CN114436637B - High-dielectric constant high-power microwave ferrite material and preparation method thereof - Google Patents
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Abstract
The invention discloses a high-dielectric constant high-power microwave ferrite material, which belongs to the technical field of microwave and magnetic materials, and has the chemical formula of Y 3‑x‑y‑a‑b‑c‑d‑e‑ f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5‑δ‑e‑f O 12 Wherein x is more than or equal to 0.8 and less than or equal to 1.6,0, y+z is more than or equal to 0.2, a is more than or equal to 0 and less than or equal to 0.7,0, b+c is more than or equal to 0.06,0.005, d is more than or equal to 0.05,0.25, e+f is more than or equal to 0.55, delta is iron deficiency, and delta is more than or equal to 0.03 and less than or equal to 0.1. The invention has high dielectric constant (both refer to relative dielectric constant epsilon) r ) The high-power garnet type microwave ferrite material has high dielectric constant and high power characteristics and excellent electromagnetic performance; relative dielectric constant epsilon-optical-fiber r > 20, dielectric loss tan delta ε ＜2×10 ‑4 Spin wave linewidth Δh k More than 5 Oe, the ferromagnetic resonance line width delta H is less than or equal to 40 Oe,4 pi Ms is more than or equal to 1700G, and the Curie temperature Tc is more than 270 ℃; the high-dielectric constant high-power garnet type microwave ferrite material can effectively reduce the design size of a high-power microwave circulator isolator device and meet the miniaturization requirement.
Description
Technical Field
The invention relates to the technical field of microwaves and magnetic materials, in particular to a high-dielectric constant high-power microwave ferrite material and a preparation method thereof.
Background
The high-power material mainly solves the problem that the high-power nonlinear effect of the common material causes the low power bearing capacity of the device under high power. The research purpose of the high dielectric constant microwave ferrite material is to reduce the design size of devices such as circulators, isolators and the like so as to meet the requirement of miniaturization and integration; if the dielectric constant of the microwave ferrite is increased to more than 20, the size of the related device can be reduced by 20% or more, and if the material applied to the high-power microwave device can be made to have the high dielectric constant performance required by the small-size design, the material is very beneficial to the miniaturization of the power microwave device.
Along with the development of related technologies, the requirements on ferrite materials widely applied to microwave devices such as circulators, isolators and the like are higher and higher, and further, the development of ferrite materials suitable for devices with excellent performance becomes one of important technical directions in the field.
The peak power capacity of the device is mainly determined by the high power critical field h of the material c The higher critical field can effectively avoid the situation that the loss is increased due to the high-power nonlinear effect of the material caused by the working environment of the device. High power critical field and spin wave linewidth ΔH of material k Closely related, h c ∝ΔH k (ω/ω m ) While DeltaH k Is a sign of high-power performance of the material, and the peak power P is more than h c 2 ∝ΔH k 2 Therefore, ΔH is increased k Is a precondition for increasing peak power. Spin wave linewidth ΔH k The product performance is difficult to meet the requirement of the device on low magnetic loss while meeting the high power capacity of the device. Doping of fast relaxing ions in the dodecahedral sites of garnet type ferrite is used to boost Δh k However, the Δh increases sharply, and substitution of octahedral sites to suppress deterioration of Δh causes a significant decrease in curie temperature, which affects the temperature characteristics of the material.
In addition, the dielectric constant epsilon of the current high-power garnet material also exists r The problem of lower dielectric constant is generally raised by Bi at the dodecahedron position 3+ Element substitution Y 3+ But a large amount of Bi 3+ A significant increase in dielectric constant also causes an increase in Δh, which deteriorates insertion loss.
There are only single garnet ferrite materials with high dielectric constant and high power characteristicsA report of a high-power performance microwave ferrite or a single high-dielectric constant performance ferrite, such as that disclosed in Chinese patent CN106220158A, has a spin-wave linewidth ΔH of 13 Oe k However, the Δh of 130 Oe makes it impractical; sm disclosed in CN 105347782B 3+ The dielectric constant of the doped yttrium-gadolinium high-power microwave ferrite material is only 14 as the conventional value of garnet ferrite material, and the doped yttrium-gadolinium high-power microwave ferrite material still has a slightly higher delta H of 40-70 Oe, the Curie temperature Tc is 200-240 ℃, and the delta H is k But are not mentioned; the garnet ferrite with high dielectric constant described in CN112456998A, CN 106242547A and the like has dielectric constant of more than 20, but has the defects of lower saturation magnetization 4 pi Ms, slightly higher ferromagnetic resonance line width delta H, curie temperature of only about 200 ℃ or failure in controlling dielectric loss and the like; the high dielectric garnet material described in CN 111285673A has a curie temperature of 200 ℃ or higher, a saturation magnetization of 1800G or higher, and a ferroresonance line width of 40 to 50 Oe, but the dielectric loss is not described, and the high-power characteristics are not provided.
