WO2023284190A1 - 一种高饱和低损耗双组分微波铁氧体材料及其制备方法与应用 - Google Patents

一种高饱和低损耗双组分微波铁氧体材料及其制备方法与应用 Download PDF

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WO2023284190A1
WO2023284190A1 PCT/CN2021/129668 CN2021129668W WO2023284190A1 WO 2023284190 A1 WO2023284190 A1 WO 2023284190A1 CN 2021129668 W CN2021129668 W CN 2021129668W WO 2023284190 A1 WO2023284190 A1 WO 2023284190A1
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optionally
ferrite material
microwave ferrite
diameter
ball milling
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PCT/CN2021/129668
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English (en)
French (fr)
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王媛珍
张利康
吕飞雨
杜阳忠
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横店集团东磁股份有限公司
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Publication of WO2023284190A1 publication Critical patent/WO2023284190A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
    • H01F1/0311—Compounds
    • H01F1/0313—Oxidic compounds
    • H01F1/0315—Ferrites
    • 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
    • H01F41/02—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 manufacturing cores, coils, or magnets

Definitions

  • the application relates to the fields of microwave communication and magnetic materials, and relates to a high-saturation and low-loss two-component microwave ferrite material and its preparation method and application.
  • Microwave ferrite devices occupy an important position in microwave technology and are widely used in aerospace, satellite communications, electronic countermeasures, mobile communications and medical fields. Microwave ferrite materials, as the core of devices, are widely used in various fields. 5G communication is an important part of the future information infrastructure. This technology requires the use of microwaves as a means of transmission, and circulators and isolators are indispensable components. The task of miniaturization and weight reduction is particularly important.
  • the dielectric constant of the existing microwave ferrite is between 12-16, and the device size is too large when designing low-frequency circulator isolators, which cannot meet the needs of miniaturization and integration.
  • the dielectric constant ⁇ ' which is one of the main parameters in device design, is closely related to the device size.
  • the medium wavelength of the electromagnetic wave propagating in the medium is inversely proportional to the square root of the dielectric constant, and the improvement of the dielectric constant of the material becomes an important means of device miniaturization.
  • the ferrite radius R has the following approximate formula:
  • k is the effective wave number
  • ⁇ is the operating angular frequency
  • c is the speed of light
  • ⁇ f is the real part ⁇ ' of the ferrite permittivity
  • ⁇ eff is the effective permeability.
  • ⁇ m ⁇ Ms
  • Ms the saturation magnetization
  • ⁇ the gyromagnetic ratio
  • the circulator with high field work has dual characteristics, it has circulator characteristics in the fundamental band (f 1 -f 2 ); it has forward and reverse isolation characteristics in the second harmonic band (2f 1 -2f 2 ), that is, it It has the characteristics of low-pass filter (LPF) and plays the role of circulator and harmonic suppression.
  • values of the three frequency points (2f 1 , f 1 + f 2 , 2f 2 ) are calculated, respectively
  • (0.091,0.058,0.024), so its non-reciprocity
  • CN 102584200A discloses an ultra-low loss, small linewidth microwave ferrite material and its preparation.
  • the chemical formula of the material is Y 3-2x-y Ca 2x+y Fe 5-xyz V x Zry Al z O 12 .
  • the preparation method includes: calculating and weighing raw materials according to stoichiometry, vibrating ball milling, pre-burning, vibrating coarse pulverizing, sand milling fine pulverizing, spraying granulation, pressing and sintering.
  • This technical solution can be used in the fields of microwave communication and magnetic materials.
  • This method provides a microwave ferrite material with ultra-low loss and small linewidth. In the preparation process, high pre-sintering temperature and sintering temperature are required, which is not conducive to production and Environmental friendly.
  • US8696925B2 discloses a high dielectric constant garnet ferrite whose chemical formula is Y 2.15-2x Bi 0.5 Ca 0.35+2x Zr 0.35 V x Fe 4.65-x O 12 and Bi 0.9 Ca 0.9+2x Y 1.2-2x Zr 0.7 Nb 0.1 V x Fe 4.2-x O 12 , the x ranges are 0-0.8 and 0-0.6 respectively, the corresponding dielectric constant is 20-30, and 4 ⁇ Ms is 1000-2000Gs.
  • the dielectric constant of this patent is still difficult to meet the actual needs, and the preparation method is cumbersome, and the toxic V 2 O 5 environment is not friendly.
  • the purpose of this application is to provide a high saturation and low loss two-component microwave ferrite material and its preparation method and application.
  • the two-component microwave ferrite material provided by the application has the characteristics of small line width, high Curie temperature, high saturation magnetic moment and low loss, which greatly improves the stability and reliability of the microwave ferrite material; and the application
  • the process method is stable and repeatable, suitable for mass production, and greatly reduces production costs.
  • the "high saturation and low loss" mentioned in this application means: the saturation magnetization is between 1950Gs and 1960Gs, and the dielectric loss is between 1.48 ⁇ 10 -4 -2 ⁇ 10 -4 .
  • the present application provides a high-saturation and low-loss two-component microwave ferrite material
  • the preparation raw materials of the high-saturation and low-loss two-component microwave ferrite material include the first microwave ferrite material and the second two microwave ferrite materials;
  • the first microwave ferrite material is: Y 3-a Ca a Fe 5-abc Zr a In b Mn c O 12 , where 0 ⁇ a ⁇ 0.7, for example, can be 0, 0.1, 0.2, 0.3, 0.4 , 0.5, 0.6 or 0.7, but not limited to the listed values, other unlisted values within the range of values are also applicable;
  • 0 ⁇ b ⁇ 0.7 for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 or 0.7, but not limited to the listed values, other unlisted values within the range of values are also applicable;
  • 0 ⁇ c ⁇ 0.7 for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 or 0.7, but not limited to the listed values, other unlisted values within the range of values are also applicable;
  • the second microwave ferrite material is: Gd 3-A Ca A Fe 5-ABC Ge A In B Ti CO 12 , where 0 ⁇ A ⁇ 0.7 , for example, can be 0, 0.1, 0.2, 0.3, 0.4 , 0.5, 0.6 or 0.7, but not limited to the listed values, other unlisted values within the range of values are also applicable;
  • 0 ⁇ B ⁇ 0.7 for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 or 0.7, but not limited to the listed values, other unlisted values within the range of values are also applicable;
  • 0 ⁇ C ⁇ 0.7 for example, can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6 or 0.7, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
  • the mass ratio of the first microwave ferrite material to the second microwave ferrite material is (1-3):(1-3), for example, it can be 1:1, 1:2, 1: 3, 2:3, 3:2 or 3:1, but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • Pure yttrium iron garnet ferrite has low power carrying capacity, large ferromagnetic resonance line width and dielectric loss, and its sintering temperature is high, so its performance is relatively simple.
  • This application focuses on replacing part of the octahedral Fe 3+ with Zr 4+ , which can reduce the anisotropy constant of the magnetocrystal and reduce the ferromagnetic resonance line width, but Zr 4+ should not be too much, too much will make the ferromagnetic
  • the resonance line width increases rapidly; Ca 2+ is a low-melting point substance, and their incorporation can reduce the sintering temperature; replacing part of Fe 3+ with a small amount of Mn 2+ can reduce the ferromagnetic resonance line width and dielectric loss of the material; Gd 3 + ions to replace Y 3+ can improve the Ms temperature coefficient, thereby maintaining a higher Curie temperature.
  • This application adjusts the composition of microwave ferrite materials and utilizes the coordination of the electromagnetic characteristics of each element to obtain a higher saturation magnetization 4 ⁇ Ms, a narrower ferromagnetic resonance linewidth ⁇ H, and a lower dielectric loss tg ⁇ e And microwave ferrite materials with higher Curie temperature Tc.
  • the present application provides a method for preparing a high-saturation and low-loss two-component microwave ferrite material as described in the first aspect.
  • the preparation method includes the following steps:
  • step (2) drying the ball abrasive obtained in step (1), granulating after sieving;
  • step (3) The granulated particles in step (2) are sequentially molded and sintered to obtain the two-component microwave ferrite material.
  • the wet ball milling in step (1) is to mix the preparation raw materials, grinding balls and dispersant according to the mass ratio 1:(4-7.5):(0.6-2.5), and perform wet ball milling, for example, it can be 1 :4:0.6, 1:5:0.8, 1:6:1.2, 1:7:1.5, 1:7.5:2, 1:6.5:1.5, 1:4.5:2.5 or 1:5.5:2.5, but not limited to For the numerical values listed, other unlisted numerical values within the numerical range are also applicable.
  • the rotating speed of the wet ball milling described in step (1) is 20-80r/min, such as 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min or 80r /min, but not limited to the listed values, other unlisted values within the value range are also applicable.
  • the time of wet ball milling in step (1) is 10-40h, for example, it can be 10h, 15h, 20h, 25h, 30h, 35h or 40h, but it is not limited to the listed values. The listed values also apply.
  • the grinding balls include zirconium balls and/or steel balls.
  • the grinding balls include large-diameter grinding balls and small-diameter grinding balls.
  • the diameter of the large-diameter grinding ball is 5-10 mm, such as 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm, but not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the diameter of the small-diameter grinding ball is 1-4 mm, for example, 1 mm, 2 mm, 3 mm or 4 mm, but is not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the mass ratio of the large-diameter grinding balls to the small-diameter grinding balls is (0.8-3):1, such as 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8 :1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, but not limited to the listed values, other unlisted values within the value range are also applicable.
  • the dispersant includes any one or a combination of at least two of deionized water, alcohol, acetone, n-acetone or ammonia
  • a typical but non-limiting combination includes a combination of deionized water and alcohol, deionized A combination of deionized water and acetone, a combination of deionized water and ammonia, a combination of deionized water, alcohol, and ammonia, or a combination of deionized water, alcohol, and acetone.
  • step (1) of the present application will affect the temperature required for sintering, and finally determine the sintering density and line width of the material, properties such as dielectric loss; different ball milling media will affect the effect of ball milling, and the grinding ball
  • the choice will affect the stability and control difficulty of the process control. Through the above ball milling conditions, a better ball milling effect can be obtained, the fineness can be reduced, the activity of the material can be improved, and the sintering temperature can be lowered.
  • the drying temperature in step (2) is 100-150°C, such as 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, but not limited to the listed values, the values Other unrecited values within the range also apply.
  • the end point of drying in step (2) is to reduce the moisture content to 0.01-10%, such as 0.01%, 0.1%, 1%, 3%, 5%, 7%, 9% or 10% %, but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the mesh size of the sieve used for sieving in step (2) is 30-100 mesh, such as 30 mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh or 100 mesh , but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the granulation in step (2) is to uniformly mix the sieved ball mill with the adhesive, and sieve under pressure to obtain granulated granules.
  • the binder includes an aqueous solution of polyvinyl alcohol.
  • the concentration of the polyvinyl alcohol solution is 5-20wt%, for example, it can be 5wt%, 10wt%, 15wt% or 20wt%, but it is not limited to the listed values, and other unlisted values within the numerical range are the same Be applicable.
  • the mass of the polyvinyl alcohol solution is 5-10% of the powder mass, such as 5%, 6%, 7%, 8%, 9% or 10%, but not limited to the listed values , other unlisted values within the value range are also applicable.
  • the sieving pressure is 300-1200kg/cm 2 , such as 300kg/cm 2 , 500kg/cm 2 , 700kg/cm 2 , 900kg/cm 2 , 1100kg/cm 2 or 1200kg/cm 2 , but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the forming in step (3) is: putting the granulated particles in step (2) into a mold and pressing them into a green body of a specified shape.
  • the molding density of the green body is 3.0-4.0g/cm 3 , for example, 3.0g/cm 3 , 3.2g/cm 3 , 3.4g/cm 3 , 3.6g/cm 3 , 3.8g/cm 3 , 3.8g/cm 3 cm 3 or 4.0g/cm 3 , but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the sintering in step (3) is as follows: the sintering temperature is 1200-1500°C, for example, it can be 1200°C, 1300°C, 1400°C or 1500°C, but not limited to the listed values, within the range of values Other values not listed also apply.
  • the sintering temperature mentioned in this application is too low or too high, the sintering density will decrease, the line width will increase, and the dielectric loss will increase.
  • the sintering holding time is 5-30h, for example, 5h, 10h, 15h, 20h, 25h or 30h, but not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the heating rate of the sintering is 1-5°C/min, such as 1°C/min, 2°C/min, 3°C/min, 4°C/min or 5°C/min, but not limited to Values listed, other unlisted values within the range of values also apply.
  • the start time of oxygen circulation during sintering in step (3) is 1-6h before the end of the heat preservation, for example, it can be 1h, 2h, 3h, 4h, 5h or 6h, but not limited to the listed values, the values Other unrecited values within the range also apply.
  • the time for ending oxygen flow during sintering in step (3) is: after the heat preservation is over, when the temperature drops by 100-500°C, stop oxygen flow, for example, it can be 100°C, 200°C, 300°C, 400°C or 500°C, but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the preparation method of the first microwave ferrite material described in step (1) comprises the following steps:
  • step (b) drying, sieving and pre-calcining the ball abrasive obtained in step (a) in sequence to obtain the first microwave ferrite material;
  • the first microwave ferrite material is: Y 3-a Ca a Fe 5-abc Zr a In b Mn c O 12 , wherein, 0 ⁇ a ⁇ 0.7, 0 ⁇ b ⁇ 0.7, 0 ⁇ c ⁇ 0.7;
  • the raw materials for preparing the first microwave ferrite material are: Y 2 O 3 , CaCO 3 , Fe 2 O 3 , ZrO 2 , SnO 2 and MnCO 3 .
