NiCuZn microwave ferrite material with high spin wave line width and preparation method

Abstract

The invention discloses a NiCuZn microwave ferrite material with high spin wave line width and a preparation method, relates to the technical field of electronic information materials and microwave electronics, and comprises a NiCuZn microwave ferrite material with high performance through a multi-ion synergistic effect method, and by adding In < 3 + > ions and Ga < 3 + > ions capable of reducing ferromagnetic resonance line width, the high-performance NiCuZn microwave ferrite material with high spin wave line width can be obtained. The NiCuZn microwave ferrite material with the high spin wave line width is obtained by adding a high-speed relaxation ion Ho < 3 + > to replace Zn < 2 + > ions on the A site of spinel, adding a rapid relaxation ion Ho < 3 + > to replace Ni < 2 + > ions on the B site of spinel, and then replacing trivalent Fe < 3 + > ions with Mn < 2 + > ions to regulate and control element and electricity price balance in the ferrite and obtain the NiCuZn microwave ferrite material with the high spin wave line width. The material can meet the power bearing capacity of a microwave device under high power, and the device performance is excellent.

Description

Technical Field

[0001] This invention relates to the fields of electronic information materials and microwave electronics, specifically to a NiCuZn microwave ferrite material with high spin linewidth and its preparation method. Background Technology

[0002] Spin-wave ferrite materials are ferrite materials exhibiting gyromagnetic effects. Their core characteristic is the ability to rotate the polarization plane of electromagnetic waves under a high-frequency magnetic field. They are widely used in high-frequency microwave electronic devices, primarily based on the propagation and manipulation capabilities of spin waves. Their important applications are mainly reflected in three aspects: First, in microwave devices, spin-wave ferrite devices are used to manufacture microwave circulators and isolators, utilizing their non-reciprocal phase shift to achieve unidirectional transmission of electromagnetic waves, protecting oscillators and other devices in microwave communication systems from transmission interference. Second, in the field of information processing, spin-wave ferrites can be used to construct magnetostatic delay lines, filters, and signal-to-noise ratio (SNR) enhancers, enabling precise control of signal delay time in delay lines, controllable narrowband frequency selection in filters, and limiting effects in SNR enhancers. Third, spin-wave ferrites are used in ultrafast logic devices in high-frequency spintronics, achieving functions such as coherent spin-wave modulation based on the material's spin-wave properties.

[0003] However, existing NiCuZn microwave ferrite materials with high spin linewidths face the following problems in their use: Currently commercially available microwave ferrite materials (such as YIG, NiZn, and LiZn-based materials) have different advantages, but they all generally face a key technical issue: to improve the capacity of microwave devices to withstand high peak power, the spin linewidth ΔHk of the ferrite material should be higher. However, when reducing the ferromagnetic resonance linewidth and increasing the dielectric constant of the material, the spin linewidth tends to be low, thus limiting the application of microwave ferrite devices under high peak power conditions. According to magnetic physics theory, the spin linewidth of ferrites is mainly affected by the degree of grain refinement, the rapid relaxation characteristics of ions, and the porosity of the material. Summary of the Invention

[0004] The purpose of this invention is to provide a NiCuZn microwave ferrite material with high spin linewidth and its preparation method, so as to solve the related problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a NiCuZn microwave ferrite material with high spin wave linewidth, wherein the high spin wave microwave ferrite material is based on spinel ferrite, and its chemical formula is: Ni0.43-xHoxCu0.11Zn0.46-y-zGayInzFe2-xy-zMnx+y+zO4, x=0.01-0.08, y=0.01-0.10, z=0.01-0.10, where x, y, and z are molar stoichiometric ratios.

[0006] Furthermore, the NiCuZn microwave ferrite material with high spin linewidth exhibits a spinel structure and is synthesized from raw materials NiO, Ho2O3, CuO, ZnO, Ga2O3, In2O3, Fe2O3 and MnO via a solid-state sintering method at a high temperature of 1050ºC~1250ºC.

[0007] Furthermore, the saturation magnetization 4πMs of the NiCuZn microwave ferrite material with high spin wave linewidth described herein is 3900 Gs~4500 Gs, the ferromagnetic resonance linewidth ΔH is 60 Oe~90 Oe, the spin wave linewidth ΔHk is 15-28 Oe, the microwave dielectric constant ε is 15-18, and the microwave dielectric loss tangent tan δε is 3~8×10-3.