Thus, if ΔH and ΔH can be coordinated while compounding high dielectric constant and high power characteristics k The development of a high-power microwave ferrite material with high dielectric constant is beneficial to the miniaturization and integration of a high-power microwave circulator isolator by controlling the deterioration of good dielectric property and magnetic property.
Disclosure of Invention
One of the objectives of the present invention is to provide a microwave ferrite material with low loss, high curie temperature, high dielectric constant and high power, so as to solve the above problems.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a high-dielectric constant high-power microwave ferrite material has the chemical formula of Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x is more than or equal to 0.8 and less than or equal to 1.6,0, y+z is more than or equal to 0.2, a is more than or equal to 0 and less than or equal to 0.7, b+c is more than or equal to 0 and less than or equal to 0.06,0.005, d is more than or equal to 0.05,e+f is more than or equal to 0.25 and less than or equal to 0.55, delta is the iron deficiency, and delta is more than or equal to 0.03 and less than or equal to 0.1
The dielectric constant of the common garnet type high-power microwave ferrite is low, usually around 14, and the control is due to delta H k The curie temperature is lowered by the sharp increase of Δh caused by the rise and the octahedral position substitution with large radius ions, and the increase of Δh and the deterioration of dielectric loss are easily caused by the dodecahedron substitution with Bi element which is commonly used. The invention provides a garnet microwave ferrite material with low loss, high Curie temperature and high dielectric constant and high power, which aims to solve the problems of ferrite performance deterioration and the like caused by two performances. The invention uses rare earth ion Gd 3+ 、Dy 3+ 、Sm 3+ 、Nd 3+ Combined substitution, lifting of Δh of material k Meanwhile, the temperature stability of the material is ensured; proper amount of Bi 3+ Instead of raising the dielectric constant of the material, and lowering the material sintering temperature; by a certain amount of rare earth ions La 3+ 、Lu 3+ The combined substitution of (2) can improve the Curie temperature of the material, offset the Curie temperature which is reduced due to the substitution of the large-radius nonmagnetic ions at the octahedral position and improve the temperature characteristic of the material; zr (Zr) 4+ 、Sn 4+ Ion substitution reduces the anisotropy constant of the material, thereby reducing magnetic loss; the appropriate iron deficiency suppresses deterioration of dielectric loss of the material.
The invention adopts the method that the dodecahedron Y in the garnet structure 3+ And octahedral Fe 3+ The substitution and doping are combined with the two characteristics of high power performance and high dielectric constant, so that the material has high dielectric constant epsilon r And Gao Zixuan wave linewidth ΔH k The design size of the device can be reduced, which is beneficial to the miniaturization and the light weight of the microwave ferrite high-power device, and meanwhile, the ferrite has high Curie temperature T c And low dielectric loss tan delta ε The lower ferroresonance linewidth delta H is beneficial to the performance stability of the power device.
The second purpose of the invention is to provide a preparation method of the material, which adopts the technical scheme that the preparation method comprises the following steps:
(1) According to the chemical formula: Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 wherein x is more than or equal to 0.8 and less than or equal to 1.6,0, y+z is more than or equal to 0.2, a is more than or equal to 0 and less than or equal to 0.7,0, b+c is more than or equal to 0.06,0.005, d is more than or equal to 0.05,0.25, e is more than or equal to 0.55, delta is iron deficiency, delta is more than or equal to 0.03 and less than or equal to 0.1, each raw material is calculated and weighed, and the raw material is Y 2 O 3 、Gd 2 O 3 、Dy 2 O 3 、Sm 2 O 3 、Nd 2 O 3 、La 2 O 3 、Lu 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、ZrO 2 、Fe 2 O 3 ；
(2) Performing first wet ball milling on the raw materials, and performing first mixed wet ball milling on the raw materials obtained in the step (1);
(3) Presintering, namely drying the slurry obtained in the step (2), presintering powder, wherein the presintering temperature is 900-1000 ℃, and preserving heat for 4-6 h;
(4) Performing secondary wet ball milling, namely performing secondary wet ball milling on the pre-sintered powder obtained in the step (3) to obtain slurry of the pre-sintered material;
(5) Granulating, namely drying the slurry obtained in the step (4), and then adding adhesive to uniformly mix for granulating;
(6) Molding, namely performing compression molding on the powder particles obtained after the granulation in the step (5) to obtain a green body;
(7) Sintering, namely sintering the green body obtained in the step (6) at 1050-1100 ℃ for more than 20 hours.
