CN115947595B - Microwave ferrite material and preparation method and application thereof - Google Patents
Microwave ferrite material and preparation method and application thereof Download PDFInfo
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- CN115947595B CN115947595B CN202211666205.4A CN202211666205A CN115947595B CN 115947595 B CN115947595 B CN 115947595B CN 202211666205 A CN202211666205 A CN 202211666205A CN 115947595 B CN115947595 B CN 115947595B
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000002223 garnet Substances 0.000 claims abstract description 20
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims description 42
- 238000005469 granulation Methods 0.000 claims description 40
- 230000003179 granulation Effects 0.000 claims description 40
- 239000004576 sand Substances 0.000 claims description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000003292 glue Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 6
- 230000001070 adhesive effect Effects 0.000 claims 6
- 239000002131 composite material Substances 0.000 claims 1
- 229910052747 lanthanoid Inorganic materials 0.000 abstract description 8
- 150000002602 lanthanoids Chemical class 0.000 abstract description 8
- 230000005415 magnetization Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
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- 229910052797 bismuth Inorganic materials 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
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Abstract
The invention relates to a microwave ferrite material, a preparation method and application thereof, wherein the microwave ferrite material is metal-doped yttrium iron garnet; the doping metal comprises lanthanide metal La, and the doping molar weight is 0-0.1 and is not 0. By doping lanthanide metal La in yttrium iron garnet and controlling the doping molar quantity within the range of 0-0.1 and not 0, the dielectric constant of yttrium iron garnet is improved to more than 16, the problem that the dielectric constant of gyromagnetic garnet ferrite is about 15 is overcome, and the gyromagnetic garnet ferrite has stable saturation magnetization, high Curie temperature, narrow linewidth and low loss.
Description
Technical Field
The invention belongs to the technical field of electronic ceramics, and relates to a microwave ferrite material and a preparation method and application thereof.
Background
The microwave ferrite circulator is an indispensable basic device in 5G communication, and is mainly applied to base station and mobile station systems. With the continuous development of mobile communication technology, the basic requirements of mobile communication on a circulator are low insertion loss, high isolation, high echo, higher power, high temperature stability, high intermodulation value, small size, light weight and low cost. Gyromagnetic ferrite is a key material of a circulator, and has stable saturation magnetization, high Curie temperature, narrow line width, high dielectric constant and low loss.
However, the dielectric constant of gyromagnetic garnet ferrite in the existing circulator is about 15, the performance stability is poor, the production period is long, the mass production is difficult, and the requirement of 5G communication products is difficult to meet.
Disclosure of Invention
In order to solve the technical problems, the invention provides a microwave ferrite material, a preparation method and application thereof, wherein lanthanide metal La is doped in yttrium iron garnet, the doping molar quantity is controlled within the range of 0-0.1 and not 0, the dielectric constant of yttrium iron garnet is improved to more than 16, the problem that the dielectric constant of gyromagnetic garnet ferrite is about 15 is solved, and the microwave ferrite material has stable saturation magnetization, high Curie temperature, narrow linewidth and low loss.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a microwave ferrite material which is a metal-doped yttrium iron garnet; the doping metal includes lanthanide metal La, the doping mole amount is 0-0.1 and not 0, for example, 0.02, 0.05, 0.1, 0.5 or 0.9, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
According to the microwave ferrite material provided by the invention, the lanthanide metal La is doped in the yttrium iron garnet, the doping molar quantity is controlled within the range of 0-0.1 and not 0, the dielectric constant of the yttrium iron garnet is improved to be more than 16, the problem that the dielectric constant of the gyromagnetic garnet ferrite is about 15 is solved, and the microwave ferrite material has stable saturation magnetization, high Curie temperature, narrow linewidth and low loss.
Preferably, the doping metal of the microwave ferrite material comprises any one or a combination of at least two of Gd, la, bi, al, mn, zr or Ti, typically but not limited to combinations comprising Gd and La, la and Bi, bi and Al, mn and Zr, gd, la and Bi, la, bi and Al, mn and Zr, mn, zr and Ti.