[0008] Furthermore, the fabrication process of high-permeability, low-ferromagnetic-resonance-linewidth microwave ferrite materials includes the following steps: Step 1: Using NiO, Ho2O3, CuO, ZnO, Ga2O3, In2O3, Fe2O3, and MnO as reactants, weigh the reactants according to the stoichiometric ratio of Ni0.43-xHoxCu0.11Zn0.46-y-zGayInzFe2-xy-zMnx+y+zO4, where x=0.01-0.08, y=0.01-0.10, and z=0.01-0.10, to obtain a raw material mixture system. Step 2: Place the raw material mixture weighed in Step 1 into a planetary ball mill for wet ball milling, using zirconia balls and deionized water as the grinding media, and perform one ball milling. The ball milling time is 12-24 hours and the speed is 200-280 rpm. After completion, the raw material mixture slurry from the first ball milling is obtained. Step 3: Place the raw material mixture slurry obtained in Step 2 into a forced-air drying oven and dry it at a temperature of 60 ºC-100 ºC. After drying, grind the mixture and pass it through a 40-mesh sieve to obtain the first dry mixed powder. Step 4: The first mixed powder obtained in step 3 is pre-sintered in a high-temperature muffle furnace at 850 ºC ~ 1000 ºC for 3 to 8 hours to allow the first mixed powder to undergo a pre-sintering reaction and obtain pre-sintered powder. Step 5: Perform a second ball milling on the pre-calcined powder obtained in Step 4, using zirconia balls and deionized water as the grinding medium. The ball milling time is 12-18 hours and the rotation speed is 200-280 rpm. After completion, the mixed slurry from the second ball milling is obtained. Step 6: Dry the secondary ball-milled slurry obtained in Step 5 in an oven at 60 ºC-100 ºC and then crush it. Add 8wt%~15wt% PVA (polyvinyl alcohol) binder to granulate, and then pass it through an 80-mesh sieve to obtain uniformly mixed granules. Step 7: Dry the mixed particles obtained in Step 6 in a forced-air drying oven at 60 ºC-100 ºC for 3-5 minutes, and then press them into round green sheets under the vertical pressure of a hydraulic press. Step 8: Place the green embryo obtained in step 7 into a high-temperature muffle furnace and sinter it at 1050ºC~1250ºC for 4~8 hours to obtain NiCuZn microwave ferrite material with high spin linewidth.

[0009] Furthermore, in steps 2 and 5, the diameter of the zirconia spheres is 2-5 mm.

[0010] Furthermore, in step 4, during the pre-sintering process, the heating rate of the muffle furnace is controlled at 2~5°C / min.

[0011] Furthermore, in step 4, during the pre-sintering process, the heating and cooling rates of the muffle furnace are both controlled at 2~5°C / minute.

[0012] Furthermore, in step 6, the weight concentration of the granulating agent PVA solution is 10%; a nylon sieve is used for sieving.

[0013] Furthermore, in step 7, the hydraulic press pressure is controlled at 8~20 MPa, and the pressure holding time is set to 30~60 seconds.

[0014] Furthermore, in step 7, the thickness of the disc is between 1 mm and 2.5 mm.

[0015] Furthermore, in step 8, during the final sintering process, the heating rate of the muffle furnace is controlled at 2~5°C / minute. The specific sintering curve is as follows: first, the furnace temperature is raised to 450°C~600°C. After reaching this temperature, it is maintained for 2~5 hours for debinding. After debinding is completed, the temperature is raised to the required sintering temperature according to the set heating rate.

