CN114436635B - Microwave ferrite material with Gao Zixuan wave line width and preparation method thereof - Google Patents

Abstract

The invention discloses a microwave ferrite material with high spin wave linewidth, which belongs to the field of microwave ferrite materials, and the chemical formula of the microwave ferrite material comprises the following components: y is Y _3‑a‑b Ca _a Gd _b Fe _{5‑c‑d‑e‑f‑g‑δ} Zr _c Sn _d V _e In _f Hf _g O ₁₂ The invention also discloses a preparation method of the material, wherein a is more than or equal to 0 and less than or equal to 0.7,0, b is more than or equal to 0 and less than or equal to 0.7,0, c is more than or equal to 0.6,0, d is more than or equal to 0.7,0, e is more than or equal to 0.7,0, f is more than or equal to 0.7,0, g is more than or equal to 0.3, delta is iron deficiency, the material can effectively regulate and control the spin wave line width of the microwave ferrite material, the microwave ferrite material can meet different power capacities of small, medium and high, and the material can be widely applied to the fields of power type microwave devices, such as radar communication and the like.

Description

Microwave ferrite material with high spin wave linewidth and preparation method thereof

technical field

The invention relates to the field of microwave ferrite materials, in particular to a microwave ferrite material with high spin wave line width and a preparation method thereof.

Background technique

Microwave ferrite materials have many performance parameters, such as: saturation magnetization, ferromagnetic resonance linewidth, Curie temperature, spin wave linewidth, and temperature stability. According to different application environments of ferrite devices, different performance parameters are pursued. For example, in 4/5G communication, in order to pursue low loss and high bandwidth of devices, microwave ferrite mainly chooses low ferromagnetic resonance linewidth and high saturation magnetization. High-strength garnet material; in the application scenario of wide temperature range, not only the material is required to have a low ferromagnetic resonance linewidth but also a low temperature coefficient; in the application of spaceborne high power, the device needs microwave ferrite The material bears a relatively large power, which requires a large spin wave linewidth of the material. At present, in the garnet system, the main means to increase the spin wave linewidth of the material is doping with Dy ³⁺ , Tb ³⁺ , Ho ³⁺ plasma or refining the grain of the material, but the refinement of the grain increases the spin wave line width. Wide is rarely used in specific projects.

Contents of the invention

One of the objectives of the present invention is to provide a microwave ferrite material with high spin wave linewidth to solve the above problems.

In order to achieve the above object, the technical scheme adopted in the present invention is as follows: a kind of microwave ferrite material with high spin wave linewidth, its chemical formula is composed of:

Y _3-ab Ca _a Gd _b Fe _5-cdefg-δ Zr _c Sn _d V _e In _f Hf _g O ₁₂ , where 0≤a≤0.7, 0≤b≤0.7, 0≤c≤0.6, 0≤d≤ 0.7, 0≤e≤0.7, 0≤f≤0.7, 0<g≤0.3, δ is iron deficiency.

The above-mentioned ferrite material disclosed by the present invention can significantly increase the spin wave line width of the material by doping an appropriate amount of Hf ⁴⁺ at the Fe ³⁺ site, and can be widely used to improve the spin wave line width of microwave ferrite materials. In the wide formula design, the technical means to control the spin wave linewidth are enriched.

The invention adjusts the spin wave line width of the material by doping Hf ⁴⁺ , changes the traditional Dy ³⁺ , Tb ³⁺ , Ho ³⁺ plasma substitution, or increases the spin wave line width by refining the crystal grains.

The second object of the present invention is to provide a method for preparing the above-mentioned material, and the technical solution adopted is to include the following steps:

(1) Preparation of primary material: Weigh the raw material according to the content of the chemical formula, add a solvent for ball milling, the ball milling time is 4-12 hours, then filter, dry and sieve, carry out pre-calcination treatment at 1200-1280 ° C, after cooling, get a material;

(2) Preparation of secondary material: pulverize the primary material obtained in step (1), add solvent ball mill for 4 to 12 hours, filter and dry to obtain secondary material;

(3) Granulation: add a certain amount of cement to the prepared secondary material, and carry out granulation and sieving;

(4) Molding: the granulated fine powder is put into the mold for pressing, the pressing pressure is 50MPa～250MPa, and the material green body is obtained

(5) Sintering: put the green body into an air atmosphere or an oxidizing atmosphere furnace for sintering to obtain a sample.

As a preferred technical solution: the raw materials in step (a) are analytically pure, and their chemical formulas are Fe ₂ O ₃ , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ .

As a preferred technical solution: in step (1), the ball-to-material ratio is 4:0.6, and the ball milling time is 4h.