Preferably, the microwave ferrite material has a chemical formula of Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 。
Where 0.1< x <0.2, for example, may be 0.12, 0.14, 0.16, 0.18 or 0.19, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
0< y <0.1, for example, may be 0.02, 0.04, 0.06, 0.08, or 0.09, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
0.1< z <0.25, for example, may be 0.12, 0.15, 0.2, 0.22 or 0.25, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
0< h <0.1 and is not 0, and may be, for example, 0.02, 0.05, 0.07, 0.08 or 0.09, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
0< m <0.1, for example, may be 0.02, 0.05, 0.07, 0.08 or 0.09, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
0< n <0.1, for example, may be 0.02, 0.05, 0.07, 0.08 or 0.09, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the molar amount of Gd is 0.14-0.16, for example, 0.14, 0.145, 0.15, 0.155 or 0.16, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the molar amount of La is 0.04 to 0.06, for example, 0.04, 0.045, 0.05, 0.055 or 0.06, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the molar amount of Bi is 0.04 to 0.06, for example, 0.04, 0.045, 0.05, 0.055 or 0.06, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the molar amount of Al is 0.01 to 0.03, for example, 0.01, 0.015, 0.02, 0.025 or 0.03, but the present invention is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the molar amount of Mn is 0.24 to 0.28, for example, 0.24, 0.25, 0.26, 0.27 or 0.28, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the molar amount of Zr is 0.18 to 0.22, for example, 0.18, 0.19, 0.2, 0.21 or 0.22, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the molar amount of Ti is 0.05 to 0.07, for example, 0.05, 0.055, 0.06, 0.065 or 0.07, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the microwave ferrite material has a chemical formula of Y 2.75 Gd 0.15 La 0.05 Bi 0.05 Fe 4.46 Al 0.02 Mn 0.26 Zr 0.2 Ti 0.06 O 12 。
The microwave ferrite material obtained by controlling the doped metal elements and the content thereof generates synergistic effect and has the saturation induction intensity of more than 1650Gs, the line width of less than 30Oe, the dielectric constant of more than 16 and the dielectric constant of 1.5 multiplied by 10 -4 The dielectric loss tangent below and the Curie temperature above 280 ℃.
In a second aspect, the present invention provides a method for preparing the microwave ferrite material according to the first aspect, the method comprising the steps of:
(1) Mixing an iron source, an yttrium source and a doped metal source, and performing primary sanding and primary spray granulation to obtain primary spray granulation materials;
(2) Presintering the obtained primary spray granulation to obtain a presintering material;
(3) Performing secondary sand grinding and secondary spray granulation on the obtained presintered material to obtain secondary spray granulation materials;
(4) And (3) compacting and sintering the obtained secondary spray granulation material to obtain the microwave ferrite material.
Preferably, the iron source, yttrium source and doped metal source of step (1) are iron oxide, yttrium oxide and doped metal oxide, respectively.
Preferably, the mixing of step (1) further comprises a solvent and an abrasive article.
Preferably, the mass ratio of the raw materials consisting of the iron source, the yttrium source and the doped metal source to the solvent and the grinding tool is 1 (0.8-1.2): (3-3.5), for example, 1:1:3.3, 1:0.8:3, 1:1.2:3.5, 1:0.8:3.5 or 1:1.2:3, but not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the rotational speed of the primary sanding in the step (1) is 200-400 rpm, for example, 200 rpm, 250 rpm, 300 rpm, 350 rpm or 400 rpm, but the present invention is not limited to the listed values, and other values not listed in the numerical range are equally applicable.
Preferably, the time of the primary sanding in the step (1) is 10 to 50min, for example, 10min, 20min, 30min, 40min or 50min, but the present invention is not limited to the listed values, and other values not listed in the numerical range are applicable.
Preferably, the primary spray granulation in step (1) further comprises mixing a primary sand abrasive and a glue.