As a preferred embodiment, the purity of the raw material in step (1) is analytically pure.
As a preferable technical scheme, the ball milling time in the step (2) is 4-6 hours.
As a preferable technical scheme, the adhesive in the step (5) is a polyvinyl alcohol (PVA) aqueous solution, and the concentration of the adhesive is 5-15 wt%.
Compared with the prior art, the invention has the advantages that: the invention adopts the combination substitution of a plurality of rare earth ions to achieve the characteristic of high power, and the obtained garnet type microwave ferrite material with high dielectric constant and high power has the characteristics of high dielectric constant and high power, excellent electromagnetic performance, higher saturation magnetization 4 pi Ms and low dielectric loss tan delta ε A smaller ferroresonance linewidth DeltaH, a wider range of high dielectric constant epsilon and spin wave linewidth DeltaH k The method comprises the steps of carrying out a first treatment on the surface of the Dielectric constant epsilon r > 20, dielectric loss tan delta ε ＜2×10 -4 Spin wave linewidth Δh k More than 5 Oe, the ferromagnetic resonance line width delta H is less than or equal to 40 Oe,4 pi Ms is more than or equal to 1700G, and the Curie temperature Tc is more than 270 ℃; the high-dielectric constant high-power garnet type microwave ferrite material has stable process route and process parameters, can effectively reduce the design size of a high-power microwave circulator isolator device, and meets the miniaturization requirement.
Drawings
FIG. 1 is a phase analysis XRD pattern for the ferrite material of example 1;
FIG. 2 is a phase analysis XRD plot of the ferrite material of example 2;
FIG. 3 is a plot of XRD results for phase analysis of the ferrite material of example 3;
fig. 4 is a phase analysis XRD result pattern of the ferrite material of example 4.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1
A low-loss high-Curie temperature high-dielectric constant high-power microwave ferrite material has a chemical formula of Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Where x=0.8, y=0.1, z=0, a, b, c=0, d=0.005, e=0.3, f=0, δ=0.1;
the preparation method comprises the following steps:
according to chemical formula Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x=0.8, y=0.1, z=0, a, b, c=0, d=0.005, e=0.3, f=0, δ=0.1, each raw material is calculated and weighed, and the raw material is Y 2 O 3 、La 2 O 3 、Dy 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Carrying out first mixing wet ball milling on the weighed raw materials, drying the slurry, then carrying out powder presintering, wherein the presintering temperature is 1000 ℃, and the heat preservation is 5 h; carrying out secondary wet ball milling on the presintered powder, drying the slurry, adding adhesive, uniformly mixing and granulating; then carrying out compression molding; and sintering the formed green body at 1080 ℃ and preserving heat by more than 20 and h to obtain the high-dielectric constant high-power microwave ferrite material.
The prepared material was subjected to phase analysis using an X-ray diffraction analyzer (Panalytical X' Pert Powder, netherlands) and the results are shown in FIG. 1.
Example 2
A low-loss high-Curie temperature high-dielectric constant high-power microwave ferrite material has a chemical formula of Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Where x=1.0, y=0.05, z=0.05, a=0, b=0.005, c=0.005, d=0.03, e=0.30.3, f=0.1, δ=0.1;
the preparation method comprises the following steps:
according to chemical formula Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x=1.0, y=0.5, z=0.5, a=0, b=0.005, c=0.005, d=0.03, e=0.3, f=0.1, δ=0.1, each raw material is calculated and weighed, and the raw material is Y 2 O 3 、Dy 2 O 3 、La 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、ZrO 2 、Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Carrying out first mixing wet ball milling on the weighed raw materials, drying the slurry, then carrying out powder presintering, wherein the presintering temperature is 950 ℃, and the heat preservation is 5 h; carrying out secondary wet ball milling on the presintered powder, drying the slurry, adding adhesive, uniformly mixing and granulating; then carrying out compression molding; and sintering the formed green body at 1070 ℃ and preserving heat by more than 20 and h to obtain the high-dielectric constant high-power microwave ferrite material.
