CN112960977B - High-dielectric-constant microwave ferrite material and preparation method and application thereof - Google Patents

High-dielectric-constant microwave ferrite material and preparation method and application thereof Download PDF

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CN112960977B
CN112960977B CN202110239907.3A CN202110239907A CN112960977B CN 112960977 B CN112960977 B CN 112960977B CN 202110239907 A CN202110239907 A CN 202110239907A CN 112960977 B CN112960977 B CN 112960977B
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sintering
ball milling
ferrite
wet ball
sintering material
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CN112960977A (en
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王春明
张典鹏
王昆仑
谢国辉
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SUZHOU INDUSTRIAL PARK KAYMAX PRECISION ENGINEERING CO LTD
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Abstract

The invention provides a high dielectric constant microwave ferrite material and a preparation method and application thereof, wherein the high dielectric constant microwave ferrite material passes through Sn 4+ 、Al 3+ And Sm 3 The dielectric constant is improved by the synergistic addition, so that the saturation magnetization of the obtained material is between 1800-2000Gs, and the dielectric constant is more than 18; and the invention passes through Bi 3+ And Cu 2+ The synergistic addition of the components reduces the sintering temperature of the material, avoids the excessive growth of crystal grains caused by overhigh sintering temperature and overlong time, is beneficial to forming a ferrite material with good grain size distribution, ensures that the Curie temperature is over 180 ℃, and ensures that the resonance line width is not more than 28 Oe; the preparation method is simple to operate, improves the bonding strength of the material through grading, reduces the porosity in the ferrite material, and reduces the ferromagnetic resonance line width of the finally obtained garnet ferrite. The ferrite material provided by the invention can meet the requirements of miniaturization and light weight of a 5G base station circulator.

Description

High-dielectric-constant microwave ferrite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of magnetic materials, relates to a ferrite material and a preparation method and application thereof, and particularly relates to a high-dielectric-constant microwave ferrite material and a preparation method and application thereof.
Background
The circulator is an important part in a 5G base station, the ferrite material is a main component of the circulator, and the main raw material of the ferrite material is yttrium iron garnet ferrite. The ferrite material serves as the core of the circulator, and the performance of the ferrite material directly determines the performance of the circulator.
In recent years, with the rapid development of 5G communication technology, the demand for miniaturization and weight reduction of devices is more and more urgent, and the size and weight reduction of ferrite components is particularly important because the ferrite components are much larger than other components. While increasing the dielectric constant is an important means to reduce the size of the circulator.
The dielectric constant of the ferrite material commonly used in the microwave communication field is generally between 12 and 16, and the dielectric constant of the ferrite can be improved by adjusting the formula and doping certain elements, but the ferromagnetic resonance line width is increased and the Curie temperature is reduced, so that the ferrite loses the practical value. The technical difficulty is that the dielectric constant of ferrite is required to be improved, and other performances of the ferrite are required to be kept not to be deteriorated, so that the problem of the ferrite material is solved, and obstacles are eliminated for miniaturization and light weight of communication devices.
CN 109867518A discloses a garnet ferrite with high temperature stability, the structural formula of the garnet ferrite is Y 2.7-x Ca 0.3-z Gd x Al y Fe 4.68-y-z Zr 0.3 Mn 0.02 V z O 12 Wherein x is more than or equal to 0.2 and less than or equal to 0.8, y is more than or equal to 0.6 and less than or equal to 1.4, and z is more than or equal to 0.05 and less than or equal to 0.2. The high temperature stable garnet ferrite is prepared by simultaneously introducing Gd 3+ 、Al 3+ And V 5+ Substituted, and doped with Bi 2 O 3 The garnet ferrite material obtained by the additive has stable saturation magnetic induction intensity in the range of-55 ℃ to 85 ℃, has Curie temperature of 110-165 ℃ and has good temperature stability. However, the garnet ferrite of the high-temperature stable stone needs to be sintered for 4-6h at 1360-1420 ℃, the sintering temperature is high, and the sintering time is long.
