CN118063203A - High-power low-loss Li-based microwave ferrite for LTCC and preparation method - Google Patents
High-power low-loss Li-based microwave ferrite for LTCC and preparation method Download PDFInfo
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 25
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 16
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims description 27
- 238000005245 sintering Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 230000005418 spin wave Effects 0.000 abstract description 25
- 150000002500 ions Chemical class 0.000 abstract description 18
- 239000000919 ceramic Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 230000005350 ferromagnetic resonance Effects 0.000 description 13
- 230000005415 magnetization Effects 0.000 description 13
- 230000005291 magnetic effect Effects 0.000 description 12
- 239000011787 zinc oxide Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 206010022971 Iron Deficiencies Diseases 0.000 description 2
- -1 Mn3+ ions Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 239000000374 eutectic mixture Substances 0.000 description 1
- 230000005293 ferrimagnetic effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
A high-power low-loss Li-based microwave ferrite for LTCC and a preparation method thereof belong to the technical field of electronic ceramics. According to the content ：Li2CO3 11.80～12.24mol％,ZnO19.87～20.41mol％,TiO2 10.78～11.08mol％,Mn3O4 0.39～2.65mol％,Co3O40.04～0.58mol％,Fe2O3 54.70～56.18mol％,Bi2O3 0.09mol％. of the ferrite calculated according to the respective standard substance, the invention introduces high valence Mn ions into the Li-series microwave ferrite to change the grain size distribution of the ferrite, and especially the increase of the small grain ratio leads to the improvement of the spin wave linewidth; on the basis of grain refinement, a proper amount of Co ions with rapid relaxation property are introduced, so that the spin wave linewidth of ferrite is further improved.
Description
Technical Field
The invention belongs to the technical field of electronic ceramics, and particularly relates to a high-power low-loss Li-based microwave ferrite for LTCC and a preparation method thereof.
Background
With the development of phased array radar systems toward miniaturization, integration and multifunction, phase shifters, a key device, are required to have lower insertion loss, higher peak power and faster response speed. Li-based ferrite has the advantages of high rectangle degree, high saturation magnetization (4pi M s), high Curie temperature (T c), low ferromagnetic resonance line width (delta H) and the like, and is used as an excellent candidate material for a microwave ferrite phase shifter. In order to meet the requirements of miniaturization and integration of microwave ferrite devices, the current research work on lithium-based ferrites is mainly focused on the following two aspects: 1) Reducing the sintering temperature of ferrite to around 900 ℃ by introducing additives such as low-melting-point oxide, glass and the like so as to realize matching cofiring with a silver electrode; 2) The ion substitution is used for improving the serious problems of dielectric loss and magnetic loss performance degradation of the low-temperature sintered lithium ferrite. Furthermore, microwave ferrite devices for high power applications should have high power handling capabilities in addition to requiring low electromagnetic losses. Therefore, the combination of the spin wave linewidth, dielectric loss, magnetic loss and other properties of the Li-based ferrite material under the low-temperature sintering condition is an urgent problem to be solved.
The invention patent with the application number 202010379833.9 discloses a high-power torque ferrite material for Ku wave band and a preparation method thereof, the invention obtains the maximum value of spin wave line width delta H k of a sample under 1000 ℃ sintering condition as 3.88Oe, the low range of ferromagnetic resonance line width delta H as 298Oe and the low range of dielectric loss tangent tan delta ε as 5.7X10 -4 by changing the substitution amount of Zn 2+ and Ti 4+ ions in Li ferrite and assisting with auxiliaries such as Bi 2O3、V2O5, the material prepared by the method has higher sintering temperature, cannot be compatible with the LTCC technology, and has lower spin wave line width delta H k and higher microwave magnetic loss delta H. The invention patent with the application number 202110372118.7 discloses a narrow linewidth LTCF gyromagnetic substrate material and a preparation method thereof, wherein the invention changes the substitution amount of Zn 2+、Ti4+ ions in Li ferrite, and simultaneously, B 2O3-ZnO-Bi2O3 (BZB) glass auxiliary agent and Bi 2O3 oxide are added, and ferrite samples with the delta H of 90Oe are obtained under the sintering condition of 900 ℃, but the tan delta ε is as high as 6.5 multiplied by 10 -4, the low magnetic loss and the low dielectric loss cannot be simultaneously achieved, and the delta H k parameter is not shown. The invention patent with the application number 201811483879.4 discloses a spinel Li ferrite material for a lock phase shifter from an X band to a millimeter wave band, which is prepared by adopting Zn 2+、Ti4+、Mg2+、Cu2+、Co2+、Bi3+ and Mn 2+ plasma to jointly replace Li ferrite, obtaining a spin wave line width delta H k of a sample under 980 ℃ sintering condition as high as 10.0Oe, a ferromagnetic resonance line width delta H as low as 145Oe and a dielectric loss tangent tan delta ε as low as 2.3 multiplied by 10 -4, wherein the sintering temperature and spin wave line width are further optimized, bi 2O3 auxiliary agent is added in ."Effect of Bi2O3contents on magnetic and electromagnetic properties of LiZnMn ferrite ceramics[J],Eur.Ceram.Soc.42(2022)3463–3472" articles, the sintering at 1075 ℃ obtains low magnetic loss (delta H= -158 Oe) and low dielectric loss (tan delta ε＝～5.49×10-4), but the spin wave linewidth is only ～1.87Oe."Low-temperature sintering and ferrimagnetic properties of LiZnTiMn ferrites with Bi2O3–Nb2O5 eutectic mixture[J],J.Mater.Sci.Mater.Electron.33(2022)20162–20169" article, bi 2O3–Nb2O5 composite auxiliary agent is added, and the lower magnetic loss (delta H= -161 Oe) is realized under the sintering condition of 920 ℃, but no report of dielectric loss tangent and spin wave linewidth parameters is seen.