Preferably, the dry glue content of the glue is 1-1.5%, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Preferably, the mass ratio of the primary sand abrasive to the glue is 8-12:1, for example, it may be 8:1, 9:1, 10:1, 11:1 or 12:1, but is not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Preferably, the solid content of the primary sand abrasive is 40-60%, for example, 40%, 45%, 50%, 55% or 60%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the temperature of the pre-sintering in the step (2) is 1000 to 1300 ℃, for example, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or 1300 ℃, but the pre-sintering temperature is not limited to the values listed, and other values not listed in the numerical range are applicable.
Preferably, the pre-sintering time in the step (2) is 150-200 min, for example, 150min, 160min, 170min, 180min, 190min or 200min, but not limited to the listed values, and other values not listed in the range are applicable.
Preferably, the step (3) further comprises a mixed solvent and an abrasive tool before the secondary sanding.
Preferably, the mass ratio of the pre-sintering material, the solvent and the grinding tool is 1 (0.5-0.6): (3-3.5), for example, may be 1:0.55:3.3, 1:0.5:3, 1:0.6:3.5, 1:0.5:3.5 or 1:0.6:3, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the rotational speed of the secondary sanding in the step (3) is 300-500 rpm, for example, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm, but the present invention is not limited to the listed values, and other values not listed in the numerical range are equally applicable.
Preferably, the time of the secondary sanding in the step (3) is 80-120 min, for example, 80min, 90min, 100min, 110min or 120min, but the present invention is not limited to the listed values, and other values not listed in the range of values are equally applicable.
According to the preparation method adopted in the invention, the sanding time is different from the conventional sanding time in terms of hours, and only two times of sanding in a short time are needed, so that the time is saved, and the efficiency is improved.
Preferably, the secondary sand material obtained after the secondary sand in the step (3) has a slurry particle size of 0.6 to 1 μm, for example, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1 μm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, preferably 0.8 μm.
The size of the slurry of the secondary sand abrasive is 0.6-1 mu m, so that the slurry can better match the loss entering quantity of grinding balls, the spray granulation material particles are more uniform, the formed and sintered crystal phase structure is better, and the performance is better; when the granularity of the slurry is too large, the grinding time is short, the grinding ball loss is small, the activity of the spray granulation material is poor, the physical and chemical reaction is slow, the crystal phase structure is poor, and the performance is poor; when the granularity of the slurry is too small, the grinding time is long, the grinding ball loss is large, the activity of the spray granulation material is too good, the physical and chemical reaction is too fast, the crystal phase structure is unstable, the control is difficult, and the performance is poorer.
Preferably, the secondary spray granulation of step (3) further comprises mixing a secondary sand abrasive and a glue.
Preferably, the dry glue content of the glue is 1-1.5%, for example, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Preferably, the mass ratio of the secondary sand abrasive to the glue is 8-12:1, for example, it may be 8:1, 9:1, 10:1, 11:1 or 12:1, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the solid content of the secondary sand abrasive is 60-70%, for example, 60%, 62%, 65%, 68% or 70%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the secondary spray granulation in the step (3) further comprises sieving with a 60-200 mesh sieve, for example, 60 mesh, 100 mesh, 150 mesh, 180 mesh or 200 mesh, but not limited to the listed values, and other non-listed values in the range of values are equally applicable.
Preferably, the green density obtained after the profiling in the step (4) is 3.3-3.6 g/cm 3 For example, it may be 3.3g/cm 3 、3.35g/cm 3 、3.4g/cm 3 、3.5g/cm 3 Or 3.6g/cm 3 But are not limited to, the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the sintering temperature in step (4) is 1440 to 1460 ℃, for example 1440 ℃, 1445 ℃, 1450 ℃, 1455 ℃ or 1460 ℃, but the sintering temperature is not limited to the values listed, and other values not listed in the numerical range are applicable.
Preferably, the sintering time in the step (4) is 350-400 min, for example, 350min, 360min, 370min, 380min, 390min or 400min, but the sintering time is not limited to the listed values, and other values not listed in the numerical range are applicable.