The prepared material was subjected to phase analysis using an X-ray diffraction analyzer (Panalytical X' Pert Powder, netherlands) and the results are shown in FIG. 2.
Example 3
A low-loss high-Curie temperature high-dielectric constant high-power microwave ferrite material has a chemical formula of Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Where x=1.3, y=0.1, z=0.05, a=0.3, b=0.02, c=0.02, d=0, e=0.1, f=0.35, δ=0.1;
the preparation method comprises the following steps:
according to chemical formula Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x=1.3, y=0.1, z=0.05, a=0.3, b=0.02, c=0.02, d=0, e=0.1, f=0.35, δ=0.1, each raw material is calculated and weighed, and the raw material is Y 2 O 3 、Lu 2 O 3 、Bi 2 O 3 、Sm 2 O 3 、Nd2O 3 、CaCO 3 、SnO 2 、ZrO 2 、Fe 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Ball milling the weighed raw materials by a first mixing wet method, drying the slurry, pre-sintering powder, keeping the pre-sintering temperature at 920 ℃, and preserving the temperature for 5h, performing H; carrying out secondary wet ball milling on the presintered powder, drying the slurry, adding adhesive, uniformly mixing and granulating; then carrying out compression molding; and sintering the formed green body at 1050 ℃, and preserving heat by more than 20 and h to obtain the high-dielectric constant high-power microwave ferrite material.
The prepared material was subjected to phase analysis using an X-ray diffraction analyzer (Panalytical X' Pert Powder, netherlands) and the results are shown in FIG. 3.
Example 4
A low-loss high-Curie temperature high-dielectric constant high-power microwave ferrite material has a chemical formula of Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Where x=1.6, y=0.15, z=0.05, a=0.6, b=0.03, c=0.03, d=0, e=0.1, f=0.45, δ=0.1;
the preparation method comprises the following steps:
according to chemical formula Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x=1.6, y=0.15, z=0.05, a=0.5, b=0.03, c=0.03, d=0, e=0.1, f=0.45, δ=0.1, each raw material is calculated and weighed, and the raw material is Y 2 O 3 、Lu 2 O 3 、Gd 2 O 3 、Bi 2 O 3 、Nd2O 3 、CaCO 3 、SnO 2 、ZrO 2 、Fe 2 O 3 . Carrying out first mixing wet ball milling on the weighed raw materials, drying the slurry, then carrying out powder presintering, wherein the presintering temperature is 900 ℃, and the heat preservation is 5 h; carrying out secondary wet ball milling on the presintered powder, drying the slurry, adding adhesive, uniformly mixing and granulating; then carrying out compression molding; and sintering the formed green body at 1040 ℃ and preserving heat by more than 20 and h to obtain the high-dielectric constant high-power microwave ferrite material.
The prepared material was subjected to phase analysis using an X-ray diffraction analyzer (Panalytical X' Pert Powder, netherlands) and the results are shown in FIG. 4.
For clarity of comparison of the single factors, the following comparative examples are based on example 1, with each comparative example having only one factor removed for comparison, and the performance parameters in the subsequent tables changed accordingly.
Comparative example 1
The comparative example differs from example 1 in that the chemical formula is:
Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 ferrite was prepared according to the process procedure of example 1, with the modification of the burn-in temperature to 1200 ℃, the sintering temperature and the holding time to 1400 ℃ and 20 hours or more, with x=0, y=0.1, z=0, a, b, c=0, d=0.005, e=0.3, f=0, δ=0.1. Comparison factor description: comparative example 1 Bi was eliminated based on example 1 3+ Substitution, retention of non-magnetic rare earth ions La 3+ Trace substitution and retention of fast relaxation rare earth ion Dy 3+ For the purpose of comparison of Bi 3+ The effect on the dielectric constant is improved, and the effect on other parameters is not obvious, and other substituted ions have almost no influence on the dielectric constant.
Sintering temperature change description: sintering temperature of garnet type ferrite formula with high dielectric constant and oxide Bi 2 O 3 The content of (2) is closely related, bi 2 O 3 The sintering temperature can be greatly reduced, so that the sintering quality level of the ferrite prepared in the comparative example 1 is close to ensure that performance test comparison can be performed, the sintering temperature needs to be adjusted, and the sintering time is unified by more than 20 hours.