CN 110981461A discloses an yttrium iron garnet ferrite material, mainly comprising the following chemical formula Y 3-x-y-z Gd x Ca y Cu z Fe 5-a-b-c In a V b Al c O 12 . The preparation method comprises the steps of mixing, pre-sintering, secondary ball milling, granulation molding and sintering which are sequentially carried out, the prepared ferrite material has fine and uniform crystal grains, is beneficial to obtaining a compact microstructure, improves the high-power bearing capacity of the material, and adopts Cu to prepare the ferrite material 2+ The material sintering temperature is properly reduced, namely sintering is realized under the condition of 1000-1100 ℃, but the dielectric constant of the obtained ferrite material does not exceed 14, and the requirements of miniaturization and light weight of the 5G circulator are difficult to meet.
CN 102976740A discloses a method for preparing narrow-linewidth high-dielectric-constant microwave ferrite, and the ferrite material uses Y with purity more than or equal to 99.9% 2 O 3 And analytically pure Fe 2 O 3 ，CaCO 3 ，Bi 2 O 3 ，V 2 O 5 ，GeO 2 ，In 2 O 3 ，SnO 2 ，TiO 2 ，Al(OH) 3 ，MnCO 3 Is prepared from raw materials, and finally sintered and molded. The narrow-linewidth high-dielectric-constant microwave ferrite is prepared by adding Ti into a formula 4+ And Bi 3+ In is used 3+ 、Sn 4+ 、Ti 4+ Plasma combined substitution of octahedral Fe 3+ And Bi in dodecahedral position 3+ Partially substituted Y 3+ The method effectively improves the dielectric constant of the material, and simultaneously Bi 3+ The introduction of the Fe-O-Fe catalyst can also strengthen the super exchange effect of Fe-O-Fe, and the effect of improving the Curie temperature is achieved. However, the dielectric constant of the narrow-linewidth high-dielectric-constant microwave ferrite still cannot exceed 15, and the requirements for miniaturization and light weight of the 5G circulator are difficult to meet.
Therefore, it is required to provide a new microwave ferrite material, which not only has a low sintering temperature, but also has a dielectric constant of not less than 20, a ferromagnetic resonance line width of not more than 32Oe, and a curie temperature of more than 180 ℃, so as to meet the requirements of miniaturization and light weight of a 5G circulator.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-dielectric-constant microwave ferrite material and a preparation method and application thereof, the high-dielectric-constant microwave ferrite material provided by the invention has the saturation magnetization of 1800-2000Gs, the dielectric constant of more than 18, the Curie temperature of more than 180 ℃, the resonance line width of no more than 28Oe, and can meet the requirements of miniaturization and light weight of a 5G base station circulator.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a high dielectric constant microwave ferrite material having a chemical formula of Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.4-0.6, b is 0.1-0.2, c is 0.2-0.4, d is 0.5-0.6, e is 0.1-0.2, f is 0.05-0.1, and g is 0.3-0.6.
The invention adjusts the microwave ferriteComposition of bulk material by Sn 4+ 、Al 3+ And Sm 3 The synergistic addition of (A) and (B) improves the dielectric constant, so that the saturation magnetization of the obtained material is between 1800-2000Gs, and the dielectric constant is more than 18. That is, the high dielectric constant microwave ferrite material provided by the present invention has a dielectric constant of 18 or more, which is referred to as "high dielectric constant" in the present application.
Moreover, the chemical composition of the high dielectric constant microwave ferrite material provided by the invention passes through Bi 3+ And Cu 2+ The synergistic addition of the components reduces the sintering temperature of the material, avoids the excessive growth of crystal grains caused by overhigh sintering temperature and overlong time, and is favorable for forming the ferrite material with good grain size distribution.
The high dielectric constant microwave ferrite material has the chemical formula of Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Where a is from 0.4 to 0.6, and may be, for example, 0.4, 0.42, 0.45, 0.48, 0.5, 0.54, 0.55, 0.56 or 0.6, but is not limited to the values recited, and other values not recited in the numerical ranges are equally applicable.
b is 0.1 to 0.2, and can be, for example, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.2, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
c is from 0.2 to 0.4, and can be, for example, 0.2, 0.21, 0.24, 0.25, 0.27, 0.28, 0.3, 0.32, 0.35, 0.36 or 0.4, but is not limited to the values listed, and other values not listed in the range of values are equally suitable.