As a preferred technical solution: in step (1), the ball is zirconia, and the solvent is deionized water or alcohol.

As a preferred technical solution: in step (2), the ratio of material to solvent is 1:0.6, and the ball milling time is 4h.

When sieving in steps (1) and (3), the size of the sieve is 20 mesh to 60 mesh.

As a preferred technical solution: in step (3), the adhesive is an aqueous polyvinyl alcohol solution with a concentration of 5wt% to 12wt%.

As a preferred technical solution: in step (5), the sintering temperature is 1350° C. to 1450° C., and the temperature is kept for more than 6 hours.

Compared with the prior art, the present invention has the following obvious differences:

The doping elements are different: In the previous technology, the spin wave line width of garnet material was improved by doping Dy ³⁺ , Tb ³⁺ , Ho ³⁺ plasma, but the present invention discloses the doping at the Fe ³⁺ site for the first time. Hf ⁴⁺ can also significantly increase the spin wave linewidth of garnet gyromagnetic materials;

The position of doping is different: In the previous technology, the spin wave linewidth of the garnet material was improved by doping at the Y position, but the present invention is doped at the Fe site to increase the spin wave linewidth of the garnet material , which has never been reported in previous studies.

Compared with the prior art, the advantage of the present invention is that the technology of the present invention can effectively control the spin wave linewidth and the ferromagnetic resonance linewidth of the microwave ferrite material, and can make the microwave ferrite material satisfy small, medium, Highly different power capacity devices can be widely used in power microwave devices, especially for radar communication and other fields.

Detailed ways

The present invention will be further described below.

Example 1: Weigh Fe ₂ O 3 , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ according to the chemical formula Y 3 _{- ab} Ca _a Gd _b Fe _5-cdefg-δ Zr _{c Sn} d V _e In _f Hf _g O ₁₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , where a=0.3, b=0, c=0, d=0.2, e=0, f=0.1, g=0.05 , δ=0.05.

Example 2: Weigh Fe ₂ O 3 , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ according to the chemical _formula Y _3-ab Ca _a Gd _b Fe _5-cdefg-δ Zr _{c Sn} d V _e In _f Hf _g O ₁₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , where a=0.3, b=0, c=0, d=0.2, e=0, f=0.1, g=0.1 , δ=0.05.

Example 3: Weigh Fe ₂ O 3 , Gd 2 O ₃ , CaCO ₃ , ZrO ₂ according to _the chemical formula Y _3-ab Ca _a Gd _b Fe _{5 -cdefg-δ} Zr _{c Sn} d V _e In _f Hf _g O ₁₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , where a=0.3, b=0, c=0, d=0.2, e=0, f=0.1, g=0.15 , δ=0.05.

Example 4: Weigh Fe ₂ O 3 , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ according to the chemical formula Y 3 _{- ab} Ca _a Gd _b Fe _5-cdefg-δ Zr _{c Sn} d V _e In _f Hf _g O ₁₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , where a=0.3, b=0, c=0, d=0.2, e=0, f=0.1, g=0.2 , δ=0.05.

Example 5: Weigh Fe ₂ O 3 , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ according to the chemical formula Y _{3-ab Ca a} Gd _b Fe _5-cdefg-δ Zr _{c Sn} d V _e In _f Hf _g O ₁₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , where a=0.25, b=0.4, c=0.1, d=0.1, e=0.05, f=0, g=0.05 , δ=0.05.

Example 6: Weigh Fe ₂ O 3 , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ according to the chemical formula Y 3 _{- ab} Ca _a Gd _b Fe _5-cdefg-δ Zr _{c Sn d} V _e In _f Hf _g O ₁₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ , where a=0.25, b=0.4, c=0.1, d=0.1, e=0.05, f=0, g=0.1 , δ=0.05.

Preparation method: Weigh the raw materials according to Examples 1-6, and the raw materials are all analytically pure;

Preparation of the primary material: wet ball milling of the weighed raw materials, the ratio of ball: material: diluent is 4:1:1, (the ball is zirconia, the diluent is deionized water or alcohol), wet ball milling 4h, then filter, dry and sieve, pre-burn at 1260°C, and then cool naturally;

Preparation of secondary material: crush the prepared primary material, pour it into a ball mill tank, and perform secondary ball milling. The ratio of ball:material:diluent is 4:1:0.6, wet ball milling for 4 hours, and then filter and dry;

Granulation: Add the secondary material to a polyvinyl alcohol aqueous solution with a concentration of 9 wt%, and sieve after mixing thoroughly;

Forming: put the granulated particles into the mold for pressing, the pressing pressure is 100MPa, and obtain the material green body;