[0016] The beneficial effects of the NiCuZn microwave ferrite material with high spin linewidth and its preparation method of the present invention are as follows: This invention aims to improve the performance of microwave devices and further develop high-spin-wave ferrite materials that meet the application requirements of microwave devices. It achieves the synergistic goal of low ferromagnetic resonance linewidth and high spin-wave linewidth. Addressing the issue of low high-spin-wave linewidth in spinel microwave ferrites, this invention proposes a multi-ion synergistic method to achieve high-performance NiCuZn microwave ferrite materials. This is achieved by adding In3+ and Ga3+ ions, which reduce ferromagnetic resonance linewidth, to replace Zn2+ ions at the A-site of the spinel. Simultaneously, Ho3+ ions, which rapidly relax, replace Ni2+ ions at the B-site of the spinel. Then, Mn2+ ions replace trivalent Fe3+ ions, thus regulating the elemental and valence balance in the ferrite and obtaining a high-spin-wave-linewidth NiCuZn microwave ferrite material. This microwave ferrite material can achieve the goals of high power carrying capacity and excellent device performance in high-power microwave devices, meeting the basic material requirements of core components in microwave communication and high-frequency electronic circuit systems. It provides a practical and effective solution for promoting the development of electronic devices towards high power, integrated systems, and multi-information transmission.

[0017] This invention is successful. Attached Figure Description

[0018] Figure 1 This is the XRD pattern of the sample from Example 1 of the present invention.

[0019] Figure 2 This is the XRD pattern of the sample from Example 2 of the present invention.

[0020] Figure 3 This is the XRD pattern of the sample in Example 3 of the present invention.

[0021] Figure 4 This is a SEM image of Embodiment 1 of the present invention.

[0022] Figure 5 This is a SEM image of Embodiment 2 of the present invention.

[0023] Figure 6 This is a SEM image of Embodiment 3 of the present invention.

[0024] Table 1 shows the test data of ferromagnetic resonance linewidth, spin linewidth, dielectric constant, and dielectric loss of the NiCuZn microwave ferrite materials with high spin linewidth prepared in Examples 1-3 of this invention. Detailed Implementation

[0025] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0026] Example 1, as Figure 1 As shown, this invention provides a technical solution: a NiCuZn microwave ferrite material with high spin linewidth and its preparation method, wherein the microwave ferrite material is based on spinel ferrite, and its chemical formula is: Ni0.43-xHoxCu0.11Zn0.46-y-zGayInzFe2-xy-zMnx+y+zO4, x=0.01-0.08, y=0.01-0.10, z=0.01-0.10, where x, y, and z are molar stoichiometric ratios, and the mixture is prepared using the following steps: Step 1: Select x=0.01, y=0.01, z=0.01, and calculate the mass of the reactants according to the chemical formula Ni0.42Ho0.01Cu0.11Zn0.44Ga0.01In0.01Fe1.97Mn0.03O4. Weigh out 3.14g of NiO, 0.19g of Ho2O3, 0.88g of CuO, 3.58g of ZnO, 0.09g of Ga2O3, 0.14g of In2O3, 15.73g of Fe2O3, and 0.21g of MnO to obtain the raw material mixture system. Step 2: Place the raw material mixture weighed in Step 1 into a planetary ball mill for wet ball milling. Use 30 2mm zirconia balls and 12 5mm zirconia balls as grinding media for one ball milling. The ball milling time is 16 hours and the rotation speed is 220 rpm. After completion, the raw material mixture slurry from the first ball milling is obtained. Step 3: Place the raw material mixture slurry obtained in Step 2 into a forced-air drying oven and dry it at a temperature of 80 ºC. After drying, grind the mixture and pass it through a 40-mesh sieve to obtain the first dry mixed powder. Step 4: Place the first mixed powder obtained in step 3 in a muffle furnace, heat it at a rate of 2ºC / min, and pre-sinter it at 950ºC for 5 hours to allow the first mixed powder to undergo a pre-sintering reaction and obtain pre-sintered powder. Step 5: The pre-calcined powder obtained in Step 4 is subjected to a second ball milling using 30 2mm zirconia balls and 12 5mm zirconia balls, and deionized water as the grinding medium. The ball milling time is 12 hours and the rotation speed is 220 rpm. After completion, the mixed slurry of the second ball milling is obtained. Step 6: Dry the secondary ball-milled slurry obtained in Step 5 in an oven at 80 °C and then crush it. Add 12 wt% PVA (polyvinyl alcohol) binder to granulate, and then pass it through an 80-mesh sieve to obtain uniformly mixed granules. Step 7: Dry the mixed particles obtained in Step 6 in an 80ºC forced-air drying oven for 3 minutes, and then press them into round green discs under a vertical pressure of 10MPa using a hydraulic press. Step 8: Place the green embryo obtained in Step 7 into a high-temperature muffle furnace, heat at a rate of 2ºC / min, hold at 450ºC for 3 hours to remove the binder, then heat to 1100ºC for 6 hours and sinter, and allow to cool naturally to obtain a NiCuZn microwave ferrite material with high spin linewidth.