As a preferred technical scheme of the preparation method according to the second aspect of the present invention, the preparation method comprises the following steps:
(1) Mixing raw materials of an iron source, an yttrium source and a doped metal source according to the mass ratio of 1 (0.8-1.2) (3-3.5), mixing the raw materials, a solvent and a grinding tool, performing primary sanding for 10-50 min at the rotating speed of 200-400 rpm to obtain a primary sand abrasive with the solid content of 40-60%, mixing the primary sand abrasive with the mass ratio of 8-12:1 and glue with the dry glue content of 1-1.5%, and performing primary spray granulation to obtain primary spray granulation materials;
(2) Presintering the primary spray granulation at 1000-1300 ℃ for 150-200 min to obtain a presintering material;
(3) Mixing the pre-sintered material, the solvent and the grinding tool according to the mass ratio of (0.5-0.6) (3-3.5), performing secondary sanding for 80-120 min at the rotating speed of 300-500 r/min to obtain secondary sand grinding materials with the slurry granularity of 0.5-1 mu m and the solid content of 60-70%, mixing the secondary sand grinding materials with the glue with the dry glue content of 1-1.5% according to the mass ratio of 8-12:1, performing secondary spray granulation, and sieving with a 60-200 mesh sieve to obtain secondary spray granulating materials;
(4) Profiling the obtained secondary spray granulation material to obtain a green compact with the density of 3.3-3.6 g/cm 3 And sintering the obtained green body for 350-400 min at 1440-1460 ℃ to obtain the microwave ferrite material.
In a third aspect, a use of the microwave ferrite material according to the first aspect for 5G communication.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the microwave ferrite material provided by the invention, the lanthanide metal La is doped in the yttrium iron garnet, the doping molar quantity is controlled within the range of 0-0.1 and not 0, the dielectric constant of the yttrium iron garnet is improved to be more than 16, the problem that the dielectric constant of the gyromagnetic garnet ferrite is about 15 is solved, and the microwave ferrite material has stable saturation magnetization, high Curie temperature, narrow linewidth and low loss.
(2) The microwave ferrite material obtained by controlling the doped metal elements and the content thereof generates synergistic effect and has the structure of 1Saturated magnetic induction of 650Gs or more, line width of 30Oe or less, dielectric constant of 16 or more, 1.5X10 -4 The dielectric loss tangent below and the Curie temperature above 280 ℃.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a microwave ferrite material with a chemical formula of Y 2.75 Gd 0.15 La 0.05 Bi 0.05 Fe 4.46 Al 0.02 Mn 0.26 Zr 0.2 Ti 0.06 O 12 The preparation method comprises the following steps:
(1) Mixing Fe 2 O 3 、Y 2 O 3 Mixing raw materials, a solvent and a grinding tool according to the mass ratio of 1:1:3.3, performing primary sanding for 30min at the rotating speed of 300 revolutions per minute to obtain a primary sand abrasive with the solid content of 50%, mixing the primary sand abrasive with the mass ratio of 10:1 and glue with the dry glue content of 1.2%, and performing primary spray granulation to obtain primary spray granulation materials;
(2) Pre-sintering the primary spray granulation at 1100 ℃ for 180min to obtain a pre-sintering material;
(3) Mixing the pre-sintered material, the solvent and the grinding tool according to the mass ratio of 1:0.55:3.3, performing secondary sanding for 100min at the rotating speed of 400 rpm to obtain secondary sand grinding materials with the slurry granularity of 0.8 mu m and the solid content of 65%, mixing the secondary sand grinding materials with the glue with the dry glue content of 1.2% according to the mass ratio of 10:1, performing secondary spray granulation, and sieving the mixture with a 100-mesh sieve to obtain secondary spray granulation materials;
(4) The obtained secondary spray granulation material was subjected to compression molding to obtain a green compact having a density of 3.5g/cm 3 And sintering the obtained green compact at 1450 ℃ for 380min to obtain the microwave ferrite material.
Example 2
The embodiment provides a microwave ferriteThe chemical formula of the material is Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.12, y=0.02, z=0.12, h=0.03, m=0.05, n=0.06, the production method was the same as in example 1.