Sintering: put the green body into an air atmosphere furnace for sintering, the sintering temperature is 1400°C, after holding time for 8 hours, cool naturally;

Test: The sintered samples were tested for performance, including density, saturation magnetization, ferromagnetic resonance linewidth, and spin wave linewidth. The test results are shown in Table 1;

Table 1: The performance of the ferrite of embodiment 1-4

Analyze the above performance data:

Comparative Examples 1-4: With the increase of Hf element, the spin wave linewidth and ferromagnetic resonance linewidth increase significantly; Examples 1, 2, and 3 of the present invention all achieve better microwave performance, while taking into account the engineering Material ferromagnetic resonance linewidth and spin wave linewidth requirements.

Comparative Examples 5 and 6: The ferromagnetic resonance linewidth and the spin wave linewidth have the same variation trend as those of Examples 1-4.

Compared with the prior art, the present invention has the following obvious differences:

The doping elements are different: In the previous technology, the spin wave line width of garnet material was improved by doping Dy ³⁺ , Tb ³⁺ , Ho ³⁺ plasma, but the present invention discloses the doping at the Fe ³⁺ site for the first time. Hf ⁴⁺ can also significantly increase the spin wave linewidth of garnet gyromagnetic materials;

The position of doping is different: In the previous technology, the spin wave linewidth of the garnet material was improved by doping at the Y position, but the present invention is doped at the Fe site to increase the spin wave linewidth of the garnet material , which has never been reported in previous studies.

The technology of the present invention can effectively control the spin wave linewidth and ferromagnetic resonance linewidth of microwave ferrite materials, and can make microwave ferrite materials meet small, medium and high power capacity devices, and can be widely used in power type Among microwave devices, it is especially suitable for radar communication and other fields.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.

Claims (9)

1. A microwave ferrite material that regulates spin wave linewidth by doping Hf ⁴⁺ , is characterized in that: its chemical formula consists of: Y _3-ab Ca _a Gd _b Fe _5-cdefg-δ Zr _c Sn _d V _e In _f Hf _g O ₁₂ , where 0<a≤0.3, 0≤b≤0.4, 0≤c≤0.1, 0<d≤ 0.2, 0≤e≤0.05, 0<f≤0.1, 0<g≤0.3, δ is iron deficiency; or 0<a≤0.3, 0<b≤0.4, 0<c≤0.1, 0<d≤0.2 , 0<e≤0.05, 0≤f≤0.1, 0<g≤0.3, δ is iron deficiency. 2. the preparation method of the microwave ferrite material of claim 1 by doping Hf ⁴⁺ regulation and control spin wave linewidth, it is characterized in that, comprises the following steps: (1) Preparation of primary material: Weigh the raw materials according to the chemical formula composition, add solvent for ball milling, the ball milling time is 4-12 hours, then filter, dry and sieve, pre-calcine at 1200-1280 ℃, after cooling, obtain the primary material ; (2) Preparation of secondary material: crush the primary material obtained in step (1), add solvent and ball mill for 4-12 hours, filter and dry to obtain secondary material; (3) Granulation: add the prepared secondary material to the adhesive, and carry out granulation and sieving; (4) Molding: Put the granulated fine powder into the mold for pressing, the pressing pressure is 50MPa～250MPa, and the material green body is obtained; (5) Sintering: Put the green body into an air atmosphere or an oxidizing atmosphere furnace for sintering. 3. The method according to claim 2, characterized in that: the raw materials in step (a) are analytically pure, and their chemical formulas are Fe ₂ O ₃ , Gd ₂ O ₃ , CaCO ₃ , ZrO ₂ , SnO ₂ , V ₂ O ₅ , In ₂ O ₃ , HfO ₂ , Y ₂ O ₃ . 4. The method according to claim 2, characterized in that: in step (1), the ball-to-material ratio during ball milling is 4:0.6, and the ball milling time is 4 hours. 5. The method according to claim 2, characterized in that: in step (1), the balls in ball milling are zirconia, and the solvent is deionized water or alcohol. 6. The method according to claim 2, characterized in that: in step (2), the ratio of material to solvent is 1:0.6, and the ball milling time is 4 hours. 7. The method according to claim 2, characterized in that: when sieving in steps (1) and (3), the size of the sieve is 20 mesh to 60 mesh. 8. The method according to claim 2, characterized in that: in step (3), the adhesive is an aqueous polyvinyl alcohol solution with a concentration of 5wt%-12wt%. 9. The method according to claim 2, characterized in that in step (5), the sintering temperature is 1350° C. to 1450° C., and the temperature is kept for more than 6 hours.