[0027] Example 2 The difference between this embodiment and Embodiment 1 is that the process in step 1 is as follows: Using x=0.08, y=0.10, and z=0.10, the mass of the reactants was calculated according to the chemical formula Ni0.38Ho0.05Cu0.11Zn0.36Ga0.05In0.05Fe1.85Mn0.15O4. 2.84g of NiO, 0.94g of Ho2O3, 0.88g of CuO, 2.93g of ZnO, 0.47g of Ga2O3, 0.69g of In2O3, 14.77g of Fe2O3, and 1.06g of MnO were weighed to obtain the raw material mixture system. The remaining steps were the same as in Example 1.

[0028] Example 3 The difference between this embodiment and Embodiment 1 is that the process in step 1 is as follows: With x=0.08, y=0.10, and z=0.10 selected, the mass of the reactants was calculated according to the chemical formula Ni0.35Ho0.08Cu0.11Zn0.26Ga0.10In0.10Fe1.72Mn0.28O4. 2.61g of NiO, 1.51g of Ho2O3, 0.88g of CuO, 2.11g of ZnO, 0.94g of Ga2O3, 1.39g of In2O3, 13.73g of Fe2O3, and 1.99g of MnO were weighed to obtain the raw material mixture system. The remaining steps were the same as in Example 1.

[0029] The high spin linewidth NiCuZn microwave ferrite materials prepared in Examples 1 to 3 above were subjected to XRD tests and SEM morphology characterization, as shown below. Figure 1 and Figure 2 As shown, the ferromagnetic resonance linewidth, spin wave linewidth, dielectric constant, and dielectric loss of the material were tested simultaneously.

[0030] As shown in Table 1 below: Depend on Figure 1 , Figure 2 and Figure 3 It can be seen that the NiCuZn microwave ferrite materials doped with multiple ions all formed a standard spinel phase, indicating that the prepared NiCuZn microwave ferrite materials with high spin linewidth have no impurity phases and belong to spinel ferrites. Depend on Figure 4 , Figure 5 and Figure 6 It can be seen that in the microstructure of the NiCuZn microwave ferrite material doped with multiple ions, the sample grains are uniform and exhibit a cubic grain morphology, and the sample has good compactness. As shown in Table 1, the ferromagnetic resonance linewidth, spin wave linewidth, dielectric constant, and dielectric loss of the NiCuZn microwave ferrite material doped with multiple ions are as follows: As shown in Table 1, the NiCuZn microwave ferrite material doped with multiple ions has a high saturation magnetization and a low ferromagnetic resonance linewidth, maintaining the excellent characteristics of high dielectric constant and low dielectric loss of ferrite, while also having a high spin wavelinewidth.

[0031] In summary, this invention provides a NiCuZn microwave ferrite material with high spin linewidth and its preparation method. By adding In3+ and Ga3+ ions, which can reduce the ferromagnetic resonance linewidth, to replace Zn2+ ions at the A-site of the spinel, and simultaneously adding fast relaxation ions Ho3+ ions to replace Ni2+ ions at the B-site of the spinel, and then replacing trivalent Fe3+ ions with Mn2+ ions, the elemental and valence balance in the ferrite is controlled, thus obtaining a NiCuZn microwave ferrite material with high spin linewidth. This microwave ferrite material can achieve the goals of high power carrying capacity and excellent device performance in microwave devices under high power conditions, meeting the basic material requirements of core components in microwave communication and high-frequency electronic circuit systems, and providing a practical and effective solution for promoting the development of electronic devices towards high power, integrated systems, and multi-information transmission.

[0032] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, and is not intended to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions made by those skilled in the art to the technical solution of the present invention do not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A NiCuZn microwave ferrite material with high spin linewidth, comprising a ferrite material formulated with Ni0.43-xHoxCu0.11Zn0.46-y-zGayInzFe2-xy-zMnx+y+zO4, characterized in that: The microwave ferrite material is based on spinel ferrite, and its chemical formula is Ni0.43-xHoxCu0.11Zn0.46-y-zGayInzFe2-xy-zMnx+y+zO4, where x=0.01-0.08, y=0.01-0.10, z=0.01-0.10, and x, y, and z are molar stoichiometric ratios.