Comparative example 2 (comparative likewise based on example 1)
The comparative example differs from example 1 in that the chemical formula is:
Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 wherein x=0.8, y=0.1, z=0, a=0, b=0, c=0, d=0, e=0.3, f=0, δ=0.1, ferrite preparation was performed according to the procedure of example 1.
Description: comparative example 2 eliminates the fast-relaxing rare earth ion Dy compared with example 1 3+ Is substituted by (1) to retain Bi 3+ Substituted and non-magnetic rare earth ions La 3+ The purpose is to comparatively illustrate the spin wave linewidth Δh of the fast-relaxation rare earth ions k To improve the effect of (1) and simultaneously explain Bi 3+ For spin wave linewidth DeltaH k There is no obvious effect, and the fast relaxation rare earth ions do not have obvious contribution to the dielectric constant.
Comparative example 3 (comparative based on example 1 as well)
The comparative example differs from example 1 in that the chemical formula is:
Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 wherein x=0.8, y=0, z=0, a=0, b=0, c=0, d=0.005, e=0.3, f=0, δ=0.1, ferrite was prepared according to the process flow of example 3, the burn-in temperature was changed to 1200 ℃, and the sintering temperature and holding time were 1400 ℃ and 20 hours or more.
Description: comparative example 3 formulation formula eliminates the nonmagnetic rare earth ion La compared to example 1 3+ Is substituted by (A) to retain the fast relaxation ion and rare earth Gd 3+ Bi and Bi 3+ Instead, the purpose is to comparatively illustrate the effect of non-magnetic rare earth ions in the material of the invention on increasing the Curie temperature, and simultaneously illustrate that the non-magnetic rare earth ions have no obvious contribution to the dielectric constant and spin wave linewidth. Also here due to the absence of Bi 2 O 3 It is also necessary to raise the sintering temperature to ensure similar sintering levels for comparison.
The ferrites prepared in examples 1-4 and comparative examples 1-3 described above were subjected to relevant electromagnetic performance tests using the following methods:
saturation magnetization of ferrite material 4 pi Ms, spin wave linewidth delta H k Curie temperature Tc, ferroresonance linewidth Δh, dielectric loss tan δ ε Dielectric constant epsilon r The test was conducted according to GB/T9633-2012, and the test results are shown in Table 1.
Carrying out phase analysis on the prepared material by using an X-ray diffraction analyzer (Panalytical X' Pert Powder, netherlands), wherein the XRD pattern of the analysis result is shown in the attached figures 1-4;
with respect to the drawings, it should be explained that: examples 1-4 are ferrites with high dielectric constant and high power performance, so the figures only show figures 1-4, because the ferrites of the examples are all completely solid solution substituted, and no XRD characteristic peaks except garnet phase exist in theory and test results, the test XRD peak patterns of all examples are similar, and the substituted ions are not present in other oxide impurity phases in the ferrites obtained in the examples;
the high power characteristic is represented by spin wave linewidth DeltaH in the present invention k Performance is embodied, and the line width delta H of the conventional pomegranate Dan Zixuan wave is k Typically very small, < 2 Oe, the ferrite ΔH of the present embodiment k The conventional garnet ferrite material has only one characteristic of high dielectric or high power, combines two characteristics of high power and high dielectric constant, and has good higher Curie temperature Tc to ensure that the environment application temperature of the material is higher and more stable.
Table 1 electromagnetic performance test results for examples and comparative examples
| Numbering device | ε | tanδ | ΔH（Oe） | ΔH k （Oe） | 4πM s （G） | T c （℃） |
| Example 1 | 21.3 | 7.4×10 -5 | 21 | 5.3 | 1955 | 284 |
| Example 2 | 23.5 | 9.2×10 -5 | 40 | 21 | 1950 | 279 |
| Example 3 | 26 | 1.0×10 -4 | 26 | 11.2 | 1824 | 282 |
| Example 4 | 30.2 | 1.2×10 -4 | 32 | 15 | 1706 | 271 |
| Comparative example 1 | 14 | 1.6×10 -4 | 20 | 5.1 | 1950 | 280 |
| Comparative example 2 | 22.1 | 1.0×10 -4 | 21 | ＜2 | 1983 | 274 |
| Comparative example 3 | 21.8 | 1.4×10 -4 | 24 | 5.3 | 1965 | 261 |
The contrast factors are three: bi (Bi) 3+ Ions; magnetic rare earth ion Gd 3+ 、Sm 3+ 、Nd 3+ 、Dy 3+ Wherein Sm is 3+ 、Nd 3+ 、Dy 3 + Is a fast relaxing rare earth ion; non-magnetic rare earth ion La 3+ 、Lu 3+ . The three kinds of ions respectively correspond to the ferrite performanceDielectric constant epsilon r Spin wave linewidth ΔH k Regulating and controlling Curie temperature Tc.