d is 0.5 to 0.6, and can be, for example, 0.5, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59 or 0.6, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
e is 0.1 to 0.2, and can be, for example, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19 or 0.2, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
f is 0.05 to 0.1, and can be, for example, 0.05, 0.06, 0.07, 0.08, 0.09 or 0.1, but is not limited to the values listed, and other values not listed in the numerical range are equally suitable.
g is 0.3 to 0.6, and can be, for example, 0.3, 0.32, 0.35, 0.36, 0.4, 0.42, 0.45, 0.48, 0.5, 0.54, 0.55, 0.56 or 0.6, but is not limited to the values listed, and other values not listed in the numerical ranges are equally applicable.
Preferably, the sum of c, d and e is 0.9 to 1.1, and may be, for example, 0.9, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98, 0.99, 1.0, 1.02, 1.05, 1.06, 1.08 or 1.1, but is not limited to the values recited, and other values not recited within the numerical range are equally applicable.
Preferably, the sum of a and f is 0.48 to 0.66, and may be, for example, 0.48, 0.5, 0.54, 0.55, 0.58, 0.6, 0.62, 0.64 or 0.66, but is not limited to the values recited, and other values not recited within the numerical range are equally applicable.
In a second aspect, the present invention provides a method for preparing a high dielectric constant microwave ferrite material as described in the first aspect, said method comprising the steps of:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture;
(2) pre-sintering the mixture obtained in the step (1) under the auxiliary condition of an electric field to obtain a pre-sintered material;
(3) dividing the pre-sintering material obtained in the step (2) into at least 2 parts, and performing wet ball milling on the at least 2 parts of pre-sintering material respectively to obtain at least 2 parts of ball grinding materials with different average particle sizes;
(4) uniformly mixing a binder and at least 2 parts of the ball grinding material obtained in the step (3), and granulating to obtain ferrite powder;
(5) and (4) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering to obtain the high-dielectric-constant microwave ferrite material.
According to the invention, at least 2 parts of ball milling materials with different average particle sizes are mixed, so that the bonding strength of ferrite powder is improved, the porosity in the ferrite material is reduced, and the ferromagnetic resonance line width of the finally obtained ferrite is reduced; in addition, the electric field is added in the pre-sintering process, so that the time for pre-sintering is reduced, the tissues undergo transition growth, elements after pre-sintering are uniformly distributed, and the electromagnetic performance of the obtained high-dielectric-constant microwave ferrite material is favorably improved by matching with the components of the preparation raw materials.
Preferably, the preparation raw material of step (1) comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 。
Preferably, the raw materials are immersed in absolute ethyl alcohol during the wet ball milling in the step (1).
Preferably, the average particle size of the blend obtained in step (1) is 30 to 80 μm, and may be, for example, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm or 80 μm, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
Preferably, the electric field intensity assisted by the electric field in step (2) is 400-600V/cm, such as 400V/cm, 420V/cm, 450V/cm, 480V/cm, 500V/cm, 520V/cm, 540V/cm, 560V/cm or 600V/cm, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the temperature of the pre-sintering in step (2) is 600-.
Preferably, the pre-sintering time in step (2) is 1-2h, such as 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the pre-sintering material obtained in the step (2) is divided into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1 (1-2) to (1-2), and the mass ratio can be, for example, 1:1:1, 1:1:2, 1:2:1 or 1:2:2, but the invention is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the raw materials are immersed in absolute ethyl alcohol during the wet ball milling in the step (3).
Preferably, the first ball abrasives obtained by wet ball milling of the first pre-sintered material have an average particle size of 60 to 80 μm, for example, 60 μm, 62 μm, 64 μm, 65 μm, 66 μm, 68 μm, 70 μm, 72 μm, 75 μm, 78 μm or 80 μm, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the average particle size of the second ball milling material obtained by wet ball milling of the second pre-sintered material is 40 to 50 μm, for example, 40 μm, 41 μm, 42 μm, 43 μm, 44 μm, 45 μm, 46 μm, 47 μm, 48 μm, 49 μm or 50 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the average particle size of the third ball abrasive obtained by wet ball milling the third pre-sintered material is 30-40 μm, such as 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the average particle size of the ferrite powder obtained in step (4) is 100-200 μm, and may be, for example, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm or 200 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the binder of step (4) is added in an amount of 1-2wt% of the ferrite powder, for example, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, or 2wt%, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the binder of step (4) comprises an aqueous solution of polyvinyl alcohol and/or carboxymethyl cellulose.