2. The NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: The crystal structure exhibits a spinel structure. It is prepared by solid-state sintering of raw materials NiO, Ho2O3, CuO, ZnO, Ga2O3, In2O3, Fe2O3 and MnO at a high temperature of 1050ºC~1250ºC.

3. The NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: The device exhibits excellent microwave gyromagnetic properties: saturation magnetization 4πMs is 3900 Gs~4500 Gs, ferromagnetic resonance linewidth ΔH is 60 Oe~90 Oe, spin wave linewidth ΔHk is 15-28 Oe, microwave dielectric constant ε is 15-18, and microwave dielectric loss tangent tan δε is 3~8×10-3.

4. The method for preparing a NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: The solid-state sintering method includes the following steps: Step 1: Using NiO, Ho2O3, CuO, ZnO, Ga2O3, In2O3, Fe2O3, and MnO as reactants, weigh the reactants according to the stoichiometric ratio of Ni0.43-xHoxCu0.11Zn0.46-y-zGayInzFe2-xy-zMnx+y+zO4, where x=0.01-0.08, y=0.01-0.10, and z=0.01-0.10, to obtain a raw material mixture system. Step 2: Place the raw material mixture weighed in Step 1 into a planetary ball mill for wet ball milling, using zirconia balls and deionized water as the grinding media, and perform one ball milling. The ball milling time is 12-24 hours and the speed is 200-280 rpm. After completion, the raw material mixture slurry from the first ball milling is obtained. Step 3: Place the raw material mixture slurry obtained in Step 2 into a forced-air drying oven and dry it at a temperature of 60 ºC-100 ºC. After drying, grind the mixture and pass it through a 40-mesh sieve to obtain the first dry mixed powder. Step 4: The first mixed powder obtained in step 3 is pre-sintered in a high-temperature muffle furnace at 850 ºC ~ 1000 ºC for 3 to 8 hours to allow the first mixed powder to undergo a pre-sintering reaction and obtain pre-sintered powder. Step 5: Perform a second ball milling on the pre-calcined powder obtained in Step 4, using zirconia balls and deionized water as the grinding medium. The ball milling time is 12-18 hours and the rotation speed is 200-280 rpm. After completion, the mixed slurry from the second ball milling is obtained. Step 6: After drying the secondary ball milling mixture obtained in Step 5 in an oven at 60 ºC-100 ºC, crush it, add 8wt%~15wt% PVA (polyvinyl alcohol) binder to granulate, and pass it through an 80-mesh sieve to obtain uniformly mixed granules. Step 7: Dry the mixed particles obtained in Step 6 in a forced-air drying oven at 60 ºC-100 ºC for 3-5 minutes, and then press them into round green sheets under the vertical pressure of a hydraulic press. Step 8: Place the green embryo obtained in step 7 into a high-temperature muffle furnace and sinter it at 1050ºC~1250ºC for 4~8 hours to obtain NiCuZn microwave ferrite material with high spin linewidth.

5. A NiCuZn microwave ferrite material with high spin linewidth according to claim 4, characterized in that: In steps 2 and 5, the diameter of the zirconia spheres is 2-5 mm.

6. The NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: In step 4, during the pre-sintering process, the heating rate of the muffle furnace is controlled at 2~5°C / min.

7. The NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: In step 6, the weight concentration of the granulating agent PVA solution is 10%; a nylon sieve is used for sieving.

8. The NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: In step 7, the hydraulic press pressure is controlled at 8~20 MPa, and the pressure holding time is set to 30~60 seconds.

9. A NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: In step 7, the thickness of the disc is between 1 mm and 2.5 mm.

10. A NiCuZn microwave ferrite material with high spin linewidth according to claim 1, characterized in that: In step 8, during the final sintering process, the heating rate of the muffle furnace is controlled at 2~5°C / minute. The specific sintering curve is as follows: First, the furnace temperature is raised to 450°C~600°C. After reaching this temperature, it is maintained for 2~5 hours for debinding. After debinding is completed, the temperature is raised to the required sintering temperature according to the set heating rate.

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