Example 3
The embodiment provides a microwave ferrite material with a chemical formula of Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.15, y=0.02, z=0.12, h=0.03, m=0.05, n=0.06, the production method was the same as in example 1.
Example 4
The embodiment provides a microwave ferrite material with a chemical formula of Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.18, y=0.02, z=0.12, h=0.03, m=0.05, n=0.06, the production method was the same as in example 1.
Example 5
The embodiment provides a microwave ferrite material with a chemical formula of Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.15, y=0.02, z=0.12, h=0.05, m=0.05, n=0.06, the preparation method was the same as in example 1.
Example 6
The embodiment provides a microwave ferrite material with a chemical formula of Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.15, y=0.02, z=0.12, h=0.07, m=0.05, n=0.06, the production method was the same as in example 1.
Example 7
The present embodiment provides a microwave ferrite material,the chemical formula is Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.15, y=0.02, z=0.15, h=0.05, m=0.05, n=0.06, the production method was the same as in example 1.
Example 8
The embodiment provides a microwave ferrite material with a chemical formula of Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+ n Zr z Ti n O 12 Where x=0.15, y=0.02, z=0.24, h=0.05, m=0.05, n=0.06, the preparation method was the same as in example 1.
Example 9
This example provides a microwave ferrite material differing from example 1 in that the secondary sand abrasive of step (3) has a slurry particle size of 0.5 μm.
Example 10
This example provides a microwave ferrite material differing from example 1 in that the secondary sand abrasive of step (3) has a slurry particle size of 1.2 μm.
Example 11
The embodiment provides a microwave ferrite material with a chemical formula of Y 2.705 Gd 0.15 La 0.095 Bi 0.05 Fe 4.46 Al 0.0 2 Mn 0.26 Zr 0.2 Ti 0.06 O 12 。
Example 12
The embodiment provides a microwave ferrite material with a chemical formula of Y 2.795 Gd 0.15 La 0.005 Bi 0.05 Fe 4.46 Al 0.0 2 Mn 0.26 Zr 0.2 Ti 0.06 O 12 。
Comparative example 1
The comparative example provides a microwave ferrite material with a chemical formula of Y 2.8 Gd 0.15 Bi 0.05 Fe 4.46 Al 0.02 Mn 0.26 Zr 0.2 Ti 0.06 O 12 The difference from example 1 is that the metal La is undoped.
Comparative example 2
The comparative example provides a microwave ferrite material with a chemical formula of Y 2.68 Gd 0.15 Bi 0.05 La 0.12 Fe 4.46 Al 0.02 Mn 0.26 Zr 0.2 Ti 0.06 O 12 The difference from example 1 is that the molar amount of the doping metal La is more than 0.1.
The microwave ferrite material obtained by the method is finished to a material with a proper size, and can be a ball with a diameter of 2.0mm, a magnetic needle bar with a diameter of D1.6x22 or a magnetic ring with a diameter of D25/20/8. The obtained material is subjected to 4pi Ms and dielectric constant epsilon r The dielectric loss tangent tan delta, the line width DeltaH, the Curie temperature Tc, the remanence Br and the coercivity Hc were measured, and the test results are shown in Table 1.
TABLE 1
From table 1, the following conclusions can be drawn:
(1) As can be seen from examples 1 and comparative examples 1 and 2, the microwave ferrite material provided by the invention has the advantages that the dielectric constant of yttrium iron garnet is improved to more than 16 by doping lanthanide metal La in yttrium iron garnet and controlling the doping molar quantity within the range of 0-0.1 and not 0, the problem that the dielectric constant of gyromagnetic garnet ferrite is about 15 is overcome, and the microwave ferrite material has stable saturation magnetization, high curie temperature, narrow linewidth and low loss.
(2) As is clear from examples 1 to 8, the microwave ferrite material obtained by controlling the doped metal element and the content thereof in the present invention has a saturation induction of 1650Gs or more, a line width of 30Oe or less, a dielectric constant of 16 or more, and a dielectric constant of 1.5X10 -4 The dielectric loss tangent below and the Curie temperature above 280 ℃.