Preferably, the compression molding in step (5) is performed by cold isostatic pressing at a pressure of 100-200MPa, such as 100MPa, 110MPa, 120MPa, 130MPa, 140MPa, 150MPa, 160MPa, 170MPa, 180MPa, 190MPa or 200MPa, but not limited to the values recited, and other values not recited in the numerical ranges are also applicable.
Preferably, the sintering temperature in step (5) is 1180-1250 ℃, and may be, for example, 1180 ℃, 1190 ℃, 1200 ℃, 1210 ℃, 1220 ℃, 1230 ℃, 1240 ℃ or 1250 ℃, but is not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the sintering time in step (5) is 4-6h, such as 4h, 4.5h, 5h, 5.5h or 6h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical solution of the preparation method according to the second aspect of the present invention, the preparation method comprises the steps of:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 30-80 mu m; the raw materials are immersed by absolute ethyl alcohol during wet ball milling;
(2) pre-sintering the mixture obtained in the step (1) under the electric field intensity of 400-600V/cm to obtain a pre-sintered material; the presintering temperature is 600-800 ℃, and the presintering time is 1-2 h;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1 (1-2) to 1-2; and performing wet ball milling on the three pre-sintered materials respectively, wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling, the average particle size of the obtained first ball grinding material is 60-80 mu m, the average particle size of the obtained second ball grinding material is 40-50 mu m, and the average particle size of the obtained third ball grinding material is 30-40 mu m;
(4) uniformly mixing the binder and the three ball grinding materials obtained in the step (3), and granulating to obtain ferrite powder with the average particle size of 100-; the addition amount of the binder is 1-2wt% of the ferrite powder;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1180-1250 ℃ for 4-6h to obtain the high-dielectric-constant microwave ferrite material; the compression molding is carried out by cold isostatic pressing, and the pressure is 100-200 MPa.
In a third aspect, the present invention provides a use of the high dielectric constant microwave ferrite material of the first aspect in a 5G base station circulator.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention adjusts the composition of microwave ferrite material through Sn 4+ 、Al 3+ And Sm 3 The dielectric constant is improved by the synergistic addition of the components, so that the saturation magnetization of the obtained material is between 1800-2000Gs, and the dielectric constant is more than 18; moreover, the chemical composition of the high-dielectric-constant microwave ferrite material provided by the invention passes Bi 3+ And Cu 2+ The synergistic addition of the components reduces the sintering temperature of the material, avoids the excessive growth of crystal grains caused by overhigh sintering temperature and overlong time, and is beneficial to forming a ferrite material with good grain size distribution;
(2) according to the invention, at least 2 parts of ball milling materials with different average particle sizes are mixed, so that the bonding strength of ferrite powder is improved, the porosity in the ferrite material is reduced, and the ferromagnetic resonance line width of the finally obtained ferrite is reduced; in addition, the electric field is added in the pre-sintering process, so that the time for pre-sintering is reduced, the tissues undergo transition growth, elements after pre-sintering are uniformly distributed, and the electromagnetic performance of the obtained high-dielectric-constant microwave ferrite material is favorably improved by matching with the components of the preparation raw materials;
(3) the ferrite material provided by the invention can meet the requirements of miniaturization and light weight of a 5G base station circulator, the saturation magnetization is between 1800 and 2000Gs, the dielectric constant is more than 18, the Curie temperature is more than 180 ℃, and the resonance line width is not more than 28 Oe.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.3, d is 0.55, e is 0.15, f is 0.07, g is 0.4;
the preparation method comprises the following steps:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 50 microns; the raw materials are immersed by absolute ethyl alcohol during wet ball milling; the preparation raw material comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 ；
(2) Pre-sintering the mixture obtained in the step (1) under the electric field intensity of 500V/cm to obtain a pre-sintered material; the presintering temperature is 700 ℃, and the presintering time is 1.5 h;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1:1: 1; carrying out wet ball milling on the three pre-sintered materials respectively, wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling, the average particle size of the obtained first ball grinding material is 70 micrometers, the average particle size of the obtained second ball grinding material is 45 micrometers, and the average particle size of the obtained third ball grinding material is 35 micrometers;
(4) uniformly mixing a binder and the three ball grinding materials obtained in the step (3), and granulating to obtain ferrite powder with the average particle size of 150 mu m; the addition amount of the binder is 1.5 wt% of the ferrite powder; the binder is polyvinyl alcohol;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1220 ℃ for 5h to obtain the high dielectric constant microwave ferrite material; the compression molding is carried out by cold isostatic pressing, and the pressure is 150 MPa.