  • the wet ball milling in step (a) is to mix the preparation raw materials, grinding balls, dispersant and dispersant according to the mass ratio of 1:(4-7.5):(0.6-2.5):(0.003-0.01),
  • wet ball milling for example, 1:4:0.6:0.003, 1:5:0.8:0.004, 1:6:1.2:0.005, 1:7:1.5:0.006, 1:7.5:2:0.007, 1: 5:1.5:0.008, 1:6:2.5:0.009 or 1:6.5:2.5:0.01, but not limited to the listed values, other unlisted values within the range are also applicable.
  • the rotating speed of the wet ball milling in step (a) is 20-80r/min, for example, it can be 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min or 80r /min, but not limited to the listed values, other unlisted values within the value range are also applicable.
  • the time of wet ball milling in step (a) is 10-40h, for example, it can be 10h, 15h, 20h, 25h, 30h, 35h or 40h, but not limited to the enumerated numerical values, other not included in the numerical range The listed values also apply.
  • the grinding balls in step (a) include zirconium balls.
  • the grinding balls in step (a) include large-diameter grinding balls and small-diameter grinding balls.
  • the diameter of the large-diameter grinding ball is 5-10 mm, such as 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm, but not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the diameter of the small-diameter grinding ball is 1-4mm, such as 1mm, 2mm, 3mm or 4mm, but is not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the mass ratio of the large-diameter grinding balls to the small-diameter grinding balls is (0.8-3):1, such as 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8 :1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, but not limited to the listed values, other unlisted values within the value range are also applicable.
  • the dispersant used in the wet ball milling in step (a) includes any one or a combination of at least two of deionized water, alcohol, acetone, normal acetone or ammonia, and a typical but non-limiting combination includes deionized water A combination of deionized water and alcohol, a combination of deionized water and acetone, a combination of deionized water and ammonia, a combination of deionized water, alcohol and ammonia, or a combination of deionized water, alcohol and acetone.
  • the dispersant used in the wet ball milling in step (a) includes ammonium citrate and/or ammonia water.
  • the length of the wet ball milling time will affect the degree of ion occupancy, and ultimately affect the product performance under the existing pre-burning temperature conditions; different ball milling media will affect the effect of ball milling, and the selection of grinding balls will affect the stability of process control and control difficulty.
  • a better ball milling effect can be obtained, and the pure pre-phased first microwave ferrite material can be obtained in the ball milling process of the two-component microwave ferrite preparation process, and the impurity phase can be removed to obtain a suitable
  • the particle size distribution and activity are beneficial to the solid phase reaction in the subsequent pre-sintering and sintering process.
  • the drying temperature in step (b) is 100-150°C, such as 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, but not limited to the listed values, the values Other unrecited values within the range also apply.
  • the end point of drying in step (b) is to reduce the moisture content to 0.01-10%, such as 0.01%, 1%, 3%, 5%, 7%, 9% or 10%, but Not limited to the numerical values listed, other unlisted numerical values within the numerical range are also applicable.
  • the mesh size of the sieve used for sieving in step (b) is 30-100 mesh, such as 30 mesh, 50 mesh, 70 mesh, 90 mesh or 100 mesh, but not limited to the listed values, Other unrecited values within the range of values also apply.
  • the pre-calcination temperature in step (b) is 1100-1400°C, for example, it can be 1100°C, 1200°C, 1300°C or 1400°C, but it is not limited to the listed values, other unlisted values within the range Numerical values also apply.
  • the heat preservation time of the pre-burning described in step (b) is 6-15h, such as 6h, 8h, 10h, 12h, 14h or 15h, but not limited to the listed values, other unlisted values within the range of values Numerical values also apply.
  • the heating rate of the pre-burning in step (b) is 0.3-4°C/min, such as 0.3°C/min, 1°C/min, 2°C/min, 3°C/min or 4°C/min , but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the pre-sintering described in this application can reduce the inhomogeneity of the chemical activity of the ball abrasive after drying, and can also reduce the shrinkage rate of subsequent sintered products and reduce deformation.
  • the preparation method of the second microwave ferrite material described in step (1) comprises the following steps:
  • step (1) The ball abrasive obtained in step (1) is dried, sieved and pre-fired in sequence to obtain the second microwave ferrite material;
  • the second microwave ferrite material is: Gd 3 -A Ca A Fe 5 -ABC Ge A In B Ti CO 12 , wherein 0 ⁇ A ⁇ 0.7 , 0 ⁇ B ⁇ 0.7, 0 ⁇ C ⁇ 0.7.
  • the raw materials for preparing the second microwave ferrite material in step (I) are Gd 2 O 3 , CaCO 3 , Fe 2 O 3 , GeO 2 , InO 2 and TiO 2 .
  • the wet ball milling described in step (I) is to mix the preparation raw materials, grinding balls, dispersant and dispersant according to the mass ratio 1:(4-7.5):(0.6-2.5):(0.003-0.01),
  • 1:4:0.6:0.008, 1:5:0.8:0.009, 1:6:1.2:0.01, 1:7:1.5:0.003, 1:7.5:2:0.004, 1: 1.5:1.5:0.005, 1:1:2.5:0.006 or 1:5:2.5:0.007 but not limited to the listed values, other unlisted values within the range are also applicable.
  • the grinding balls of the wet ball milling in step (I) include zirconium balls and/or steel balls.
  • the grinding balls in step (I) include large-diameter grinding balls and small-diameter grinding balls.
  • the diameter of the large-diameter grinding ball is 5-10 mm, such as 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm, but not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the diameter of the small-diameter grinding ball is 1-4mm, such as 1mm, 2mm, 3mm or 4mm, but is not limited to the listed values, and other unlisted values within the range of values are also applicable.
  • the mass ratio of the large-diameter grinding balls to the small-diameter grinding balls in step (1) is (0.8-3):1, for example, it can be 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6 :1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, but not limited to the listed values, other unlisted values within the range are also applicable.
  • the dispersant in step (I) includes any one or a combination of at least two of deionized water, alcohol, acetone, n-propanol or ammonia.
  • the dispersant in step (I) includes ammonium citrate and/or ammonia water.
  • the rotating speed of the wet ball milling described in step (1) is 20-80r/min, such as 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min or 80r /min, but not limited to the listed values, other unlisted values within the value range are also applicable.
  • the time of wet ball milling in step (I) is 10-40h, for example, it can be 10h, 15h, 20h, 25h, 30h, 35h or 40h, but not limited to the enumerated numerical value, other not included in the numerical range The listed values also apply.
  • drying temperature in step (II) is 100-150°C, such as 100°C, 110°C, 120°C, 130°C, 140°C or 150°C, but not limited to the listed values, the values Other unrecited values within the range also apply.
  • the end point of drying in step (II) is to reduce the moisture content to 0.01-10%, such as 0.01%, 0.1%, 1%, 3%, 5%, 7%, 9% or 10% %, but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the mesh size of the sieve used for sieving in step (II) is 30-100 mesh, for example, it can be 30 mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh or 100 mesh , but not limited to the listed values, other unlisted values within the range of values are also applicable.
  • the pre-calcination temperature in step (II) is 1100-1400°C, for example, it can be 1100°C, 1200°C, 1300°C or 1400°C, but it is not limited to the listed values, other unlisted values within the range Numerical values also apply.
  • the heat preservation time of the pre-burning described in step (II) is 8-20h, such as can be 8h, 10h, 12h, 14h, 16h, 18h or 20h, but not limited to the numerical values listed, other not included in the numerical range The listed values also apply.
  • the heating rate of the pre-burning in step (II) is 0.3-4°C/min, such as 0.3°C/min, 2°C/min, 3°C/min or 4°C/min, but not limited to Listed values, other unlisted values within the range of values also apply.
  • the pre-sintering described in this application can reduce the inhomogeneity of the chemical activity of the ball abrasive after drying, and can also reduce the shrinkage rate of subsequent sintered products and reduce deformation.
  • the preparation method described in the second aspect includes the following steps:
  • step (2) drying the ball mill material obtained in step (1) under the condition of 100-250°C until the water content is reduced to 0.01-10%, and granulating after passing through a 30-100 mesh sieve;
  • the granulation is to uniformly mix the sieved ball abrasive with the binder, pass through a 30-100 mesh sieve under a pressure of 300-1200kg/ cm2 , and obtain granulated particles;
  • step (2) The granulated particles in step (2) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • the pellets are pressed into a green body of a specified shape in a mold, and the molding density of the green body is 3.0-4.0g/cm 3 ;
  • the temperature of the sintering is 1200-1500°C, and the holding time of the sintering is 5-30h,
  • the heating rate of the sintering is 1-5°C/min, and the start time of oxygen flow during the sintering is 1-6h before the end of the heat preservation. After the heat preservation is completed, when the temperature drops by 100-500°C, the oxygen flow is ended;
  • the preparation method of the first microwave ferrite material described in step (1) comprises:
  • step (b) The ball abrasive obtained in step (a) is dried in sequence, passed through a 30-100 mesh sieve, and pre-fired to obtain the first microwave ferrite material; the drying temperature is 100-250°C, and the drying end point is The moisture content is reduced to 0.01-10%; the temperature of the pre-burning is 1100-1350°C; the holding time of the pre-burning is 6-15h; the heating rate of the pre-burning is 0.3-4°C/min;
  • the preparation method of the second microwave ferrite material described in step (1) comprises:
  • step (II) The ball abrasive obtained in step (I) is dried, sieved and pre-fired in sequence to obtain the second microwave ferrite material; the drying temperature is 100-250° C., and the end point of drying is to reduce the moisture content to 0.01-10%; the temperature of the pre-burning is 1100-1400°C; the holding time of the pre-burning is 8-20h.
  • the present application provides an application of the high-saturation, low-loss, high-saturation, low-loss two-component microwave ferrite as described in the first aspect, and the high-saturation and low-loss two-component microwave ferrite is used for microwave communication device.
  • the microwave ferrite material prepared by this application using a two-component composite process has high saturation magnetic moment, high Curie temperature, low line width, and low loss; the saturation magnetic moment intensity is 1950Gs-1960Gs, and the dielectric loss is 1.58 ⁇ 10 -4 -2 ⁇ 10 -4 , the Curie temperature can reach over 260°C, and the line width is less than 18Oe;
  • the preparation method of the present application has a stable process and good repeatability, which is beneficial to industrial production.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material
  • the high-saturation and low-loss two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material .
  • the preparation method of the high saturation and low loss two-component microwave ferrite material comprises the following steps:
  • the wet ball mill is prepared raw materials, zirconium Balls and deionized water are mixed according to the mass ratio of 1:4:0.6, and the rotating speed is 20r/min, and the wet ball milling time is 26h;
  • the mass ratio of the large-diameter zirconium balls and small-diameter zirconium balls is 3:1, and the The diameter of the large-diameter zirconium ball is 5 mm, and the diameter of the small-diameter zirconium ball is 2 mm;
  • step (2) Under the condition of 120 °C, dry the ball mill obtained in step (1) until the water content is reduced to 5.5%, and then granulate after passing through a 30-mesh sieve; Mix evenly, pass through a 30-mesh sieve under a pressure of 1200kg/cm 2 to obtain granulated particles; The aqueous solution is 5% of the ball mill mass after sieving;
  • step (2) The granulated particles in step (2) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • a green body of a specified shape is pressed in a pellet mold with a molding density of 3.5g/cm 3 ;
  • the sintering temperature is 1250°C
  • the sintering holding time is 5h
  • the sintering heating rate is 1°C/min
  • the starting time of oxygen flow during the sintering is 3 hours before the end of the heat preservation, and after the end of the heat preservation, when the temperature drops by 200°C, the oxygen flow is ended;
  • the preparation method of the first microwave ferrite material described in step (1) comprises:
  • step (b) The ball abrasive obtained in step (a) is dried, passed through a 30-mesh sieve, and pre-fired in sequence to obtain the first microwave ferrite material; the drying temperature is 120° C., and the end point of the drying is to reduce the moisture content to 0.2%; the temperature of the pre-burning is 1150°C; the holding time of the pre-burning is 6h; the heating rate of the pre-burning is 0.5°C/min;
  • the preparation method of the second microwave ferrite material described in step (1) comprises:
  • step (II) The ball abrasive obtained in step (I) is dried, sieved and pre-fired in sequence to obtain the second microwave ferrite material; the drying temperature is 100° C., and the end point of drying is to reduce the moisture content to 0.5%. ; The temperature of the pre-burning is 1120°C; the holding time of the pre-burning is 8h.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material
  • the high-saturation and low-loss two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material .
  • the preparation method of the high saturation and low loss two-component microwave ferrite material comprises the following steps:
  • step (2) Under the condition of 150 °C, dry the ball mill obtained in step (1) until the moisture content is reduced to 6.5%, and then granulate after passing through a 50-mesh sieve; Mix evenly, and pass through a 50 - mesh sieve under a pressure of 1000kg/cm to obtain granulated particles;
  • the binder is an aqueous solution of polyvinyl alcohol, and the concentration of the aqueous solution of polyvinyl alcohol is 10wt%.
  • the aqueous solution is 6% of the ball mill quality after sieving;
  • step (2) The granulated particles in step (2) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • a green body of a specified shape is pressed in a pellet mold with a molding density of 4g/cm 3 ;
  • the sintering temperature is 1260°C, the sintering holding time is 10h, and the sintering heating rate is 3 °C/min, the starting time of oxygen flow during the sintering is 4 hours before the end of the heat preservation, and after the heat preservation is completed, when the temperature drops by 300°C, the oxygen flow is ended;
  • the preparation method of the first microwave ferrite material described in step (1) comprises:
  • step (b) The ball abrasive obtained in step (a) is dried in turn, passed through a 50-mesh sieve, and pre-fired to obtain the first microwave ferrite material; the drying temperature is 150° C., and the end point of drying is to reduce the moisture content to 5.5%; the temperature of the pre-burning is 1100°C; the holding time of the pre-burning is 7h; the heating rate of the pre-burning is 3.2°C/min;
  • the preparation method of the second microwave ferrite material described in step (1) comprises:
  • step (II) The ball mill material obtained in step (I) is dried successively, passed through a 50-mesh sieve and pre-fired to obtain the second microwave ferrite material; the drying temperature is 150° C., and the end point of drying is to reduce the moisture content to 3.2%; the temperature of the pre-burning is 1100° C.; the holding time of the pre-burning is 9 hours.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material
  • the high-saturation and low-loss two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material .