Comparative example 1 formulation formula Bi was eliminated based on example 1 3+ Substitution, compared with example 1, due to the absence of Bi 2 O 3 The sintering temperature is reduced, so that the ceramic sintering quality can be better at the high temperature of 1400 ℃; comparative example 1 shows that there is no Bi 3+ Dielectric constant epsilon of ferrite material after substitution r Reduced, the spin-wave linewidth and curie temperature are still excellent without having high dielectric constant properties.
Comparative example 2 formula the fast-relaxing rare earth ion Dy was cancelled on the basis of example 1 3+ Instead, compared with example 1, the ferrite material obtained in comparative example 2 has a spin wave linewidth ΔH k Lower, not having high power performance, but still having a high dielectric constant and a higher curie temperature.
Comparative example 3 formulation formula non-magnetic rare earth ions La were eliminated based on example 1 3+ Instead, the ferrite obtained in comparative example 3 has a reduced curie temperature compared with example 1, but still has high power performance characteristics and high dielectric constant performance.
The foregoing embodiments further describe the technical solutions and advantageous effects of the present invention in detail, but it should not be construed that the specific implementation of the present invention is limited to these descriptions. Any modifications, equivalent substitutions, improvements, or the like, which are within the skill of the art to which the present invention pertains, are deemed to be within the scope of the present invention without departing from the concept.
Claims (5)
1. A high-dielectric constant high-power microwave ferrite material is characterized by having a chemical formula of Y 3-x-y-a-b-c-d-e- f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x is more than or equal to 0.8 and less than or equal to 1.6,0.15, y+z is more than or equal to 0.2,0.3 and less than or equal to a is more than or equal to 0.7, b+c is more than or equal to 0.04 and less than or equal to 0.06,0.005, d is more than or equal to 0.05,0.25 and e+f is more than or equal to 0.55, y and z,b. c is not zero, delta is iron deficiency, delta is more than or equal to 0.03 and less than or equal to 0.1.
2. The method for preparing the high-dielectric constant high-power microwave ferrite material as claimed in claim 1, which is characterized in that: the method comprises the following steps:
(1) According to the chemical formula Y 3-x-y-a-b-c-d-e-f Bi x La y Lu z Gd a Nd b Sm c Dy d Ca e+f Sn e Zr f Fe 5-δ-e-f O 12 Wherein x is more than or equal to 0.8 and less than or equal to 1.6,0, y+z is more than or equal to 0.2, a is more than or equal to 0 and less than or equal to 0.7,0, b+c is more than or equal to 0.06,0.005, d is more than or equal to 0.05,0.25, e is more than or equal to 0.55, delta is iron deficiency, delta is more than or equal to 0.03 and less than or equal to 0.1, each raw material is calculated and weighed, and the raw material is Y 2 O 3 、Gd 2 O 3 、Dy 2 O 3 、Sm 2 O 3 、Nd 2 O 3 、La 2 O 3 、Lu 2 O 3 、Bi 2 O 3 、CaCO 3 、SnO 2 、ZrO 2 、Fe 2 O 3 ；
(2) Performing first wet ball milling on the raw materials, and performing first mixed wet ball milling on the raw materials obtained in the step (1);
(3) Presintering, namely drying the slurry obtained in the step (2), presintering powder, wherein the presintering temperature is 900-1000 ℃, and preserving heat for 4-6 h;
(4) Performing secondary wet ball milling, namely performing secondary wet ball milling on the pre-sintered powder obtained in the step (3) to obtain slurry of the pre-sintered material;
(5) Granulating, namely drying the slurry obtained in the step (4), and then adding adhesive to uniformly mix for granulating;
(6) Molding, namely performing compression molding on the powder particles obtained after the granulation in the step (5) to obtain a green body;
(7) Sintering, namely sintering the green body obtained in the step (6) at 1050-1100 ℃ for more than 20 hours.
3. The method of claim 2, wherein the purity of the starting material in step (1) is analytically pure.
4. The method according to claim 2, wherein the ball milling time in step (2) is 4 to 6 hours.
5. The method of claim 2, wherein the binder in step (5) is an aqueous solution of polyvinyl alcohol (PVA) at a concentration of 5wt% to 15wt%.
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