Example 2
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.3, d is 0.55, e is 0.15, f is 0.07, g is 0.4;
the preparation method comprises the following steps:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 30 mu m; the raw materials are immersed by absolute ethyl alcohol during wet ball milling; the preparation raw material comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 ；
(2) Pre-sintering the mixture obtained in the step (1) under the electric field strength of 400V/cm to obtain a pre-sintered material; the presintering temperature is 800 ℃, and the presintering time is 1 h;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1:1: 1; carrying out wet ball milling on the three pre-sintered materials respectively, wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling, the average particle size of the obtained first ball grinding material is 80 microns, the average particle size of the obtained second ball grinding material is 50 microns, and the average particle size of the obtained third ball grinding material is 40 microns;
(4) uniformly mixing a binder and the three ball grinding materials obtained in the step (3), and granulating to obtain ferrite powder with the average particle size of 200 mu m; the addition amount of the binder is 2wt% of the ferrite powder; the binder is carboxymethyl cellulose;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1250 ℃ for 4h to obtain the high-dielectric-constant microwave ferrite material; the compression molding is carried out by cold isostatic pressing, and the pressure is 200 MPa.
Example 3
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.3, d is 0.55, e is 0.15, f is 0.07, g is 0.4;
the preparation method comprises the following steps:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 80 microns; the raw materials are immersed by absolute ethyl alcohol during wet ball milling; the preparation raw material comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 ；
(2) Pre-sintering the mixture obtained in the step (1) under the electric field intensity of 600V/cm to obtain a pre-sintered material; the presintering temperature is 600 ℃, and the presintering time is 2 hours;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1:1: 1; carrying out wet ball milling on the three pre-sintered materials respectively, wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling, the average particle size of the obtained first ball grinding material is 60 micrometers, the average particle size of the obtained second ball grinding material is 40 micrometers, and the average particle size of the obtained third ball grinding material is 30 micrometers;
(4) uniformly mixing a binder and the three ball grinding materials obtained in the step (3), and granulating to obtain ferrite powder with the average grain diameter of 100 mu m; the addition amount of the binder is 1 wt% of the ferrite powder; the binder is carboxymethyl cellulose;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1180 ℃ for 6 hours to obtain the high-dielectric-constant microwave ferrite material; the compression molding is carried out by cold isostatic pressing, and the pressure is 100 MPa.
Example 4
This example provides a method for preparing a high dielectric constant microwave ferrite material, which is the same as that of example 1 except that the mass ratio of the first pre-sintered material, the second pre-sintered material and the third pre-sintered material is 1:2: 1.
Example 5
This example provides a method for preparing a high dielectric constant microwave ferrite material, which is the same as that of example 1 except that the mass ratio of the first pre-sintered material, the second pre-sintered material and the third pre-sintered material is 1:1: 2.
Example 6
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.42, b is 0.12, c is 0.25, d is 0.52, e is 0.13, f is 0.06, g is 0.35;
the preparation method is the same as in example 1.
Example 7
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.58, b is 0.18, c is 0.35, d is 0.57, e is 0.18, f is 0.08, g is 0.5;
the preparation method is the same as in example 1.
Example 8
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.2, d is 0.5, e is 0.1, f is 0.07, g is 0.4;
the preparation method is the same as in example 1.
Example 9
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.4, d is 0.6, e is 0.2, f is 0.07, g is 0.4;
the preparation method is the same as in example 1.