  • the preparation method of the high saturation and low loss two-component microwave ferrite material comprises the following steps:
  • step (2) Under the condition of 200 °C, dry the ball mill obtained in step (1) until the water content is reduced to 0.01%, and then granulate after passing through an 80-mesh sieve; Mix evenly, and pass through a 50-mesh sieve under a pressure of 1000kg/ cm2 to obtain granulated particles;
  • the binder is an aqueous solution of polyvinyl alcohol, and the concentration of the aqueous solution of polyvinyl alcohol is 5 wt%.
  • the aqueous solution is 8% of the ball mill quality after sieving;
  • step (2) The granulated particles in step (2) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • a green body of a specified shape is pressed in a pellet mold with a molding density of 3.2g/cm 3 ;
  • the sintering temperature is 1400°C, the sintering holding time is 15h, and the sintering heating rate is 3.5°C/min, the start time of oxygen flow during sintering is 2 hours before the end of the heat preservation, after the end of the heat preservation, when the temperature drops by 400°C, the oxygen flow is ended;
  • the preparation method of the first microwave ferrite material described in step (1) comprises:
  • step (b) The ball abrasive obtained in step (a) is dried in turn, passed through a 50-mesh sieve, and pre-fired to obtain the first microwave ferrite material; the drying temperature is 200° C., and the end point of drying is to reduce the moisture content to 0.01%; the temperature of the pre-burning is 1250°C; the holding time of the pre-burning is 8h; the heating rate of the pre-burning is 2.8°C/min;
  • the preparation method of the second microwave ferrite material described in step (1) comprises:
  • step (II) The ball mill material obtained in step (I) is dried successively, passed through a 50-mesh sieve, and pre-fired to obtain the second microwave ferrite material; the drying temperature is 200° C., and the end point of drying is to reduce the moisture content to 0.01%; the temperature of the pre-burning is 1200°C; the holding time of the pre-burning is 7h.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material
  • the high-saturation and low-loss two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material .
  • the preparation method of the high saturation and low loss two-component microwave ferrite material comprises the following steps:
  • the wet ball mill is prepared raw materials, zirconium The ball and acetone are mixed according to the mass ratio of 1:7.5:2.5, and the wet ball milling is carried out at a speed of 80r/min and a time of 40h; the mass ratio of the large-diameter zirconium ball and the small-diameter zirconium ball is 3.5:4, and the large-diameter
  • the diameter of the zirconium ball is 7 mm, and the diameter of the small-diameter zirconium ball is 1 mm;
  • step (2) Under the condition of 200 °C, dry the ball mill obtained in step (1) until the water content is reduced to 8%, and then granulate after passing through a 100-mesh sieve; Mix evenly, and pass through a 100-mesh sieve under a pressure of 300kg/ cm2 to obtain granulated particles;
  • the binder is an aqueous solution of polyvinyl alcohol, and the concentration of the aqueous solution of polyvinyl alcohol is 8wt%.
  • the aqueous solution is 7% of the ball mill quality after sieving;
  • step (2) The granulated particles in step (2) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • a green body of a specified shape is pressed in a pellet mold with a molding density of 3g/cm 3 ;
  • the sintering temperature is 1500°C
  • the sintering holding time is 20h
  • the sintering heating rate is 4.8 °C/min
  • the start time of oxygen flow during the sintering is 1 hour before the end of the heat preservation, and after the heat preservation is completed, when the temperature drops by 500°C, the oxygen flow is ended;
  • the preparation method of the first microwave ferrite material described in step (1) comprises:
  • step (b) The ball abrasive obtained in step (a) is dried, passed through a 100-mesh sieve, and pre-fired in sequence to obtain the first microwave ferrite material; the drying temperature is 250° C., and the drying end point is to reduce the moisture content to 6.9%; the temperature of the pre-burning is 1300°C; the holding time of the pre-burning is 10h; the heating rate of the pre-burning is 5.2°C/min;
  • the preparation method of the second microwave ferrite material described in step (1) comprises:
  • the wet ball milling time is 20h; the mass ratio of the large-diameter grinding ball and the small-diameter grinding ball is 1:1; the diameter of the large-diameter grinding ball is 6mm, and the diameter of the small-diameter grinding ball is 2mm; the obtained ball grinding material
  • step (II) The ball mill material obtained in step (I) is dried successively, passed through a 100-mesh sieve and pre-calcined to obtain the second microwave ferrite material; the drying temperature is 250° C., and the end point of drying is to reduce the moisture content to 8.2%; the temperature of the pre-burning is 1250°C; the holding time of the pre-burning is 15h.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material
  • the high-saturation and low-loss two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material .
  • the preparation method of the high saturation and low loss two-component microwave ferrite material comprises the following steps:
  • step (2) Under the condition of 180 °C, dry the ball abrasive obtained in step (1) until the water content is reduced to 10%, and then granulate after passing through a 60-mesh sieve; Mix evenly, pass through a 6-mesh sieve under a pressure of 800kg/cm 2 to obtain granulated particles;
  • the binder is an aqueous solution of polyvinyl alcohol, and the concentration of the aqueous solution of polyvinyl alcohol is 5wt%, The aqueous solution is 10% of the ball mill mass after sieving;
  • step (2) The granulated particles in step (2) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • a green body of a specified shape is pressed in a pellet mold with a molding density of 3.6g/cm 3 ;
  • the sintering temperature is 1200°C, the sintering holding time is 30h, and the sintering heating rate is 3.9°C/min, the start time of oxygen flow during sintering is 6 hours before the end of the heat preservation, after the end of the heat preservation, when the temperature drops by 100°C, the oxygen flow is ended;
  • the preparation method of the first microwave ferrite material described in step (1) comprises:
  • step (b) The ball abrasive obtained in step (a) is dried in turn, passed through a 60-mesh sieve, and pre-fired to obtain the first microwave ferrite material; the drying temperature is 180° C., and the end point of drying is to reduce the moisture content to 6.9%; the temperature of the pre-burning is 1350°C; the holding time of the pre-burning is 15h; the heating rate of the pre-burning is 4.2°C/min;
  • the preparation method of the second microwave ferrite material described in step (1) comprises:
  • step (II) The ball mill material obtained in step (I) is dried successively, passed through a 100-mesh sieve and pre-calcined to obtain the second microwave ferrite material; the drying temperature is 250° C., and the end point of drying is to reduce the moisture content to 8.2%; the temperature of the pre-burning is 1250°C; the holding time of the pre-burning is 15h.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material, the preparation method of the high-saturation and low-loss two-component microwave ferrite material is divided into The mass ratio of the bulk material to the second microwave ferrite material was changed to 1:3, and the rest were the same as in Example 1.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material, the preparation method of the high-saturation and low-loss two-component microwave ferrite material is divided into The mass ratio of the bulk material to the second microwave ferrite material was changed to 3:1, and the rest were the same as in Example 1.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material
  • the high-saturation and low-loss two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material .
  • the preparation method of the high-saturation and low-loss two-component microwave ferrite material is the same as that in Example 1.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material.
  • the sintering temperature described in step (3) is replaced by 800 DEG C, the rest are the same as in Example 1.
  • This embodiment provides a high-saturation and low-loss two-component microwave ferrite material.
  • the sintering temperature described in step (3) is replaced by 2000 DEG C, the rest are the same as in Example 1.
  • the preparation method of described microwave ferrite comprises the steps:
  • step (2) The ball abrasive obtained in step (1) is dried, passed through a 30-mesh sieve, and pre-fired in sequence to obtain a microwave ferrite material precursor; the drying temperature is 120 ° C, and the end point of drying is to reduce the moisture content to 0.2%; the temperature of the pre-burning is 1150°C; the holding time of the pre-burning is 6h; the heating rate of the pre-burning is 0.5°C/min;
  • step (3) crush the microwave ferrite material precursor described in step (2) to obtain the powder, pass through a 30-mesh sieve, and then mix the powder, zirconium balls and deionized water according to the mass ratio of 1:4:0.6,
  • the rotating speed is 20r/min, and the time is wet ball milling for 26h;
  • the mass ratio of the large-diameter zirconium ball and the small-diameter zirconium ball is 3:1, the diameter of the large-diameter zirconium ball is 5mm, and the mass ratio of the small-diameter zirconium ball is 5 mm.
  • the diameter is 2 mm;
  • step (3) Under the condition of 120 °C, dry the ball mill obtained in step (3) until the moisture content is reduced to 5.5%, and then granulate after passing through a 30-mesh sieve; Mix evenly, pass through a 30-mesh sieve under a pressure of 1200kg/cm 2 to obtain granulated particles; The aqueous solution is 5% of the ball mill mass after sieving;
  • step (4) The granulated particles in step (4) are sequentially molded and sintered to obtain the high-saturation and low-loss two-component microwave ferrite material;
  • a green body of a specified shape is pressed in a pellet mold with a molding density of 3.5g/cm 3 ;
  • the sintering temperature is 1250°C
  • the sintering holding time is 5h
  • the sintering heating rate is 1°C/min
  • the start time of oxygen flow during sintering is 3 hours before the end of the heat preservation
  • the temperature of ending oxygen flow during sintering is 200°C lower than the sintering temperature.
  • the preparation method of the microwave ferrite provided in this comparative example is the same as that of comparative example 1.
  • this comparative example provides a microwave ferrite material
  • the microwave ferrite material is: Y 1.5 Ca 1.2 Fe 3.9 V 0.6 Al 0.2 Zr 0.3 In 0.3 Mn 0.1 O 12 .
  • the preparation method of the microwave ferrite material comprises the following steps:
  • step (2) The ball abrasive obtained in step (1) is dried successively, passed through a 30-mesh sieve and pre-calcined; the temperature of drying is 100° C., and the end point of drying is to reduce the moisture content to 0.5%; the temperature of the pre-calcined is 1150°C, and the holding time of the pre-burning is 6h; the heating rate of the pre-burning is 2.6°C/min;
  • step (3) 250 DEG C of drying step (3) obtained ball abrasive until the water content is reduced to 8%, and granulate after passing through a 40-mesh sieve; the granulation is to uniformly mix the sieved ball abrasive with the binder, Cross 30 mesh sieves under the pressure of 300kg/cm , obtain the granule after granulation ;
  • Described binding agent is the polypropylene alcohol solution of 5wt%;
  • the quality of polypropylene alcohol solution is step (3) ball abrasive after drying 7% of mass;
  • step (4) The granulated particles in step (4) are sequentially molded and sintered to obtain the two-component microwave ferrite material; Pressed into a circular green body, the molding density of the circular green body is 3.8g/cm 3 ; the sintering is: sintering at 1500°C, the holding time is 10h, and the heating rate of the sintering is 0.8°C/cm3 min; oxygen flow was started 6 hours before the end of the heat preservation, and the oxygen flow was stopped when the temperature dropped to 1000°C after the sintering.
  • this comparative example provides a microwave ferrite material
  • the microwave ferrite material is: Y 2.65 Ca 0.35 Fe 4.6 Sn 0.35 Mn 0.05 O 12 .
  • the preparation method of the microwave ferrite material comprises the following steps:
  • step (2) The ball abrasive obtained in step (1) is dried successively, passed through a 30-mesh sieve and pre-calcined; the temperature of drying is 100° C., and the end point of drying is to reduce the moisture content to 0.5%; the temperature of the pre-calcined is 1180°C, and the holding time of the pre-burning is 7h; the heating rate of the pre-burning is 1.8°C/min;
  • step (3) 250 DEG C of drying step (3) obtained ball abrasive until the water content is reduced to 8%, and granulate after passing through a 40-mesh sieve; the granulation is to uniformly mix the sieved ball abrasive with the binder, Cross 30 mesh sieves under the pressure of 300kg/cm , obtain the granule after granulation ;
  • Described binding agent is the polypropylene alcohol solution of 5wt%;
  • the quality of polypropylene alcohol solution is step (3) ball abrasive after drying 8% of mass;
  • step (4) The granulated particles in step (4) are sequentially molded and sintered to obtain the two-component microwave ferrite material; Pressed into a circular green body, the molding density of the circular green body is 3.8g/cm 3 ; the sintering is: sintering at 1420°C, the holding time is 11h, and the heating rate of the sintering is 0.8°C/ min; oxygen flow was started 6 hours before the end of the heat preservation, and the oxygen flow was stopped when the temperature dropped to 900°C after the sintering.
  • this comparative example provides a microwave ferrite material
  • the microwave ferrite material is: Y 2.6 Ca 0.4 Fe 4.2 Al 0.4 Zr 0.4 O 12 .
  • the preparation method of the microwave ferrite material comprises the following steps:
  • step (2) The ball abrasive obtained in step (1) is dried successively, passed through a 40-mesh sieve and pre-calcined; the temperature of drying is 120° C., and the end point of drying is to reduce the moisture content to 0.5%; the temperature of the pre-calcined is 1250°C, and the holding time of the pre-burning is 8h; the heating rate of the pre-burning is 1°C/min;
  • step (3) 250 DEG C of drying step (3) obtained ball abrasive until the water content is reduced to 8%, and granulate after passing through a 40-mesh sieve; the granulation is to uniformly mix the sieved ball abrasive with the binder, Cross 30 mesh sieves under the pressure of 350kg/cm , obtain the granule after granulation ;
  • Described binding agent is the polypropylene alcohol solution of 5wt%;
  • the quality of polypropylene alcohol solution is step (3) ball abrasive after drying 8% of mass;
  • step (4) The granulated particles in step (4) are sequentially molded and sintered to obtain the two-component microwave ferrite material; Pressed into a circular green body, the molding density of the circular green body is 3.8g/cm 3 ; the sintering is: sintering at 1470°C, the holding time is 12h, and the heating rate of the sintering is 4°C/cm3 min; oxygen flow was started 6 hours before the end of the heat preservation, and the oxygen flow was stopped when the temperature dropped to 1000°C after the sintering.