(4) As can be seen from the comparison of the embodiment 1 with the embodiment 9 and the embodiment 10, the slurry granularity of the secondary sand abrasive is 0.6-1 μm, so that the secondary sand abrasive can better match the loss of the grinding balls, the particles of the spray granulation material are more uniform, the crystalline phase structure after molding and sintering is better, and the performance is better; when the granularity of the slurry is too large, the grinding time is short, the grinding ball loss is small, the activity of the spray granulation material is poor, the physical and chemical reaction is slow, the crystal phase structure is poor, and the performance is poor; when the granularity of the slurry is too small, the grinding time is long, the grinding ball loss is large, the activity of the spray granulation material is too good, the physical and chemical reaction is too fast, the crystal phase structure is unstable, the control is difficult, and the performance is poorer.
(5) As is clear from a comparison of example 1 with examples 11 and 12, when the content of the doped lanthanide metal La exceeds the preferred range of the present invention, the saturation magnetization, high curie temperature, narrow linewidth, low loss, and the like of the microwave ferrite material are affected.
The performance of the circulator was measured using the microwave ferrite material obtained in example 1, and the results are shown in table 2.
TABLE 2
In summary, the gyromagnetic ferrite material provided by the invention has high saturation magnetization, high Curie temperature, low loss, good performance consistency and suitability for mass production, and has the saturation magnetic induction intensity of 1650Gs or more, the line width of 30Oe or less, the dielectric constant of 16 or more and 1.5X10 -4 The dielectric loss tangent below and the Curie temperature above 280 ℃ can well meet the parameter requirements of the circulator and the isolator, and the third-order intermodulation is good.
The detailed process equipment and process flow of the present invention are described by the above embodiments, but the present invention is not limited to, i.e., it does not mean that the present invention must be practiced depending on the detailed process equipment and process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (32)
1. A microwave ferrite material characterized in that the microwave ferrite material is metal-doped yttrium iron garnet;
the chemical formula of the microwave ferrite material is Y 3-x-h-m Gd x La h Bi m Fe 5-y-2z-2n Al y Mn z+n Zr z Ti n O 12 Wherein 0.1<x<0.2，0.01<y<0.03，0.12<z<0.25，0.04<h<0.06，0.04<m<0.06 and 0.05<n<0.07。
2. The microwave ferrite material according to claim 1, wherein the molar amount of Gd is 0.14-0.16.
3. The microwave ferrite material according to claim 1, wherein the molar amount of Mn is 0.24-0.28.
4. The microwave ferrite material according to claim 1, wherein the molar amount of Zr is 0.18-0.22.
5. The microwave ferrite material of claim 1, wherein the microwave ferrite material has a chemical formula Y 2.75 Gd 0.15 La 0.05 Bi 0.05 Fe 4.46 Al 0.02 Mn 0.26 Zr 0.2 Ti 0.06 O 12 。
6. The method of preparing a microwave ferrite material according to any one of claims 1-5, characterized in that the preparation method comprises the steps of:
(1) Mixing an iron source, an yttrium source and a doped metal source, and performing primary sanding and primary spray granulation to obtain primary spray granulation materials;
(2) Presintering the obtained primary spray granulation to obtain a presintering material;
(3) Performing secondary sand grinding and secondary spray granulation on the obtained presintered material to obtain secondary spray granulation materials;
(4) And (3) compacting and sintering the obtained secondary spray granulation material to obtain the microwave ferrite material.
7. The method of claim 6, wherein the source of iron, the source of yttrium, and the source of doped metal in step (1) are iron oxide, yttrium oxide, and doped metal oxide, respectively.
8. The method of claim 6, wherein the mixing of step (1) further comprises a solvent and an abrasive tool.
9. The preparation method of the composite material of the iron source, the yttrium source and the doped metal source is characterized in that the mass ratio of raw materials to solvents and grinding tools is 1 (0.8-1.2) to 3-3.5.