Example 10
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.4, b is 0.1, c is 0.3, d is 0.55, e is 0.15, f is 0.05, g is 0.3;
the preparation method is the same as in example 1.
Example 11
The embodiment provides a preparation method of a high-dielectric-constant microwave ferrite material, wherein the chemical formula of the high-dielectric-constant microwave ferrite material is Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.6, b is 0.2, c is 0.3, d is 0.55, e is 0.15, f is 0.1, g is 0.6;
the preparation method is the same as in example 1.
Comparative example 1
The present comparative example provides a method of preparing a microwave ferrite material having a chemical formula of Y 3 Bi a Ca b Sn c Al d Sm e Fe 5 V g O 12 Wherein a is 0.57, b is 0.15, c is 0.3, d is 0.55, e is 0.15, g is 0.4;
the preparation method is the same as in example 1.
Comparative example 2
The comparative example provides a method for preparing a microwave ferrite material having a chemical formula of Y 3 Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein b is 0.22, c is 0.3, d is 0.55, f is 0.57, e is 0.15, g is 0.4;
the preparation method is the same as in example 1.
Comparative example 3
The present comparative example provides a method of preparing a microwave ferrite material having a chemical formula of Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.3, d is 0.55, e is 0.15, f is 0.07, g is 0.4;
the preparation method comprises the following steps:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 50 microns; the raw materials are immersed by absolute ethyl alcohol during wet ball milling; the preparation raw material comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 ；
(2) Pre-sintering the mixture obtained in the step (1) to obtain a pre-sintered material; the presintering temperature is 700 ℃, and the presintering time is 1.5 h;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1:1: 1; wet ball milling is respectively carried out on the three pre-sintered materials, anhydrous ethanol is used for immersing the raw materials during the wet ball milling, the average grain size of the obtained first ball grinding material is 70 mu m, the average grain size of the obtained second ball grinding material is 45 mu m, and the average grain size of the obtained third ball grinding material is 35 mu m;
(4) uniformly mixing a binder and the three ball grinding materials obtained in the step (3), and granulating to obtain ferrite powder with the average particle size of 150 mu m; the addition amount of the binder is 1.5 wt% of the ferrite powder; the binder is polyvinyl alcohol;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1220 ℃ for 5h to obtain the high dielectric constant microwave ferrite material; the compression molding is cold isostatic pressing, and the pressure is 150 MPa.
Comparative example 4
The comparative example provides a method for preparing a high dielectric constant microwave ferrite material having a chemical formula of Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.5, b is 0.15, c is 0.3, d is 0.55, e is 0.15, f is 0.07, g is 0.4;
the preparation method comprises the following steps:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 50 microns; the raw materials are immersed by absolute ethyl alcohol during wet ball milling; the preparation raw material comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 ；
(2) Pre-sintering the mixture obtained in the step (1) under the electric field intensity of 500V/cm to obtain a pre-sintered material; the presintering temperature is 700 ℃, and the presintering time is 1.5 h;
(3) performing wet ball milling on the pre-sintered material obtained in the step (2), wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling, and the average particle size of the obtained ball grinding material is 70 microns;
(4) uniformly mixing a binder and the ball grinding material obtained in the step (3), and granulating to obtain ferrite powder with the average particle size of 150 mu m; the addition amount of the binder is 1.5 wt% of the ferrite powder; the binder is polyvinyl alcohol;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1220 ℃ for 5h to obtain the high dielectric constant microwave ferrite material; the compression molding is carried out by cold isostatic pressing, and the pressure is 150 MPa.
Comparative example 5
The comparative example provides a preparation method of a high dielectric constant microwave ferrite material, and the method is the same as the comparative example 4 except that the average grain diameter of the ball grinding material obtained in the step (3) is 45 microns.
Comparative example 6
The comparative example provides a preparation method of a high dielectric constant microwave ferrite material, and the method is the same as the comparative example 4 except that the average grain diameter of the ball grinding material obtained in the step (3) is 35 mu m.