  • this comparative example provides a microwave ferrite material
  • the microwave ferrite material is: Y 2.3 Ca 0.7 Fe 4.1 Sn 0.4 Zr 0.3 Mn 0.2 Ti 0.05 O 12 .
  • the preparation method of the microwave ferrite material comprises the following steps:
  • step (2) The ball abrasive obtained in step (1) is dried successively, passed through a 30-mesh sieve and pre-calcined; the temperature of drying is 100° C., and the end point of drying is to reduce the moisture content to 0.5%; the temperature of the pre-calcined It is 1320 °C, and the holding time of the pre-burning is 15h; the heating rate of the pre-burning is 3.6 °C/min;
  • step (3) 250 DEG C of drying step (3) obtained ball abrasive until the water content is reduced to 8%, and granulate after passing through a 40-mesh sieve; the granulation is to uniformly mix the sieved ball abrasive with the binder, Cross 30 mesh sieves under the pressure of 350kg/cm , obtain the granule after granulation ;
  • Described binding agent is the polypropylene alcohol solution of 5wt%;
  • the quality of polypropylene alcohol solution is step (3) ball mill after drying 8% of mass;
  • This comparative example provides a two-component microwave ferrite material, and the two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material.
  • the first microwave ferrite material is: Y 1.5 Ca 1.2 Fe 3.9 V 0.6 Zr 0.3 In 0.3 Mn 0.1 O 12 ;
  • the second microwave ferrite material is: Gd 1.5 Ca 0.85 Fe 3.2 V 0.35 Ge 0.3 In 0.3 Ti 0.1 O 12 .
  • the preparation method of the two-component microwave ferrite material provided in this comparative example is the same as that in Example 1.
  • This comparative example provides a two-component microwave ferrite material, and the two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material.
  • the first microwave ferrite material is: Y 1.5 Ca 1.2 Fe 3.9 Al 0.6 Zr 0.3 In 0.3 Mn 0.1 O 12 ;
  • the second microwave ferrite material is: Gd 1.5 Ca 0.85 Fe 3.2 Al 0.35 Ge 0.3 In 0.3 Ti 0.1 O 12 .
  • the preparation method of the two-component microwave ferrite material provided in this comparative example is the same as that in Example 1.
  • This comparative example provides a two-component microwave ferrite material, the two-component microwave ferrite material includes a first microwave ferrite material and a second microwave ferrite material;
  • the preparation method of the two-component microwave ferrite material provided in this comparative example is the same as that in Example 1.
  • Table 1 is the magnetic property parameters of the microwave ferrite materials provided by Examples 1-10 and Comparative Examples 1-9.
  • the high-saturation and low-loss two-component microwave ferrite material provided by this application has the characteristics of high saturation magnetic moment, high Curie temperature, low line width, and low loss.
  • Analysis of comparative examples 1-9 shows that the single-group Microwave ferrite materials with single-component microwave ferrite materials have wider ferromagnetic resonance linewidth, higher dielectric loss and lower Curie temperature, therefore, it will greatly affect the stability and reliability of single-component microwave ferrite materials. Sex, which in turn affects the use of microwave communication devices.
  • Analysis of Comparative Examples 7-9 and Example 1 shows that two-component microwave ferrite materials with different chemical element compositions have different magnetic properties, so that the two are used in different fields in the field of microwave communication.
  • Example 1 provides The ferrite material provided in Comparative Example 7 has a relatively high saturation magnetic moment and is suitable for the high-field operation of the circulator.
  • the ferrite material provided in Comparative Example 7 has a low saturation magnetic moment and is suitable for the low-field operation of the circulator.
  • the high saturation and low loss two-component microwave ferrite material provided by this application has the characteristics of high saturation magnetic moment, high Curie temperature, low line width, and low loss; the saturation magnetic moment intensity is 1950Gs-1960Gs, between The electric loss is between 2 ⁇ 10 -4 -1.48 ⁇ 10 -4 , the Curie temperature can reach over 260°C, and the line width is less than 20Oe; in addition, the preparation method of the present application is stable and repeatable, which is beneficial to industrial production.

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Abstract

本申请提供了一种高饱和低损耗双组份微波铁氧体材料及其制备方法与应用，该高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料与第二微波铁氧体材料。该制备方法包括如下步骤：(1)按配方量混合第一微波铁氧体材料与第二微波铁氧体材料，然后进行湿法球磨，得到球磨料；(2)烘干步骤(1)所得球磨料，过筛后进行造粒；(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料。

Description

一种高饱和低损耗双组分微波铁氧体材料及其制备方法与应用 技术领域
本申请涉及微波通信领域及磁性材料领域，涉及一种高饱和低损耗双组份微波铁氧体材料及其制备方法与应用。
背景技术
微波铁氧体器件在微波技术中占有重要地位，在航空航天、卫星通信、电子对抗、移动通信及医疗领域中有着广泛的应用，微波铁氧体材料作为器件的核心，在各领域广泛应用。5G通信是未来信息基础设施的重要组成部分，该技术需采用微波作为传输手段，环形器、隔离器作为不可缺少的器件，其小型化、轻量化的任务尤为重要。现有微波铁氧体的介电常数在12-16之间，在低频环形器隔离器设计时器件尺寸偏大，无法满足小型化、集成化的需求。作为器件设计的主要参数之一的介电常数ε′与器件尺寸密切相关。电磁波在介质中传播的介质波长与介电常数的平方根成反比，所提高材料的介电常数就成了器件小型化的重要手段。在带线环行器中铁氧体半径R有如下近似公式：
Figure PCTCN2021129668-appb-000001
其中，k为有效波数，ω是工作角频率，c为光速，ε f为铁氧体介电常数的实数部分ε′，μ eff为有效磁导率。μ eff由下式给出：
μ eff＝1-(k/μ) 2＝1-P 2
其中，(k/μ)是铁氧体分裂因子，P是铁氧体的归一化饱和磁化强度，P＝ω m/ω
其中，ω m＝γMs，Ms是饱和磁化强度，γ是旋磁比。由此可见：铁氧体圆盘半径与介电常数ε′的平方根成反比。实践也证实：提高材料的介电常数确实可以有效地减小器件尺寸。
以前对微波铁氧体材料的研究多集中在材料的微波损耗方面，而对饱和磁矩研究的较少。随着微波技术的迅猛发展，系统对元器件小型化的要求越来越迫切，而铁氧体元器件的体积远高于其他元器件，因此其小型化、轻量化的任务尤为重要。
环行器的工作磁场区有两种，即高场区和低场区。近年来，通信用环行器迅速发展，高场区环形器的用量远远超过低场区的用量，高场区工作就是铁氧体的工作内场在该工作频率的共振场以上；共振场Hr＝ω/γ确定，工作内场Hi>Hr，用一化内场表示时，σ＝Hi/Hr。当σ>1时，称为高场工作，一般取σ的1.1-2.4 范围内。高场工作环行器一般适宜于低频段。频率在4GHz以下的均可采用；高场环行器设计高场设计环行器有如下优点：
(1)高场工作条件下，材料充分饱和，避免了零场损耗，这对低损耗器件有利，目前的低线宽材料△H＝100e很适宜在高场工作，插损很小。
(2)高场工作的环行器选择材料的归一化磁矩p＝γ4πMs/ω均大于1，甚至到几十，大大缩小了样品的尺寸(或器件的尺寸)，从设计经验来看，铁氧体样品直径Df≈λ 0/40-λ 0/10(λ 0为对应频率的波长)。
高场工作的环行器具有两重特性，在基波段(f 1-f 2)它具有环行器特性；在二次谐波段(2f 1-2f 2)它具有正反向隔离特性，即它有低通滤波器(LPF)特性，起到环行器和谐波抑制作用。谐波抑制的机理如下所述：在300-500MHz的设计环形器，假设在f 1＝300MHz频率，其归一化磁场σ＝1.67，f 2＝500MHz，其σ＝1.18。在2f 1＝600MHz频率，其归一化磁场σ＝1.67/2＝0.835，对2f 2＝1000MHz，其σ＝1.18/2＝0.59，所以(2f 1-2f 2)二次谐波频域内σ∈(0.59,0.835)的低场下工作，其张量磁导率<0，因此环行器中传播消失模，所以传播系数|S12|，|S21|均很小，一般|S12|，|S21|∈(0.1，0.02)量级，所以衰减很大，一部分能量被反射|S11(dB)|≤2dB，还有一部分能量是被铁磁共振所吸收。|S11|∈(0.76，0.96)范围内变化；而二倍频的|dS|值很小，dS∈(0.02，0.1)范围内变化。利用公式
Figure PCTCN2021129668-appb-000002
计算了三个频点(2f 1，f 1+f 2，2f 2)的|dS|值，分别为|dS|＝(0.091,0.058,0.024)，所以它的非互易性|dS|值比基频时的值小以上数量级，一般环形状态下|dS|→1，所以二次谐波的|dS|参数比基波的小10～50倍；二次谐波的非互易性可以忽略。
由上可知，环形隔离器小型化、集成化的关键是使用一种线宽小、损耗低、居里温度高以及合适的4πMs的微波铁氧体材料，该微波铁氧体材料的研究具有重要意义。
CN 102584200A公开了一种超低损耗、小线宽微波铁氧体材料及其制备，该材料的化学式为Y 3-2x-yCa 2x+yFe 5-x-y-zV xZr yAl zO 12。制备方法包括：按化学计量计算并称取原材料，震动球磨，预烧，振磨粗粉碎，砂磨细粉碎，喷雾造粒，压制成型和烧结。该技术方案可用于微波通信和磁性材料领域，该法提供了一种超低损耗、小线宽微波铁氧体材料，在制备过程中需要较高的预烧温度和烧结温度，不利于生产和环保。
US8696925B2公开了一种高介电常数石榴石铁氧体，化学式为 Y 2.15-2xBi 0.5Ca 0.35+2xZr 0.35V xFe 4.65-xO 12和Bi 0.9Ca 0.9+2xY 1.2-2xZr 0.7Nb 0.1V xFe 4.2-xO 12，其x范围分别为0-0.8和0-0.6，对应的介电常数为20-30，4πMs为1000-2000Gs。但是该专利的介电常数仍难以满足实际需求，且制备方法繁琐，毒性的V 2O 5环境不友好。
发明内容
本申请的目的在于提供一种高饱和低损耗双组分微波铁氧体材料及其制备方法与应用。本申请提供的双组份微波铁氧体材料具有小线宽、高居里温度、高饱和磁矩以及低损耗的特点，极大地提高了微波铁氧体材料的稳定性和可靠性；且本申请的工艺方法稳定可重复性好，适合大批量上产，大大降低生产成本。
