3c分别为实施例1～3中制备的BaM厚膜的SEM图，图3d～3h分别为对比例1～5中制备的BaM厚膜的SEM；由图3a～3c可知，实施例1～3制备的厚膜表面更为致密、且相对平整，这也说明通过材料优化和制备工艺的改进使厚膜的晶粒紧密的压缩在一起，进一步降低晶体孔隙率，增大薄膜的密度；图3d为对比例1制备的厚膜的SEM图，和实施例1对比，有机载体的改变使厚膜存在一定孔隙，同时烧结时产生一些裂缝；图3e、3f分别为具有较大BaM粉末粒径的对比例2、3制备的厚膜的SEM形貌图，BaM粉末粒径过大使薄膜存在较多的孔隙；由图3g可知，对比例4制备的厚膜的晶粒表现处明显的面外取向，晶粒生长很完美，同时晶粒间的孔隙少且小；而对比例5制备的厚膜中晶粒差距较大且存在较多孔隙(如图3h所示)，推测是由于充磁时未加热，有机载体没有初步排除，导致烧结时有过多孔隙产生。
磁滞回线测试结果：如图4所示，其中图4a～4c分别为实施例1～3中制备的BaM厚膜的磁滞回线测试结果，图4d～4h分别为对比例1～5中制备的BaM厚膜的磁滞回线测试结果；将上述各样品的测试结果及相对密度(即厚膜的实际密度与理论密度的比值)总结于下表1中：
表1 样品的各性能参数
样品 粒径(μm) 相对密度 4πM r(kG) 4πM s(kG) H c(kOe) SQ
实施例1 0.78 0.92 3.17 3.5 3.5 0.91
实施例2 0.69 0.94 3.22 3.5 3.7 0.92
实施例3 0.68 0.89 2.93 3.25 3.7 0.9
对比例1 0.73 0.75 2.9 3.37 3.6 0.86
对比例2 1.1 0.81 3.08 3.59 3.2 0.86
对比例3 1.14 0.72 2.68 3.22 3.5 0.83
对比例4 0.82 0.78 3.24 3.43 3.6 0.94
对比例5 0.85 0.72 2.8 3.2 3.4 0.88
由表1可知，实施例1～3较之对比例，粒径较低、相对密度值较大，根据磁滞回线测试结果可知，各实施例制备的厚膜的各项磁学指标均满足自偏置环形器材料的要求。
综合上述表征及测试结果可知：
①实施例1和对比例1对比可知，当有机溶剂不在优选范围时，厚膜的晶体取向会有杂峰出现、微观孔隙率增加、密度降低，制备得到的厚膜SQ值有所降低；
②实施例1和对比例2对比可知，当粉末粒径不在优选范围时，厚膜的晶体取向变得更加杂乱、孔隙率增加导致密度降低，制备得到的厚膜SQ值降低；
③对比例2和对比例3对比可知，当有机载体不是优选时，厚膜的晶体取向更加杂乱，杂峰成为最强峰；孔隙率进一步增加，相对密度较小，此外，饱和磁化强度降低、剩余磁化强度增大，SQ也进一步降低；
④实施例1和对比例4对比可知，与普通烧结相比较，热压烧结可以增强BaM厚膜的晶体取向、降低微观的孔隙率、增强厚膜密度，经热压后厚膜相对密度从0.78提升到0.92，但是剩磁比(SQ)稍有下降，从0.94降至0.91。
⑤对比例5和对比例4对比可知，在充磁过程中，若无加热过程，厚膜的孔隙率变多、密度降低，此外，饱和磁化强度、剩余磁化强度和剩磁比都会降低。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或 变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (10)

  1. 一种六角铁氧体厚膜的制备方法，其特征在于，包括以下步骤：
    (1)将BaM粉末与有机载体混合、研磨，得到混合均匀的浆料；
    (2)将浆料通过丝网印刷法涂抹到Al 2O 3基片上，形成厚膜；
    (3)将上述厚膜与基片放置磁场中，进行加热充磁、排胶；
    (4)对充磁后的厚膜进行烧结，降温得到所述六角铁氧体厚膜。
  2. 根据权利要求1所述的一种六角铁氧体厚膜的制备方法，其特征在于，步骤(1)中，所述BaM粉末的平均粒径为0.3-0.7μm。
  3. 根据权利要求2所述的一种六角铁氧体厚膜的制备方法，其特征在于，所述BaM粉末的粒径控制的方法具体为：将烧结后的BaM粉末与玻璃料混合，加入球磨珠和无水乙醇，在200-300rpm的转速下球磨10-80h；所述玻璃料与BaM粉末的重量比为2％-8％，所述球磨珠中大、中、小球磨珠的比例为1:1-3:3-5，其中，大球磨珠的直径为11mm，中球磨珠的直径为7mm，小球磨珠的直径为5mm。
  4. 根据权利要求1所述的一种六角铁氧体厚膜的制备方法，其特征在于，步骤(1)中，所述BaM粉末与有机载体的质量比为2-4:1；所述有机载体包含按质量百分比计的以下组分：10-20％的环氧树脂、40-60％的固化剂、15-30％的松油醇、5-10％柠檬酸三丁酯及各占1-3％的其它组分；所述其它组分选自聚二甲基硅氧烷、乙基纤维素、蓖麻油、软磷脂、环氧丙烯酸酯和聚氨酯丙烯酸酯中的至少三种。
  5. 根据权利要求4所述的一种六角铁氧体厚膜的制备方法，其特征在于，所述环氧树脂为双酚A型环氧树脂，所述固化剂为脂肪胺树脂。
  6. 根据权利要求1所述的一种六角铁氧体厚膜的制备方法，其特征在于，步骤(3)中，所述磁场的强度为8000-10000Oe；所述加热充磁的温度为150-300℃，加热充磁的时间为20-50min。
  7. 根据权利要求1所述的一种六角铁氧体厚膜的制备方法，其特征在于，步骤(4)中，所述烧结为加压烧结；所述加压烧结的具体操作为：将厚膜上放置负载后置于空气气氛中，升温至烧结温度，烧结1-10h；所述负载的压力为0.5-3MPa，所述升温的速率为2-3℃/min，烧结温度为900-1200℃。
  8. 根据权利要求1所述的一种六角铁氧体厚膜的制备方法，其特征在于，步骤(4)中，所述降温的速率为2-3℃/min。
  9. 权利要求1～8任一项所述制备方法制备得到的六角铁氧体厚膜，其特征在于，所述六角铁氧体厚膜的膜厚为0.1-0.4mm。
  10. 权利要求9所述的一种六角铁氧体厚膜在自偏置环形器材料中的应用。
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