The garnet ferrite materials provided in examples 1 to 11 and comparative examples 1 to 6 were tested for curie temperature, saturation magnetization (25 ℃), dielectric constant, and ferromagnetic resonance line width. Curie temperature and saturation magnetization were measured using a vibrating sample magnetometer. The dielectric constant was measured according to IEC60556 standard at a frequency of 10.7GHz and a sample size of 1.6mm cylinder. The ferromagnetic resonance line width was measured according to GB/T9633-88, and the results are shown in Table 1.
TABLE 1
Saturation magnetization (Gs) Dielectric constant Curie temperature (. degree. C.) Resonance line width (Oe)
Example 1 1957 23.1 226 24
Example 2 1931 21.9 237 25
Example 3 1939 20.8 229 22
Example 4 1942 22.4 218 26
Example 5 1918 22.8 215 23
Example 6 1933 22.5 221 26
Example 7 1945 21.7 204 27
Example 8 1913 18.4 231 28
Example 9 1921 19.6 224 26
Example 10 1857 18.7 197 28
Example 11 1904 19.9 206 27
Comparative example 1 1674 13.8 156 35
Comparative example 2 1735 16.9 184 21
Comparative example 3 1896 20.1 213 31
Comparative example 4 1714 17.4 195 36
Comparative example 5 1756 18.1 204 32
Comparative example 6 1831 18.8 209 29
In summary, the present invention adjusts the composition of the microwave ferrite material by Sn 4+ 、Al 3+ And Sm 3 The dielectric constant is improved by the synergistic addition, so that the saturation magnetization of the obtained material is between 1800-2000Gs, and the dielectric constant is more than 18; furthermore, the present inventionThe chemical composition of the provided high dielectric constant microwave ferrite material is determined by Bi 3+ And Cu 2+ The synergistic addition of the components reduces the sintering temperature of the material, avoids the excessive growth of crystal grains caused by overhigh sintering temperature and overlong time, and is beneficial to forming a ferrite material with good grain size distribution; according to the invention, at least 2 parts of ball milling materials with different average particle sizes are mixed, so that the bonding strength of ferrite powder is improved, the porosity in the ferrite material is reduced, and the ferromagnetic resonance line width of the finally obtained ferrite is reduced; in addition, the electric field is added in the pre-sintering process, so that the time for pre-sintering is reduced, the tissues undergo transition growth, elements after pre-sintering are uniformly distributed, and the electromagnetic performance of the obtained high-dielectric-constant microwave ferrite material is favorably improved by matching with the components of the preparation raw materials; the ferrite material provided by the invention can meet the requirements of miniaturization and light weight of a 5G base station circulator, the saturation magnetization is between 1800 and 2000Gs, the dielectric constant is more than 18, the Curie temperature is more than 180 ℃, and the resonance line width is not more than 28 Oe.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (17)

1. The high-dielectric-constant microwave ferrite material is characterized in that the high-dielectric-constant microwave ferrite material has a chemical formula of Y 3 Bi a Ca b Sn c Al d Sm e Cu f Fe 5 V g O 12 Wherein a is 0.4-0.6, b is 0.1-0.2, c is 0.2-0.4, d is 0.5-0.6, e is 0.1-0.2, f is 0.05-0.1, and g is 0.3-0.6;
the sum of c, d and e is 0.9-1.1;
the sum of a and f is 0.48-0.66;
the high dielectric constant microwave ferrite material is prepared by the following preparation method, and the preparation method comprises the following steps:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture;
(2) pre-sintering the mixture obtained in the step (1) under the auxiliary condition of an electric field to obtain a pre-sintered material;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material, wherein the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is (1) (1-2) to (1-2); respectively carrying out wet ball milling on 3 parts of the pre-sintered material to obtain 3 parts of ball grinding materials with different average particle sizes; the average grain diameter of the first ball grinding material obtained by wet ball milling of the first pre-sintering material is 60-80 μm; the average grain diameter of the second ball grinding material obtained by wet ball milling of the second pre-sintering material is 40-50 mu m; the average grain diameter of a third ball grinding material obtained by wet ball milling of the third pre-sintering material is 30-40 mu m;
(4) uniformly mixing a binder and 3 parts of the ball grinding material obtained in the step (3), and granulating to obtain ferrite powder;
(5) and (4) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering to obtain the high-dielectric-constant microwave ferrite material.