本申请所述“高饱和低损耗”指：饱和磁化强度在1950Gs-1960Gs，介电损耗在1.48×10 -4-2×10 -4。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供了一种高饱和低损耗双组分微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料的制备原料包括第一微波铁氧体材料与第二微波铁氧体材料；并且
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，0≤a≤0.7，例如可以是0、0.1、0.2、0.3、0.4、0.5、0.6或0.7，但不限于所列举的数值，数值范围内其他未列举的数值同样适用；
0≤b≤0.7，例如可以是0、0.1、0.2、0.3、0.4、0.5、0.6或0.7，但不限于所列举的数值，数值范围内其他未列举的数值同样适用；
0≤c≤0.7，例如可以是0、0.1、0.2、0.3、0.4、0.5、0.6或0.7，但不限于所列举的数值，数值范围内其他未列举的数值同样适用；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，0≤A≤0.7，例如可以是0、0.1、0.2、0.3、0.4、0.5、0.6或0.7，但不限于所列举的数值，数值范围内其他未列举的数值同样适用；
0≤B≤0.7，例如可以是0、0.1、0.2、0.3、0.4、0.5、0.6或0.7，但不限于所列举的数值，数值范围内其他未列举的数值同样适用；
0≤C≤0.7，例如可以是0、0.1、0.2、0.3、0.4、0.5、0.6或0.7，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，所述第一微波铁氧体材料与第二微波铁氧体材料的质量比为(1-3):(1-3)，例如可以是1:1、1:2、1:3、2:3、3:2或3:1，但不限于所列举的数值， 数值范围内其它未列举的数值同样适用。
纯的钇铁石榴石铁氧体功率承载能力较低，铁磁共振线宽和介电损耗较大，且其烧结温度较高，在性能上比较单一。本申请着重通过采用以Zr 4+置换部分八面体的Fe 3+，可以降低磁晶的各项异性常数，使得铁磁共振线宽下降，但是Zr 4+不能过多，过多会使得铁磁共振线宽迅速增大；Ca 2+是低熔点物质，它们的掺入可以降低烧结温度；用少量Mn 2+代替部分Fe 3+可以降低材料的铁磁共振线宽和介电损耗；Gd 3+离子取代Y 3+可以改善Ms温度系数，从而使维持较高的居里温度。本申请通过调整微波铁氧体材料的组成，利用各元素电磁特点的配合作用，获得了较高的饱和磁化强度4πMs、较窄的铁磁共振线宽△H、较低的介电损耗tgδ e以及较高的居里温度Tc的微波铁氧体材料。
第二方面，本申请提供了一种如第一方面所述高饱和低损耗双组份微波铁氧体材料的制备方法，所述制备方法包括如下步骤：
(1)按配方量混合第一微波铁氧体材料与第二微波铁氧体材料，然后进行湿法球磨，得到球磨料；
(2)烘干步骤(1)所得球磨料，过筛后进行造粒；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述双组份微波铁氧体材料。
可选地，步骤(1)所述湿法球磨为将制备原料、研磨球与弥散剂按照质量比1:(4-7.5):(0.6-2.5)混合，进行湿法球磨，例如可以是1:4:0.6、1:5:0.8、1:6:1.2、1:7:1.5、1:7.5:2、1:6.5:1.5、1:4.5:2.5或1:5.5:2.5，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(1)所述湿法球磨的转速为20-80r/min，例如可以是20r/min、30r/min、40r/min、50r/min、60r/min、70r/min或80r/min，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(1)所述湿法球磨的时间为10-40h，例如可以是10h、15h、20h、25h、30h、35h或40h，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，所述研磨球包括锆球和/或钢球。
可选地，所述研磨球包括大径研磨球和小径研磨球。
所述大径研磨球的直径为5-10mm，例如可以是5mm、6mm、7mm、8mm、9mm或10mm，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
所述小径研磨球的直径为1-4mm，例如可以是1mm、2mm、3mm或4mm， 但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，所述大径研磨球与小径研磨球的质量比为(0.8-3):1，例如可以是0.8:1、1:1、1.2:1、1.4:1、1.6:1、1.8:1、2:1、2.2:1、2.4:1、2.6:1、2.8:1或3:1，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，所述弥散剂包括去离子水、酒精、丙酮、正丙酮或氨水中的任意一种或至少两种的组合，典型但非限制性的组合包括去离子水和酒精的组合，去离子水和丙酮的组合，去离子水和氨水的组合，去离子水、酒精和氨水的组合，或去离子水、酒精和丙酮的组合。
可选地，步骤(1)所述球磨料的粒径范围为D50＝0.05-2μm，D90＝0.05-4μm，例如可以是D50＝0.005μm、0.01μm、0.05μm、0.1μm、0.5μm、1μm、1.5μm或2μm，D90＝0.05μm、0.1μm、0.5μm、1μm、1.5μm、2μm、3μm或4μm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
本申请步骤(1)所述湿法球磨时间的长短会影响烧结所需的温度，最终决定材料的烧结密度和线宽，介电损耗等性能；球磨介质不同会影响球磨的效果，研磨球的选择会影响工艺控制的稳定性和控制难度。通过上述球磨条件，可以获得较好的球磨效果，降低细度，提高材料的活性，降低烧结温度。
可选地，步骤(2)所述烘干的温度为100-150℃，例如可以是100℃、110℃、120℃、130℃、140℃或150℃，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(2)所述烘干的终点为使含水率降低至0.01-10％，例如可以是0.01％、0.1％、1％、3％、5％、7％、9％或10％，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(2)所述过筛所用筛网的目数为30-100目，例如可以是30目、40目、50目、60目、70目、80目、90目或100目，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(2)所述造粒为将过筛后的球磨料与粘粘剂均匀混合，在压力下过筛，得到造粒后的颗粒。
可选地，所述粘结剂包括聚乙烯醇水溶液。
可选地，所述聚乙烯醇溶液的浓度为5-20wt％，例如可以是5wt％、10wt％、15wt％或20wt％，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，所述聚乙烯醇溶液的质量为粉料质量的5-10％，例如可以是5％、 6％、7％、8％、9％或10％，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，所述过筛的压力为300-1200kg/cm 2，例如可以是300kg/cm 2、500kg/cm 2、700kg/cm 2、900kg/cm 2、1100kg/cm 2或1200kg/cm 2，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(3)所述成型为：将步骤(2)造粒后颗粒放入模具内压制成指定形状的生坯。
可选地，所述生坯的成型密度为3.0-4.0g/cm 3，例如可以是3.0g/cm 3、3.2g/cm 3、3.4g/cm 3、3.6g/cm 3、3.8g/cm 3或4.0g/cm 3，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(3)所述烧结为：所述烧结的温度为1200-1500℃，例如可以是1200℃、1300℃、1400℃或1500℃，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
本申请所述烧结温度过低或过高均会导致烧结密度降低，线宽增大，介电损耗增大。
可选地，所述烧结的保温时间为5-30h，例如可以还5h、10h、15h、20h、25h或30h，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，所述烧结的升温速率为1-5℃/min，例如可以是1℃/min、2℃/min、3℃/min、4℃/min或5℃/min，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(3)所述烧结时通氧的起始时间为保温结束前1-6h，例如可以是1h、2h、3h、4h、5h或6h，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(3)所述烧结时结束通氧的时间为：保温结束后，温度降低100-500℃时，结束通氧，例如可以是100℃、200℃、300℃、400℃或500℃，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(1)所述第一微波铁氧体材料的制备方法包括如下步骤：
(a)按配方量混合第一微波铁氧体的制备原料，湿法球磨后得到球磨料；
(b)步骤(a)所得球磨料依次进行烘干、过筛与预烧，得到第一微波铁氧体材料；
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，0≤a≤0.7，0≤b≤0.7，0≤c≤0.7；
可选地，所述第一微波铁氧体材料的制备原料分别为：Y 2O 3、CaCO 3、Fe 2O 3、ZrO 2、SnO 2以及MnCO 3。
可选地，步骤(a)所述湿法球磨为将制备原料、研磨球、弥散剂与分散剂按照质量比1:(4-7.5):(0.6-2.5):(0.003-0.01)混合，进行湿法球磨，例如可以是1:4:0.6:0.003、1:5:0.8:0.004、1:6:1.2:0.005、1:7:1.5:0.006、1:7.5:2:0.007、1:5:1.5:0.008、1:6:2.5:0.009或1:6.5:2.5:0.01，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(a)所述湿法球磨的转速为20-80r/min，例如可以是20r/min、30r/min、40r/min、50r/min、60r/min、70r/min或80r/min，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(a)所述湿法球磨的时间为10-40h，例如可以是10h、15h、20h、25h、30h、35h或40h，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(a)所述研磨球包括锆球。
可选地，步骤(a)所述研磨球包括大径研磨球和小径研磨球。
所述大径研磨球的直径为5-10mm，例如可以是5mm、6mm、7mm、8mm、9mm或10mm，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
所述小径研磨球的直径为1-4mm，例如可以是1mm、2mm、3mm或4mm，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，所述大径研磨球与小径研磨球的质量比为(0.8-3):1，例如可以是0.8:1、1:1、1.2:1、1.4:1、1.6:1、1.8:1、2:1、2.2:1、2.4:1、2.6:1、2.8:1或3:1，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(a)所述湿法球磨所用弥散剂包括去离子水、酒精、丙酮、正丙酮或氨水中的任意一种或至少两种的组合，典型但非限制性的组合包括去离子水和酒精的组合，去离子水和丙酮的组合，去离子水和氨水的组合，去离子水、酒精和氨水的组合，或去离子水、酒精和丙酮的组合。
可选地，步骤(a)所述湿法球磨所用分散剂包括柠檬酸铵和/或氨水。
可选地，步骤(a)所述球磨料的粒径范围为D50＝0.05-2μm，D90＝0.05-4μm，例如可以是D50＝0.005μm、0.01μm、0.05μm、0.1μm、0.5μm、1μm、1.5μm或2μm，D90＝0.05μm、0.1μm、0.5μm、1μm、1.5μm、2μm、3μm或4μm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
所述湿法球磨时间的长短会影响离子占位的程度，最终影响在现有预烧温 度条件下的产品性能；球磨介质不同会影响球磨的效果，研磨球的选择会影响工艺控制的稳定性和控制难度。通过上述可选条件，可以获得较好的球磨效果，以及在双组份微波铁氧体制备过程中球磨中得到纯的预成相第一微波铁氧体材料，而且能够除去杂相，获得合适的粒度分布和活性，有利于后续的预烧和烧结过程的固相反应。
可选地，步骤(b)所述烘干的温度为100-150℃，例如可以是100℃、110℃、120℃、130℃、140℃或150℃，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(b)所述烘干的终点为使含水率降低至0.01-10％，例如可以是0.01％、1％、3％、5％、7％、9％或10％，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(b)所述过筛所用筛网的目数为30-100目，例如可以是30目、50目、70目、90目或100目，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(b)所述预烧的温度为1100-1400℃，例如可以是1100℃、1200℃、1300℃或1400℃，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(b)所述预烧的保温时间为6-15h，例如可以是6h、8h、10h、12h、14h或15h，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(b)所述预烧的升温速率为0.3-4℃/min，例如可以是0.3℃/min、1℃/min、2℃/min、3℃/min或4℃/min，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
本申请所述预烧可以降低烘干后球磨料的化学活性的不均匀性，也可以降低后续烧结产品的收缩率，减少变形。
可选地，步骤(1)所述第二微波铁氧体材料的制备方法包括如下步骤：
(I)按配方量混合第二微波铁氧体的制备原料，湿法球磨后得到球磨料；
(Ⅱ)步骤(1)所得球磨料依次进行烘干、过筛与预烧，得到第二微波铁氧体材料；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，0≤A≤0.7，0≤B≤0.7，0≤C≤0.7。
可选地，步骤(I)所述第二微波铁氧体材料的制备原料分别为Gd 2O 3、CaCO 3、Fe 2O 3、GeO 2、InO 2以及TiO 2。
可选地，步骤(I)所述湿法球磨为将制备原料、研磨球、弥散剂与分散剂按照质量比1:(4-7.5):(0.6-2.5):(0.003-0.01)混合，进行湿法球磨，例如可以是1:4:0.6:0.008、1:5:0.8:0.009、1:6:1.2:0.01、1:7:1.5:0.003、1:7.5:2:0.004、1:1.5:1.5:0.005、1:1:2.5:0.006或1:5:2.5:0.007，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(I)所述湿法球磨的研磨球包括锆球和/或钢球。
可选地，步骤(I)所述研磨球包括大径研磨球和小径研磨球。