10. The method according to claim 6, wherein the primary sanding in the step (1) is performed at a rotational speed of 200 to 400 rpm.
11. The method according to claim 6, wherein the primary sanding in the step (1) is performed for 10-50 min.
12. The method of claim 6, wherein the primary spray granulation of step (1) is preceded by mixing a primary sand abrasive and a glue.
13. The method for preparing the adhesive according to claim 12, wherein the dry adhesive content of the adhesive is 1-1.5%.
14. The preparation method of claim 12, wherein the mass ratio of the primary sand abrasive to the glue is 8-12:1.
15. The method of claim 12, wherein the primary sand abrasive has a solids content of 40-60%.
16. The method according to claim 6, wherein the temperature of the pre-sintering in the step (2) is 1000-1300 ℃.
17. The method of claim 6, wherein the pre-sintering time in step (2) is 150-200 min.
18. The method of claim 6, wherein the secondary sanding in step (3) is preceded by a solvent blend and an abrasive tool.
19. The method of claim 18, wherein the mass ratio of the pre-sintering material, the solvent and the grinding tool is 1 (0.5-0.6): 3-3.5.
20. The method according to claim 6, wherein the rotational speed of the secondary sanding in the step (3) is 300-500 rpm.
21. The method according to claim 6, wherein the secondary sanding in the step (3) is performed for 80-120 min.
22. The method according to claim 6, wherein the secondary sand grinding material obtained after the secondary sand grinding in the step (3) has a slurry particle size of 0.5-1 μm.
23. The method of claim 6, wherein the secondary spray granulation of step (3) further comprises mixing a secondary sand abrasive and a glue.
24. The method for preparing the adhesive according to claim 23, wherein the dry adhesive content of the adhesive is 1-1.5%.
25. The preparation method of claim 23, wherein the mass ratio of the secondary sand abrasive to the glue is 8-12:1.
26. The method of claim 23, wherein the secondary sand abrasive has a solids content of 60-70%.
27. The method according to claim 6, wherein the secondary spray granulation in the step (3) further comprises sieving with a 60-200 mesh sieve.
28. The method according to claim 6, wherein the green density obtained after the compacting in the step (4) is 3.3 to 3.6g/cm 3 。
29. The method according to claim 6, wherein the sintering temperature in the step (4) is 1440-1460 ℃.
30. The method according to claim 6, wherein the sintering time in the step (4) is 350-400 min.
31. The preparation method according to claim 6, characterized in that the preparation method comprises the steps of:
(1) Mixing raw materials of an iron source, an yttrium source and a doped metal source according to the mass ratio of 1 (0.8-1.2) (3-3.5), mixing the raw materials, a solvent and a grinding tool, performing primary sanding for 10-50 min at the rotating speed of 200-400 rpm to obtain a primary sand abrasive with the solid content of 40-60%, mixing the primary sand abrasive with the mass ratio of 8-12:1 and glue with the dry glue content of 1-1.5%, and performing primary spray granulation to obtain primary spray granulation materials;
(2) Presintering the primary spray granulation at 1000-1300 ℃ for 150-200 min to obtain a presintering material;
(3) Mixing the pre-sintered material, the solvent and the grinding tool according to the mass ratio of (0.5-0.6) (3-3.5), performing secondary sanding for 80-120 min at the rotating speed of 300-500 r/min to obtain secondary sand grinding materials with the slurry granularity of 0.5-1 mu m and the solid content of 60-70%, mixing the secondary sand grinding materials with the glue with the dry glue content of 1-1.5% according to the mass ratio of 8-12:1, performing secondary spray granulation, and sieving with a 60-200 mesh sieve to obtain secondary spray granulating materials;
(4) Profiling the obtained secondary spray granulation material to obtain a green compact with the density of 3.3-3.6 g/cm 3 And sintering the obtained green body for 350-400 min at 1440-1460 ℃ to obtain the microwave ferrite material.
32. Use of a microwave ferrite material according to any of claims 1-5, wherein the microwave ferrite material is used for 5G communication.
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