2. A method of preparing a high dielectric constant microwave ferrite material as claimed in claim 1, wherein said method comprises the steps of:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture;
(2) pre-sintering the mixture obtained in the step (1) under the auxiliary condition of an electric field to obtain a pre-sintered material;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material, wherein the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is (1) (1-2) to (1-2); respectively carrying out wet ball milling on 3 parts of the pre-sintered material to obtain 3 parts of ball grinding materials with different average particle sizes; the average grain diameter of the first ball grinding material obtained by wet ball milling of the first pre-sintering material is 60-80 μm; the average particle size of the second ball grinding material obtained by wet ball milling of the second pre-sintering material is 40-50 mu m; the average grain diameter of a third ball grinding material obtained by wet ball milling of the third pre-sintering material is 30-40 mu m;
(4) uniformly mixing a binder and 3 parts of the ball grinding material obtained in the step (3), and granulating to obtain ferrite powder;
(5) and (4) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering to obtain the high-dielectric-constant microwave ferrite material.
3. The method according to claim 2, wherein the preparation raw material of step (1) comprises Y 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Al(OH) 3 、Sm 2 O 3 、CuO、Fe 2 O 3 And V 2 O 5 。
4. The preparation method of claim 2, wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling in the step (1).
5. The method according to claim 2, wherein the average particle size of the mixture obtained in step (1) is 30 to 80 μm.
6. The method as claimed in claim 2, wherein the electric field strength of the electric field in step (2) is 400-600V/cm.
7. The method as claimed in claim 2, wherein the temperature of the pre-sintering in step (2) is 600-800 ℃.
8. The method according to claim 2, wherein the pre-sintering time in step (2) is 1-2 h.
9. The preparation method of claim 2, wherein the raw materials are immersed in absolute ethyl alcohol during the wet ball milling in the step (3).
10. The method according to claim 2, wherein the average particle size of the ferrite powder obtained in step (4) is 100-200 μm.
11. The method according to claim 2, wherein the binder of step (4) is added in an amount of 1 to 2wt% based on the ferrite powder.
12. The method according to claim 2, wherein the binder of step (4) comprises an aqueous solution of polyvinyl alcohol and/or carboxymethyl cellulose.
13. The production method according to claim 2, wherein the compression molding in the step (5) is performed by cold isostatic pressing at a pressure of 100 and 200 MPa.
14. The method as claimed in claim 2, wherein the sintering temperature in step (5) is 1180-1250 ℃.
15. The method according to claim 2, wherein the sintering time in step (5) is 4 to 6 hours.
16. The method of claim 2, comprising the steps of:
(1) mixing the raw materials according to the formula amount, and performing wet ball milling to obtain a mixture with the average particle size of 30-80 mu m; the raw materials are immersed by absolute ethyl alcohol during wet ball milling;
(2) pre-sintering the mixture obtained in the step (1) under the electric field intensity of 400-600V/cm to obtain a pre-sintered material; the presintering temperature is 600-800 ℃, and the presintering time is 1-2 h;
(3) dividing the pre-sintering material obtained in the step (2) into 3 parts, namely a first pre-sintering material, a second pre-sintering material and a third pre-sintering material; the mass ratio of the first pre-sintering material to the second pre-sintering material to the third pre-sintering material is 1 (1-2) to 1-2; wet ball milling is respectively carried out on the three pre-sintered materials, anhydrous ethanol is used for immersing the raw materials during the wet ball milling, the average grain diameter of the obtained first ball grinding material is 60-80 mu m, the average grain diameter of the obtained second ball grinding material is 40-50 mu m, and the average grain diameter of the obtained third ball grinding material is 30-40 mu m;
(4) uniformly mixing the binder and the three ball grinding materials obtained in the step (3), and granulating to obtain ferrite powder with the average particle size of 100-; the addition amount of the binder is 1-2wt% of the ferrite powder;
(5) carrying out compression molding on the ferrite powder obtained in the step (4), and then sintering at 1180-1250 ℃ for 4-6h to obtain the high-dielectric-constant microwave ferrite material; the compression molding is cold isostatic pressing, and the pressure is 100-200 MPa.
17. Use of the high dielectric constant microwave ferrite material of claim 1 in a 5G base station circulator.
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