所述大径研磨球的直径为5-10mm，例如可以是5mm、6mm、7mm、8mm、9mm或10mm，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
所述小径研磨球的直径为1-4mm，例如可以是1mm、2mm、3mm或4mm，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(I)所述大径研磨球与小径研磨球的质量比为(0.8-3):1，例如可以是0.8:1、1:1、1.2:1、1.4:1、1.6:1、1.8:1、2:1、2.2:1、2.4:1、2.6:1、2.8:1或3:1，但不限于所列举的数值，数值范围内其他未列举的数值同样适用。
可选地，步骤(I)所述弥散剂包括去离子水、酒精、丙酮、正丙醇或氨水中的任意一种或至少两种的组合。
可选地，步骤(I)所述分散剂包括柠檬酸铵和/或氨水。
可选地，步骤(I)所述湿法球磨的转速为20-80r/min，例如可以是20r/min、30r/min、40r/min、50r/min、60r/min、70r/min或80r/min，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(I)所述湿法球磨的时间为10-40h，例如可以是10h、15h、20h、25h、30h、35h或40h，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(I)所述球磨料的粒度范围为D50＝0.005-2μm，D90＝0.05-4μm，例如可以是D50＝0.005μm、0.01μm、0.05μm、0.1μm、0.5μm、1μm、1.5μm或2μm，D90＝0.05μm、0.1μm、0.5μm、1μm、1.5μm、2μm、3μm或4μm，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(II)所述烘干的温度为100-150℃，例如可以是100℃、110℃、120℃、130℃、140℃或150℃，但不限于所列举的数值，数值范围内其他未列 举的数值同样适用。
可选地，步骤(II)所述烘干的终点为使含水率降低至0.01-10％，例如可以是0.01％、0.1％、1％、3％、5％、7％、9％或10％，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(II)所述过筛所用筛网的目数为30-100目，例如可以是30目、40目、50目、60目、70目、80目、90目或100目，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(II)所述预烧的温度为1100-1400℃，例如可以是1100℃、1200℃、1300℃或1400℃，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(II)所述预烧的保温时间为8-20h，例如可以是8h、10h、12h、14h、16h、18h或20h，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
可选地，步骤(II)所述预烧的升温速率为0.3-4℃/min，例如可以是0.3℃/min、2℃/min、3℃/min或4℃/min，但不限于所列举的数值，数值范围内其它未列举的数值同样适用。
本申请所述预烧可以降低烘干后球磨料的化学活性的不均匀性，也可以降低后续烧结产品的收缩率，减少变形。
作为本申请的可选技术方案，第二方面所述制备方法包括如下步骤：
(1)按配方量混合第一微波铁氧体材料与第二微波铁氧体材料，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、研磨球与弥散剂按照质量比1:(4-7.5):(0.6-2.5)混合，进行转速为20-80r/min、时间为10-40h的湿法球磨；所得球磨料的粒径范围为D50＝0.005-2μm，D90＝0.05-4μm；
(2)100-250℃的条件下烘干步骤(1)所得球磨料至含水率降低至0.01-10％，过30-100目筛后进行造粒；
所述造粒为将过筛后的球磨料与粘结剂均匀混合，在300-1200kg/cm 2压力下过30-100目筛，得到造粒后的颗粒；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒在模具内压制指定形状的生坯，所述生坯的成型密度为3.0-4.0g/cm 3；所述烧结的温度为1200-1500℃，所述烧结的保温时间为5-30h，所述烧结的升温速率为1-5℃/min，所述烧结时通氧的起始时间为保温结束前1-6h，保温结束后，温度 降低100-500℃时，结束通氧；
步骤(1)所述第一微波铁氧体材料的制备方法包括：
(a)按配方量混合第一微波铁氧体材料的制备原料，湿法球磨后得到球磨料；湿法球磨的转速为20-80r/min，时间为10-40h；所得球磨料的粒度范围为D50＝0.005-2μm，D90＝0.05-4μm；
(b)步骤(a)所得球磨料依次进行烘干、过30-100目筛与预烧，得到第一微波铁氧体材料；烘干的温度为100-250℃，烘干的终点为使含水率降低至0.01-10％；所述预烧的温度为1100-1350℃；所述预烧的保温时间为6-15h；所述预烧的升温速率为0.3-4℃/min；
步骤(1)所述第二微波铁氧体材料的制备方法包括：
(I)按配方量混合第二微波铁氧体材料的制备原料，湿法球磨后得到球磨料；湿法球磨的转速为20-80r/min，时间为10-40h；所得球磨料的粒度范围为D50＝0.005-2μm，D90＝0.05-4μm；
(II)步骤(I)所得球磨料依次进行烘干、过筛与预烧，得到第二微波铁氧体材料；烘干的温度为100-250℃，烘干的终点为使含水率降低至0.01-10％；所述预烧的温度为1100-1400℃；所述预烧的保温时间为8-20h。
第三方面，本申请提供了一种如第一方面所述高饱和低损耗高饱和低损耗双组份微波铁氧体的应用，所述高饱和低损耗双组份微波铁氧体用于微波通信器件。
本申请所述的数值范围不仅包括上述例举的点值，还包括没有例举出的上述数值范围之间的任意的点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
与现有技术相比，本申请的有益效果为：
(1)本申请采用双组份复合工艺制备得到的微波铁氧体材料具有高饱和磁矩、高居里温度、低线宽、低损耗；饱和磁矩强度在1950Gs-1960Gs，介电损耗在1.58×10 -4-2×10 -4，居里温度可达260℃以上，线宽小于18Oe；
(2)本申请的制备方法工艺稳定可重复性好，有利于工业化生产。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。
实施例1
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0.3，b＝0.3，c＝0；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0.5，B＝0.1，C＝0.05。
所述高饱和低损耗双组份微波铁氧体材料的制备方法包括如下步骤：
(1)将第一微波铁氧体材料与第二微波铁氧体材料按照1:1的质量比均匀混合，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、锆球与去离子水按照质量比1:4:0.6混合，进行转速为20r/min、时间为26h的湿法球磨；所述大径锆球和小径锆球的质量比为3:1，所述大径锆球的直径为5mm，所述小径锆球的直径为2mm；所得球磨料的粒径范围为D50＝0.85μm，D90＝2.85μm；
(2)120℃的条件下烘干步骤(1)所得球磨料至含水率降低至5.5％，过30目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在1200kg/cm 2压力下过30目筛，得到造粒后的颗粒；所述粘结剂为聚乙烯醇水溶液，所述聚乙烯醇水溶液的浓度为20wt％，所述聚乙烯醇水溶液为过筛后的球磨料质量的5％；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒模具内压制指定形状的生坯，所述生坯的成型密度为3.5g/cm 3；所述烧结的温度为1250℃，所述烧结的保温时间为5h，所述烧结的升温速率为1℃/min，所述烧结时通氧的起始时间为保温结束前3h，保温结束后，温度降低200℃时，结束通氧；
步骤(1)所述第一微波铁氧体材料的制备方法包括：
(a)按配方量混合第一微波铁氧体材料的制备原料，将制备原料、研磨球、去离子水与柠檬酸铵按照质量比1:4:0.6:0.003混合，进行转速为20r/min，时间为16h的湿法球磨；所述大径研磨球与小径研磨球的质量比为3:1；所述大径研磨球的直径为5mm，所述小径研磨球的直径为2mm；所得球磨料的粒度范围为D50＝0.85μm，D90＝2.85μm；
(b)步骤(a)所得球磨料依次进行烘干、过30目筛与预烧，得到第一微波铁氧体材料；烘干的温度为120℃，烘干的终点为使含水率降低至0.2％；所述预烧的温度为1150℃；所述预烧的保温时间为6h；所述预烧的升温速率为0.5℃/min；
步骤(1)所述第二微波铁氧体材料的制备方法包括：
(I)按配方量混合第二微波铁氧体材料的制备原料，将制备原料、研磨球、去离子水与柠檬酸铵按照质量比1:4:0.6:0.003混合，进行转速为20r/min，时间为16h的湿法球磨；所述大径研磨球与小径研磨球的质量比为3:1；所述大径研磨球的直径为5mm，所述小径研磨球的直径为2mm；所得球磨料的粒度范围为D50＝0.85μm，D90＝2.85μm；
(II)步骤(I)所得球磨料依次进行烘干、过筛与预烧，得到第二微波铁氧体材料；烘干的温度为100℃，烘干的终点为使含水率降低至0.5％；所述预烧的温度为1120℃；所述预烧的保温时间为8h。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例2
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0.2，b＝0.4，c＝0.05；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0.2，B＝0.3，C＝0.3。
所述高饱和低损耗双组份微波铁氧体材料的制备方法包括如下步骤：
(1)将第一微波铁氧体材料与第二微波铁氧体材料按照1:1的质量比均匀混合，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、锆球与丙酮按照质量比1:6:1.3混合，进行转速为40r/min、时间为15h的湿法球磨；所述大径锆球和小径锆球的质量比为5:2，所述大径锆球的直径为10mm，所述小径锆球的直径为4mm；所得球磨料的粒径范围为D50＝1.2μm，D90＝1.5μm；
(2)150℃的条件下烘干步骤(1)所得球磨料至含水率降低至6.5％，过50目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在1000kg/cm 2压力下过50目筛，得到造粒后的颗粒；所述粘结剂为聚乙烯醇水溶液，所述聚乙烯醇水溶液的浓度为10wt％，所述聚乙烯醇水溶液为过筛后的球磨料质量的6％；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒模具内压制指定形状的生坯，所述生坯的成型密度为4g/cm 3；所述烧结的温度为1260℃，所述烧结的保温时间为10h，所述烧结的升温速率为3℃/min，所述烧 结时通氧的起始时间为保温结束前4h，保温结束后，温度降低300℃时，结束通氧；
步骤(1)所述第一微波铁氧体材料的制备方法包括：
(a)按配方量混合第一微波铁氧体材料的制备原料，将制备原料、锆球、酒精与柠檬酸铵按照质量比1:5.5:1.2:0.005混合，进行转速为30r/min，时间为15h的湿法球磨；所述大径研磨球与小径研磨球的质量比为4:1.5；所述大径研磨球的直径为5mm，所述小径研磨球的直径为3mm；所得球磨料的粒度范围为D50＝1μm，D90＝3μm；
(b)步骤(a)所得球磨料依次进行烘干、过50目筛与预烧，得到第一微波铁氧体材料；烘干的温度为150℃，烘干的终点为使含水率降低至5.5％；所述预烧的温度为1100℃；所述预烧的保温时间为7h；所述预烧的升温速率为3.2℃/min；
步骤(1)所述第二微波铁氧体材料的制备方法包括：
(I)按配方量混合第二微波铁氧体材料的制备原料，将制备原料、锆球、酒精与柠檬酸铵按照质量比1:5.5:1.2:0.005混合，进行转速为30r/min，时间为15h的湿法球磨；所述大径研磨球与小径研磨球的质量比为4:1.5；所述大径研磨球的直径为5mm，所述小径研磨球的直径为3mm；所得球磨料的粒度范围为D50＝1μm，D90＝3μm；
(II)步骤(I)所得球磨料依次进行烘干、过50目筛与预烧，得到第二微波铁氧体材料；烘干的温度为150℃，烘干的终点为使含水率降低至3.2％；所述预烧的温度为1100℃；所述预烧的保温时间为9h。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例3
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0.25，b＝0.25，c＝0.1；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0.2，B＝0.5，C＝0.4。
所述高饱和低损耗双组份微波铁氧体材料的制备方法包括如下步骤：
(1)将第一微波铁氧体材料与第二微波铁氧体材料按照1:1的质量比均匀混合，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、锆球与 丙酮按照质量比1:6:1.4混合，进行转速为60r/min、时间为20h的湿法球磨；所述大径锆球和小径锆球的质量比为1:1，所述大径锆球的直径为3mm，所述小径锆球的直径为3mm；所得球磨料的粒径范围为D50＝0.5μm，D90＝4μm；
(2)200℃的条件下烘干步骤(1)所得球磨料至含水率降低至0.01％，过80目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在1000kg/cm 2压力下过50目筛，得到造粒后的颗粒；所述粘结剂为聚乙烯醇水溶液，所述聚乙烯醇水溶液的浓度为5wt％，所述聚乙烯醇水溶液为过筛后的球磨料质量的8％；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒模具内压制指定形状的生坯，所述生坯的成型密度为3.2g/cm 3；所述烧结的温度为1400℃，所述烧结的保温时间为15h，所述烧结的升温速率为3.5℃/min，所述烧结时通氧的起始时间为保温结束前2h，保温结束后，温度降低400℃时，结束通氧；
步骤(1)所述第一微波铁氧体材料的制备方法包括：
(a)按配方量混合第一微波铁氧体材料的制备原料，将制备原料、锆球、丙酮与柠檬酸铵按照质量比1:7:1.3:0.006混合，进行转速为40r/min，时间为10h的湿法球磨；所述大径研磨球与小径研磨球的质量比为5:2；所述大径研磨球的直径为10mm，所述小径研磨球的直径为4mm；所得球磨料的粒度范围为D50＝1.2μm，D90＝2.5μm；
(b)步骤(a)所得球磨料依次进行烘干、过50目筛与预烧，得到第一微波铁氧体材料；烘干的温度为200℃，烘干的终点为使含水率降低至0.01％；所述预烧的温度为1250℃；所述预烧的保温时间为8h；所述预烧的升温速率为2.8℃/min；
步骤(1)所述第二微波铁氧体材料的制备方法包括：
(I)按配方量混合第二微波铁氧体材料的制备原料，将制备原料、锆球、丙酮与柠檬酸铵按照质量比1:7:1.3:0.006混合，进行转速为40r/min，时间为10h的湿法球磨；所述大径研磨球与小径研磨球的质量比为5:2；所述大径研磨球的直径为10mm，所述小径研磨球的直径为4mm；所得球磨料的粒度范围为D50＝1.2μm，D90＝2.5μm；
(II)步骤(I)所得球磨料依次进行烘干、过50目筛与预烧，得到第二微波铁氧体材料；烘干的温度为200℃，烘干的终点为使含水率降低至0.01％；所 述预烧的温度为1200℃；所述预烧的保温时间为7h。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例4
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0.35，b＝0.15，c＝0.1；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0.4，B＝0.2，C＝0.4。
所述高饱和低损耗双组份微波铁氧体材料的制备方法包括如下步骤：
(1)将第一微波铁氧体材料与第二微波铁氧体材料按照1:1的质量比均匀混合，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、锆球与丙酮按照质量比1:7.5:2.5混合，进行转速为80r/min、时间为40h的湿法球磨；所述大径锆球和小径锆球的质量比为3.5:4，所述大径锆球的直径为7mm，所述小径锆球的直径为1mm；所得球磨料的粒径范围为D50＝0.3μm，D90＝2μm；
(2)200℃的条件下烘干步骤(1)所得球磨料至含水率降低至8％，过100目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在300kg/cm 2压力下过100目筛，得到造粒后的颗粒；所述粘结剂为聚乙烯醇水溶液，所述聚乙烯醇水溶液的浓度为8wt％，所述聚乙烯醇水溶液为过筛后的球磨料质量的7％；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒模具内压制指定形状的生坯，所述生坯的成型密度为3g/cm 3；所述烧结的温度为1500℃，所述烧结的保温时间为20h，所述烧结的升温速率为4.8℃/min，所述烧结时通氧的起始时间为保温结束前1h，保温结束后，温度降低500℃时，结束通氧；
步骤(1)所述第一微波铁氧体材料的制备方法包括：
(a)按配方量混合第一微波铁氧体材料的制备原料，将制备原料、锆球、正丙酮与柠檬酸铵按照质量比1:6:1.4:0.01混合，进行转速为60r/min，时间为20h的湿法球磨；所述大径研磨球与小径研磨球的质量比为1:1；所述大径研磨球的直径为6mm，所述小径研磨球的直径为2mm；所得球磨料的粒度范围为D50＝0.5μm，D90＝4μm；
(b)步骤(a)所得球磨料依次进行烘干、过100目筛与预烧，得到第一微波铁氧体材料；烘干的温度为250℃，烘干的终点为使含水率降低至6.9％；所述预烧的温度为1300℃；所述预烧的保温时间为10h；所述预烧的升温速率为5.2℃/min；
步骤(1)所述第二微波铁氧体材料的制备方法包括：
(I)按配方量混合第二微波铁氧体材料的制备原料，将制备原料、锆球、正丙酮与柠檬酸铵按照质量比1:6:1.4:0.01混合，进行转速为60r/min，时间为20h的湿法球磨；所述大径研磨球与小径研磨球的质量比为1:1；所述大径研磨球的直径为6mm，所述小径研磨球的直径为2mm；所得球磨料的粒度范围为D50＝0.5μm，D90＝4μm；
(II)步骤(I)所得球磨料依次进行烘干、过100目筛与预烧，得到第二微波铁氧体材料；烘干的温度为250℃，烘干的终点为使含水率降低至8.2％；所述预烧的温度为1250℃；所述预烧的保温时间为15h。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例5
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
所述第一微波铁氧体材料为：Y 3-aCa abFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0.4，b＝0.1，c＝0.35；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0.6，B＝0.5，C＝0.3。
所述高饱和低损耗双组份微波铁氧体材料的制备方法包括如下步骤：
(1)将第一微波铁氧体材料与第二微波铁氧体材料按照1:1的质量比均匀混合，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、锆球与丙酮按照质量比1:5.5:2.5混合，进行转速为30r/min、时间为10h的湿法球磨；所述大径锆球和小径锆球的质量比为4:1.5，所述大径锆球的直径为5mm，所述小径锆球的直径为3mm；所得球磨料的粒径范围为D50＝1μm，D90＝3μm；
(2)180℃的条件下烘干步骤(1)所得球磨料至含水率降低至10％，过60目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在800kg/cm 2压力下过6目筛，得到造粒后的颗粒；所述粘结剂为聚乙烯醇水溶液，所述聚乙烯醇水溶液的浓度为5wt％，所述聚乙烯醇水溶液为过筛后的球磨料质量的10％；
(3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒模具内压制指定形状的生坯，所述生坯的成型密度为3.6g/cm 3；所述烧结的温度为1200℃，所述烧结的保温时间为30h，所述烧结的升温速率为3.9℃/min，所述烧结时通氧的起始时间为保温结束前6h，保温结束后，温度降低100℃时，结束通氧；
步骤(1)所述第一微波铁氧体材料的制备方法包括：
(a)按配方量混合第一微波铁氧体材料的制备原料，将制备原料、锆球、氨水与柠檬酸铵按照质量比1:7.5:2.5:0.008混合，进行转速为80r/min，时间为40h的湿法球磨；所述大径研磨球与小径研磨球的质量比为3.5:4；所述大径研磨球的直径为7mm，所述小径研磨球的直径为4mm；所得球磨料的粒度范围为D50＝0.3μm，D90＝2μm；
(b)步骤(a)所得球磨料依次进行烘干、过60目筛与预烧，得到第一微波铁氧体材料；烘干的温度为180℃，烘干的终点为使含水率降低至6.9％；所述预烧的温度为1350℃；所述预烧的保温时间为15h；所述预烧的升温速率为4.2℃/min；
步骤(1)所述第二微波铁氧体材料的制备方法包括：
(I)按配方量混合第二微波铁氧体材料的制备原料，将制备原料、锆球、酒精与氨水按照质量比1:7.5:2.5:0.008混合，进行转速为80r/min，时间为40h的湿法球磨；所述大径研磨球与小径研磨球的质量比为3.5:4；所述大径研磨球的直径为7mm，所述小径研磨球的直径为4mm；所得球磨料的粒度范围为D50＝0.3μm，D90＝2μm；
(II)步骤(I)所得球磨料依次进行烘干、过100目筛与预烧，得到第二微波铁氧体材料；烘干的温度为250℃，烘干的终点为使含水率降低至8.2％；所述预烧的温度为1250℃；所述预烧的保温时间为15h。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例6
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料的制备方法除将步骤(1)所述第一微波铁氧体材料与第二微波铁氧体材料的质量比更换为1:3，其余均与实施例1相同。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例7
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料的制备方法除将步骤(1)所述第一微波铁氧体材料与第二微波铁氧体材料的质量比更换为3:1，其余均与实施例1相同。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例8
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0，b＝0，c＝0；
所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0，B＝0，C＝0。
所述高饱和低损耗双组份微波铁氧体材料的制备方法与实施例1相同。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例9
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料的制备方法除将步骤(3)所述的烧结温度更换为800℃，其余均与实施例1相同。
获得的样品经磨加工后测量的磁性能如表1所示。
实施例10
本实施例提供了一种高饱和低损耗双组份微波铁氧体材料，所述高饱和低损耗双组份微波铁氧体材料的制备方法除将步骤(3)所述的烧结温度更换为2000℃，其余均与实施例1相同。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例1
本对比例提供了一种微波铁氧体材料，所述微波铁氧体材料为：Y 3-a-bCa a+bFe 5-a-b-cZr aIn bMn cO 12，其中，a＝0.3，b＝0.3，c＝0。
所述微波铁氧体的制备方法包括如下步骤：
(1)按配方量混合微波铁氧体材料的制备原料，将制备原料、研磨球、去离子水与柠檬酸铵按照质量比1:4:0.6:0.003混合，进行转速为20r/min，时间为16h的湿法球磨；所述大径研磨球与小径研磨球的质量比为3:1；所述大径研磨球的直径为5mm，所述小径研磨球的直径为2mm；所得球磨料的粒度范围为 D50＝0.85μm，D90＝2.85μm；
(2)步骤(1)所得球磨料依次进行烘干、过30目筛与预烧，得到微波铁氧体材料前驱体；烘干的温度为120℃，烘干的终点为使含水率降低至0.2％；所述预烧的温度为1150℃；所述预烧的保温时间为6h；所述预烧的升温速率为0.5℃/min；
(3)将步骤(2)所述微波铁氧体材料前驱体敲碎，得到粉料，过30目筛，然后按照粉料、锆球与去离子水按照质量比1:4:0.6混合，进行转速为20r/min、时间为26h的湿法球磨；所述大径锆球和小径锆球的质量比为3:1，所述大径锆球的直径为5mm，所述小径锆球的直径为2mm；所得球磨料的粒径范围为D50＝0.85μm，D90＝2.85μm；
(4)120℃的条件下烘干步骤(3)所得球磨料至含水率降低至5.5％，过30目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在1200kg/cm 2压力下过30目筛，得到造粒后的颗粒；所述粘结剂为聚乙烯醇水溶液，所述聚乙烯醇水溶液的浓度为20wt％，所述聚乙烯醇水溶液为过筛后的球磨料质量的5％；
(5)步骤(4)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(4)所得造粒后的颗粒模具内压制指定形状的生坯，所述生坯的成型密度为3.5g/cm 3；所述烧结的温度为1250℃，所述烧结的保温时间为5h，所述烧结的升温速率为1℃/min，所述烧结时通氧的起始时间为保温结束前3h，所述烧结时结束通氧的温度为低于烧结温度200℃。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例2
本对比例提供了一种微波铁氧体材料，所述微波铁氧体材料为：Gd 3-A-BCa A+BFe 5-A-B-CGe AIn BTi CO 12，其中，A＝0.5，B＝0.1，C＝0.05。
本对比例提供的微波铁氧体的制备方法与对比例1相同。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例3
根据离子取代机理，本对比例提供了一种微波铁氧体材料，所述微波铁氧体材料为：Y 1.5Ca 1.2Fe 3.9V 0.6Al 0.2Zr 0.3In 0.3Mn 0.1O 12。
该微波铁氧体材料的制备方法包括如下步骤：
(1)按照化学式计算并称取原材料；将称取的原材料将称取的原材料放入 球磨罐中，按照原材料、锆球、去离子水与柠檬酸铵按照质量比1:4:1:0.1混合，进行转速为20r/min、时间为16h的湿法球磨，所述大径锆球和小径锆球的质量比为3:1，所述大径锆球的直径为5mm，所述小径锆球的直径为2mm，所得球磨料的粒度范围为D50＝0.85μm，D90＝2.85μm；
(2)步骤(1)所得球磨料依次进行烘干、过30目筛与预烧；烘干的温度为100℃，烘干的终点为使含水率降低至0.5％；所述预烧的温度为1150℃，所述预烧的保温时间为6h；所述预烧的升温速率为2.6℃/min；
(3)将步骤(2)所得预烧后的球磨料敲碎，得到粉料，过30目筛，然后按照粉料、锆球与去离子水1:4:1的质量比混合，再次进行转速为20r/min、时间为26h的湿法球磨，所述大径锆球和小径锆球的质量比为3:1，所述大径锆球的直径为5mm，所述小径锆球的直径为2mm，所得球磨料的粒度范围为D50＝0.85μm，D90＝2.85μm；
(4)250℃烘干步骤(3)所得球磨料至含水率降低至8％，过40目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在300kg/cm 2的压力下过30目筛，得到造粒后的颗粒；所述粘结剂为5wt％的聚丙烯醇溶液；聚丙烯醇溶液的质量为步骤(3)烘干后球磨料质量的7％；
(5)步骤(4)所述造粒后的颗粒依次进行成型与烧结，得到所述双组份微波铁氧体材料；所述成型为：将步骤(4)所得造粒后的颗粒模具内压制成圆形生坯，所述圆形生坯的成型密度为3.8g/cm 3；所述烧结为：在1500℃下进行烧结，保温时间为10h，所述烧结的升温速率为0.8℃/min；在保温结束前6h开始通氧，烧结结束后温度降低至1000℃时结束通氧。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例4
根据离子取代机理，本对比例提供了一种微波铁氧体材料，所述微波铁氧体材料为：Y 2.65Ca 0.35Fe 4.6Sn 0.35Mn 0.05O 12。
该微波铁氧体材料的制备方法包括如下步骤：
(1)按照化学式计算并称取原材料；将称取的原材料将称取的原材料放入球磨罐中，按照原材料、锆球、去离子水与柠檬酸铵按照质量比1:5.5:1.2:0.03混合，进行转速为10r/min、时间为10h的湿法球磨，所述大径锆球和小径锆球的质量比为4:1.5，所述大径锆球的直径为5mm，所述小径锆球的直径为3mm，所得球磨料的粒度范围为D50＝1μm，D90＝3μm；
(2)步骤(1)所得球磨料依次进行烘干、过30目筛与预烧；烘干的温度 为100℃，烘干的终点为使含水率降低至0.5％；所述预烧的温度为1180℃，所述预烧的保温时间为7h；所述预烧的升温速率为1.8℃/min；
(3)将步骤(2)所得预烧后的球磨料敲碎，得到粉料，过30目筛，然后按照粉料、锆球与去离子水1:6:1.3的质量比混合，再次进行转速为40r/min、时间为8h的湿法球磨，所述大径锆球和小径锆球的质量比为5:2，所述大径锆球的直径为10mm，所述小径锆球的直径为4mm，所得球磨料的粒度范围为D50＝1.2μm，D90＝2.5μm；
(4)250℃烘干步骤(3)所得球磨料至含水率降低至8％，过40目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在300kg/cm 2的压力下过30目筛，得到造粒后的颗粒；所述粘结剂为5wt％的聚丙烯醇溶液；聚丙烯醇溶液的质量为步骤(3)烘干后球磨料质量的8％；
(5)步骤(4)所述造粒后的颗粒依次进行成型与烧结，得到所述双组份微波铁氧体材料；所述成型为：将步骤(4)所得造粒后的颗粒模具内压制成圆形生坯，所述圆形生坯的成型密度为3.8g/cm 3；所述烧结为：在1420℃下进行烧结，保温时间为11h，所述烧结的升温速率为0.8℃/min；在保温结束前6h开始通氧，烧结结束后温度降低至900℃时结束通氧。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例5
根据离子取代机理，本对比例提供了一种微波铁氧体材料，所述微波铁氧体材料为：Y 2.6Ca 0.4Fe 4.2Al 0.4Zr 0.4O 12。
该微波铁氧体材料的制备方法包括如下步骤：
(1)按照化学式计算并称取原材料；将称取的原材料将称取的原材料放入球磨罐中，按照原材料、锆球、去离子水与柠檬酸铵按照质量比1:7:1.3:0.09混合，进行转速为40r/min、时间为8h的湿法球磨，所述大径锆球和小径锆球的质量比为5:2，所述大径锆球的直径为10mm，所述小径锆球的直径为4mm，所得球磨料的粒度范围为D50＝1.2μm，D90＝2.5μm；
(2)步骤(1)所得球磨料依次进行烘干、过40目筛与预烧；烘干的温度为120℃，烘干的终点为使含水率降低至0.5％；所述预烧的温度为1250℃，所述预烧的保温时间为8h；所述预烧的升温速率为1℃/min；
(3)将步骤(2)所得预烧后的球磨料敲碎，得到粉料，过30目筛，然后按照粉料、锆球与去离子水1:6:1.4的质量比混合，再次进行转速为60r/min、时间为20h的湿法球磨，所述大径锆球和小径锆球的质量比为1:1，所述大径锆 球的直径为6mm，所述小径锆球的直径为2mm，所得球磨料的粒度范围为D50＝0.5μm，D90＝4μm；
(4)250℃烘干步骤(3)所得球磨料至含水率降低至8％，过40目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在350kg/cm 2的压力下过30目筛，得到造粒后的颗粒；所述粘结剂为5wt％的聚丙烯醇溶液；聚丙烯醇溶液的质量为步骤(3)烘干后球磨料质量的8％；
(5)步骤(4)所述造粒后的颗粒依次进行成型与烧结，得到所述双组份微波铁氧体材料；所述成型为：将步骤(4)所得造粒后的颗粒模具内压制成圆形生坯，所述圆形生坯的成型密度为3.8g/cm 3；所述烧结为：在1470℃下进行烧结，保温时间为12h，所述烧结的升温速率为4℃/min；在保温结束前6h开始通氧，烧结结束后温度降低至1000℃时结束通氧。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例6
根据离子取代机理，本对比例提供了一种微波铁氧体材料，所述微波铁氧体材料为：Y 2.3Ca 0.7Fe 4.1Sn 0.4Zr 0.3Mn 0.2Ti 0.05O 12。
该微波铁氧体材料的制备方法包括如下步骤：
(1)按照化学式计算并称取原材料；将称取的原材料将称取的原材料放入球磨罐中，按照原材料、锆球、去离子水与柠檬酸铵按照质量比1:7.5:2:0.1混合，进行转速为80r/min、时间为40h的湿法球磨，所述大径锆球和小径锆球的质量比为3.5:4，所述大径锆球的直径为7mm，所述小径锆球的直径为1mm，所得球磨料的粒度范围为D50＝0.3μm，D90＝2μm；
(2)步骤(1)所得球磨料依次进行烘干、过30目筛与预烧；烘干的温度为100℃，烘干的终点为使含水率降低至0.5％；所述预烧的温度为1320℃，所述预烧的保温时间为15h；所述预烧的升温速率为3.6℃/min；
(3)将步骤(2)所得预烧后的球磨料敲碎，得到粉料，过30目筛，然后按照粉料、锆球与去离子水1:5.5:1.2的质量比混合，再次进行转速为10r/min、时间为10h的湿法球磨，所述大径锆球和小径锆球的质量比为3.5:4，所述大径锆球的直径为5mm，所述小径锆球的直径为3mm，所得球磨料的粒度范围为D50＝1μm，D90＝3μm；
(4)250℃烘干步骤(3)所得球磨料至含水率降低至8％，过40目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在350kg/cm 2的压力下过30目筛，得到造粒后的颗粒；所述粘结剂为5wt％的聚丙烯醇溶液；聚 丙烯醇溶液的质量为步骤(3)烘干后球磨料质量的8％；
(5)步骤(4)所述造粒后的颗粒依次进行成型与烧结，得到所述双组份微波铁氧体材料；所述成型为：将步骤(4)所得造粒后的颗粒模具内压制成圆形生坯，所述圆形生坯的成型密度为3.8g/cm 3；所述烧结为：在1400℃下进行烧结，保温时间为5＝15h，所述烧结的升温速率为3.3℃/min；在保温结束前6h开始通氧，烧结结束后温度降低至1000℃时结束通氧。
获得的样品经磨加工后测量的磁性能如表1所示。
对比例7
本对比例提供了一种双组份微波铁氧体材料，所述双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
第一微波铁氧体材料为：Y 1.5Ca 1.2Fe 3.9V 0.6Zr 0.3In 0.3Mn 0.1O 12；
第二微波铁氧体材料为：Gd 1.5Ca 0.85Fe 3.2V 0.35Ge 0.3In 0.3Ti 0.1O 12。
本对比例提供的双组份微波铁氧体材料的制备方法与实施例1相同。
获得样品经磨加工后测量的磁性能如表1所示。
对比例8
本对比例提供了一种双组份微波铁氧体材料，所述双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料。
第一微波铁氧体材料为：Y 1.5Ca 1.2Fe 3.9Al 0.6Zr 0.3In 0.3Mn 0.1O 12；
第二微波铁氧体材料为：Gd 1.5Ca 0.85Fe 3.2Al 0.35Ge 0.3In 0.3Ti 0.1O 12。
本对比例提供的双组份微波铁氧体材料的制备方法与实施例1相同。
获得样品经磨加工后测量的磁性能如表1所示。
对比例9
本对比例提供了一种双组份微波铁氧体材料，所述双组份微波铁氧体材料包括第一微波铁氧体材料和第二微波铁氧体材料；
第一微波铁氧体材料为：Y (3-2a-c-d-e)Ca (2a+c+d+e)Fe (5-a-b-c-d-e)V aAl bZr cSn dMn eO 12，其中a＝0.35，b＝0.15，c＝0.2，d＝0.1，e＝0.04；
第二微波铁氧体材料为：Gd (3-2A-C-D)Ca (2A+C+D)Fe (5-A-B-C-D-E)V AAl BGe CIn DTi EO 12，其中，A＝0.35，B＝0.05，C＝0.1，D＝0.1，E＝0.05。
本对比例提供的双组份微波铁氧体材料的制备方法与实施例1相同。
获得样品经磨加工后测量的磁性能如表1所示。
实施例1-10以及对比例1-9所提供的微波铁氧体材料的磁性能参数表1。
表1
Figure PCTCN2021129668-appb-000003
由表1可知，本申请提供的高饱和低损耗双组份微波铁氧体材料具有高饱和磁矩、高居里温度、低线宽、低损耗的特点，分析对比例1-9可知，单组分的微波铁氧体材料具有较宽的铁磁共振线宽，较高的介电损耗以及较低的居里温度，因此，会极大地影响单组分微波铁氧体材料的稳定性和可靠性，进而影响微波通讯器件的使用。分析对比例7-9与实施例1可知，具有不同化学元素组成的双组份微波铁氧体材料，具有不同的磁性能，使得二者在微波通讯领域中的使用领域不同，实施例1提供的铁氧体材料具有较高的饱和磁矩，适用于环形器的高场工作，对比例7提供的铁氧体材料具有较低的饱和磁矩，适用于环形器的低场工作。
综上所述，本申请提供的高饱和低损耗双组份微波铁氧体材料具有高饱和磁矩、高居里温度、低线宽、低损耗的特点；饱和磁矩强度在1950Gs-1960Gs，介电损耗在2×10 -4-1.48×10 -4，居里温度可达260℃以上，线宽小于20Oe；此外，本申请的制备方法工艺稳定可重复性好，有利于工业化生产。
以上所述的具体实施例，对本申请的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本申请的具体实施例而已，并不用于限制本申请。

Claims (10)

  1. 一种高饱和低损耗双组份微波铁氧体材料，其中，所述高饱和低损耗双组份微波铁氧体材料的制备原料包括第一微波铁氧体材料与第二微波铁氧体材料；
    所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，0≤a≤0.7，0≤b≤0.7，0≤c≤0.7；并且
    所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，0≤A≤0.7，0≤B≤0.7，0≤C≤0.7。
  2. 根据权利要求1所述的高饱和低损耗双组份微波铁氧体材料，其中，所述第一微波铁氧体材料与第二微波铁氧体材料的质量比为(1-3):(1-3)。
  3. 一种如权利要求1或2所述双组份微波铁氧体材料的制备方法，其中，所述制备方法包括如下步骤：
    (1)按配方量混合第一微波铁氧体材料与第二微波铁氧体材料，然后进行湿法球磨，得到球磨料；
    (2)烘干步骤(1)所得球磨料，过筛后进行造粒；
    (3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料。
  4. 根据权利要求3所述的制备方法，其中，步骤(1)所述湿法球磨为将制备原料、研磨球与弥散剂按照质量比1:(4-7.5):(0.6-2.5)混合，进行湿法球磨；
    可选地，步骤(1)所述湿法球磨的转速为20-80r/min；
    可选地，步骤(1)所述湿法球磨的时间为10-40h；
    可选地，所述研磨球包括锆球和/或钢球；
    可选地，所述研磨球包括大径研磨球和小径研磨球；所述大径研磨球的直径为5-10mm；所述小径研磨球的直径为1-4mm；
    可选地，所述大径研磨球与小径研磨球的质量比为(0.8-3):1；
    可选地，所述弥散剂包括去离子水、酒精、丙酮、正丙酮或氨水中的任意一种或至少两种的组合；
    可选地，步骤(1)所述球磨料的粒径范围为D50＝0.05-2μm，D90＝0.05-4μm。
  5. 根据权利要求3或4所述的制备方法，其中，步骤(2)所述烘干的温度为100-150℃；
    可选地，步骤(2)所述烘干的终点为使含水率降低至0.01-10％；
    可选地，步骤(2)所述过筛所用筛网的目数为30-100目；
    可选地，步骤(2)所述造粒为将过筛后的球磨料与粘结剂均匀混合，在压 力下过筛，得到造粒后的颗粒；
    可选地，所述粘结剂包括聚乙烯醇水溶液；
    可选地，所述聚乙烯醇水溶液的浓度为5-20wt％；
    可选地，所述聚乙烯醇水溶液为过筛后的球磨料质量的5-10％；
    可选地，所述过筛的压力为300-1200kg/m 2。
  6. 根据权利要求3-5任一项所述的制备方法，其中，步骤(3)所述成型为：将步骤(2)造粒后的颗粒放入模具内，压制成指定形状的生坯；
    可选地，所述生坯的成型密度为3.0-4.0g/cm 3；
    可选地，步骤(3)所述烧结为：以1-5℃/min的升温速率升温至1200-1500℃，保温为5-30h；
    可选地，步骤(3)所述烧结时通氧的起始时间为保温结束前1-6h；
    可选地，步骤(3)所述烧结时结束通氧的时间为：保温结束后，温度降低100-500℃时，结束通氧。
  7. 根据权利要求3所述的制备方法，其中，步骤(1)所述第一微波铁氧体材料的制备方法包括如下步骤：
    (a)按配方量混合第一微波铁氧体的制备原料，湿法球磨后得到球磨料；
    (b)步骤(a)所得球磨料依次进行烘干、过筛与预烧，得到第一微波铁氧体材料；
    所述第一微波铁氧体材料为：Y 3-aCa aFe 5-a-b-cZr aIn bMn cO 12，其中，0≤a≤0.7，0≤b≤0.7，0≤c≤0.7；
    可选地，步骤(a)所述湿法球磨为将制备原料、研磨球、弥散剂与分散剂按照质量比1:(4-7.5):(0.6-2.5):(0.003-0.01)混合，进行湿法球磨；
    可选地，步骤(a)所述湿法球磨的转速为20-80r/min；
    可选地，步骤(a)所述湿法球磨的时间为10-40h；
    可选地，步骤(a)所述湿法球磨的研磨球包括锆球和/或钢球；
    可选地，步骤(a)所述湿法球磨的研磨球包括大径研磨球和小径研磨球；所述大径研磨球的直径为5-10mm；所述小径研磨球的直径为1-4mm；
    可选地，步骤(a)所述湿法球磨的研磨球中，大径研磨球与小径研磨球的质量比为(0.8-3):1；
    可选地，步骤(a)所述湿法球磨所用弥散剂包括去离子水、酒精、丙酮、正丙酮或氨水中的任意一种或至少两种的组合；
    可选地，步骤(a)所述湿法球磨所用分散剂包括柠檬酸铵和/或氨水；
    可选地，步骤(a)所述球磨料的粒径范围为D50＝0.05-2μm，D90＝0.05-4μm；
    可选地，步骤(b)所述烘干的温度为100-150℃；
    可选地，步骤(b)所述烘干的终点为使含水率降低至0.01-10％；
    可选地，步骤(b)所述过筛所用筛网的目数为30-100目；
    可选地，步骤(b)所述预烧的温度为1100-1400℃；
    可选地，步骤(b)所述预烧的保温时间为6-15h；
    可选地，步骤(b)所述预烧的升温速率为0.3-4℃/min。
  8. 根据权利要求3所述的制备方法，其中，步骤(1)所述第二微波铁氧体材料的制备方法包括如下步骤：
    (I)按配方量混合第二微波铁氧体的制备原料，湿法球磨后得到球磨料；
    (Ⅱ)步骤(I)所得球磨料依次进行烘干、过筛与预烧，得到第二微波铁氧体材料；
    所述第二微波铁氧体材料为：Gd 3-ACa AFe 5-A-B-CGe AIn BTi CO 12，其中，0≤A≤0.7，0≤B≤0.7，0≤C≤0.7；
    可选地，步骤(I)所述湿法球磨为将制备原料、研磨球、弥散剂与分散剂按照质量比1:(4-7.5):(0.6-2.5):(0.003-0.01)混合，进行湿法球磨；
    可选地，步骤(I)所述湿法球磨的研磨球包括锆球和/或钢球；
    可选地，步骤(I)所述湿法球磨的研磨球包括大径研磨球和小径研磨球；所述大径研磨球的直径为5-10mm，所述小径研磨球的直径为1-4mm；
    可选地，步骤(I)所述湿法球磨的研磨球中，大径研磨球与小径研磨球的质量比为(0.8-3):1；
    可选地，步骤(I)所述弥散剂包括去离子水、酒精、丙酮、正丙醇或氨水中的任意一种或至少两种的组合；
    可选地，步骤(I)所述分散剂包括柠檬酸铵和/或氨水；
    可选地，步骤(I)所述湿法球磨的转速为20-80r/min；
    可选地，步骤(I)所述湿法球磨的时间为10-40h；
    可选地，步骤(I)所述球磨料的粒度范围为D50＝0.005-2μm，D90＝0.05-4μm；
    可选地，步骤(II)所述烘干的温度为100-150℃；
    可选地，步骤(II)所述烘干的终点为使含水率降低至0.01-10％；
    可选地，步骤(II)所述过筛所用筛网的目数为30-100目；
    可选地，步骤(II)所述预烧的温度为1100-1400℃；
    可选地，步骤(II)所述预烧的保温时间为8-20h；
    可选地，步骤(II)所述预烧的升温速率为0.3-4℃/min。
  9. 根据权利要求3-8任一项所述的制备方法，其包括如下步骤：
    (1)按配方量混合第一微波铁氧体材料与第二微波铁氧体材料，然后进行湿法球磨，得到球磨料；所述湿法球磨为将制备原料、研磨球与弥散剂按照质量比1:(4-7.5):(0.6-2.5)混合，进行转速为20-80r/min、时间为10-40h的湿法球磨；所得球磨料的粒径范围为D50＝0.005-2μm，D90＝0.05-4μm；
    (2)100-250℃的条件下烘干步骤(1)所得球磨料至含水率降低至0.01-10％，过30-100目筛后进行造粒；所述造粒为将过筛后的球磨料与粘结剂均匀混合，在300-1200kg/cm 2压力下过30-100目筛，得到造粒后的颗粒；
    (3)步骤(2)所述造粒后的颗粒依次进行成型与烧结，得到所述高饱和低损耗双组份微波铁氧体材料；所述成型为：将步骤(2)所得造粒后的颗粒在模具内压制指定形状的生坯，所述生坯的成型密度为3.0-4.0g/cm 3；所述烧结的温度为1200-1500℃，所述烧结的保温时间为5-30h，所述烧结的升温速率为1-5℃/min，所述烧结时通氧的起始时间为保温结束前1-6h，保温结束后，温度降低100-500℃时，结束通氧；
    步骤(1)所述第一微波铁氧体材料的制备方法包括：
    (a)按配方量混合第一微波铁氧体材料的制备原料，湿法球磨后得到球磨料；湿法球磨的转速为20-80r/min，时间为10-40h；所得球磨料的粒度范围为D50＝0.005-2μm，D90＝0.05-4μm；
    (b)步骤(a)所得球磨料依次进行烘干、过30-100目筛与预烧，得到第一微波铁氧体材料；烘干的温度为100-250℃，烘干的终点为使含水率降低至0.01-10％；所述预烧的温度为1100-1350℃；所述预烧的保温时间为6-15h；所述预烧的升温速率为0.3-4℃/min；
    步骤(1)所述第二微波铁氧体材料的制备方法包括：
    (I)按配方量混合第二微波铁氧体材料的制备原料，湿法球磨后得到球磨料；湿法球磨的转速为20-80r/min，时间为10-40h；所得球磨料的粒度范围为D50＝0.005-2μm，D90＝0.05-4μm；
    (II)步骤(I)所得球磨料依次进行烘干、过筛与预烧，得到第二微波铁氧体材料；烘干的温度为100-250℃，烘干的终点为使含水率降低至0.01-10％；所述预烧的温度为1100-1400℃；所述预烧的保温时间为8-20h。
  10. 一种权利要求1或2所述的高饱和低损耗双组份微波铁氧体材料的应用，其中，所述高饱和低损耗双组份微波铁氧体材料用于微波通信器件。
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