In summary, none of the above patents and articles simultaneously obtain a Li-based ferrite material with Gao Zixuan wave width and low microwave loss under the condition of low-temperature sintering (less than or equal to 900 ℃), and a better solution is needed in the face of the requirements of microwave ferrite devices in LTCC integration technology on high power bearing capacity and low electromagnetic loss.
Disclosure of Invention
The invention aims to solve the problem that the high power bearing capacity and the low electromagnetic loss of the traditional LTCC microwave ferrite device cannot be considered, and provides a high power low loss Li microwave ferrite for LTCC and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A high-power low-loss Li-based microwave ferrite for LTCC comprises the following contents according to respective standards ：Li2CO3 11.80～12.24mol％,ZnO 19.87～20.41mol％,TiO2 10.78～11.08mol％,Mn3O4 0.39～2.65mol％,Co3O4 0.04～0.58mol％,Fe2O3 54.70～56.18mol％,Bi2O3 0.09mol％.
A preparation method of high-power low-loss Li-based microwave ferrite for LTCC comprises the following steps:
Step 1, weighing:
Taking analytically pure lithium carbonate (Li 2CO3), zinc oxide (ZnO), titanium oxide (TiO 2), manganic oxide (Mn 3O4), tricobalt tetraoxide (Co 3O4), ferric oxide (Fe 2O3) and bismuth oxide (Bi 2O3) as raw materials, and weighing the raw materials according to the content Li2CO311.80～12.24mol％,ZnO 19.87～20.41mol％,TiO2 10.78～11.08mol％,Mn3O4 0.39～2.65mol％,Co3O4 0.04～0.58mol％,Fe2O3 54.70～56.18mol％,Bi2O3 0.09mol％ of each standard substance;
Step 2, ball milling for the first time:
Adding the raw materials weighed in the step 1 into a planetary ball mill for ball milling for one time, wherein a dispersing agent is deionized water, and the mass ratio of the raw materials to the deionized water is 1:1.5, the rotating speed of the ball mill is 250r/min, and the ball milling time is 4h;
Step 3, presintering:
Drying and sieving the primary ball milling slurry obtained in the step 2, putting the slurry into a corundum crucible, presintering the slurry in an oxygen atmosphere at 750-850 ℃ for 2-3 hours, cooling the slurry to room temperature along with a furnace after the presintering, and taking out the slurry to obtain a Li-based microwave ferrite presintering material;
Step 4, secondary ball milling:
Adding the Li-based microwave ferrite pre-sintering material and deionized water obtained in the step 3 into a planetary ball mill for secondary ball milling, wherein the mass ratio of the pre-sintering material to the deionized water is 1:1.3, the rotating speed of the ball mill is 250r/min, the ball milling time is 6h, and the slurry is dried after the ball milling is completed;
step 5, molding:
Sieving the secondary ball milling material obtained in the step 4, adding a polyvinyl alcohol (PVA) adhesive with the mass of 8-12 wt.% of that of the powder material for granulating, and pressing into an annular green body sample by using a hydraulic press;
step 6, sintering:
Placing the green body sample obtained in the step 5 into a sintering furnace, heating to 600 ℃ at a speed of 1 ℃/min, and preserving heat for 1-2 h to perform glue discharging; then heating to the sintering temperature of 880-890 ℃ at the speed of 1 ℃/min, and preserving heat for 2-3 h; after sintering, cooling to 600 ℃ at a speed of 1 ℃/min; and finally, naturally cooling to room temperature along with the furnace to obtain the Li microwave ferrite.
According to the high-power low-loss Li-based microwave ferrite for LTCC, firstly, a Li-based microwave ferrite iron deficiency base formula which is jointly replaced by Zn 2+-Ti4+-Bi3 + ions is selected, and Zn 2+、Ti4+ ions are jointly introduced to regulate saturation magnetization and Curie temperature of ferrite except for changing the difference value of magnetic moment of the A-B bits of a secondary lattice and the super-exchange effect, so that densification is improved, magnetocrystalline anisotropy constants of the ferrite are reduced, and pore and magnetocrystalline anisotropy linewidth are reduced; and the substitution of a proper amount of Bi 3+ ions effectively reduces the sintering temperature and the microwave magnetic loss of the ferrite. Secondly, by adopting comprehensive measures of introducing high valence Mn ions and high valence Co ions, the generation of Fe 2+ ions is effectively inhibited, and the dielectric loss is reduced; however, co ions have a large positive magnetocrystalline anisotropy constant to increase the ferroresonance line width, and when Mn 2+ ions which tend to occupy the A-position of the tetrahedron center and Mn 3+ ions which tend to occupy the B-position of the octahedral center are introduced, the super-exchange effect of the A-B-position is weakened to reduce the magnetic loss, so that the low dielectric loss of the microwave ferrite is ensured without increasing the ferroresonance line width. In addition, the addition of Mn 2+/Mn3+ ions in the trimanganese tetroxide (Mn 3O4) causes bismuth ferrite to be separated out, thereby leading ferrite grains to be refined and shortening spin wave transit time; on the basis, co 2+/Co3+ ions with rapid relaxation property in cobaltosic oxide (Co 3O4) are introduced, so that the spin bandwidth is further improved.
The technical indexes of the Li-based microwave ferrite prepared by the invention are as follows:
sintering temperature: at a temperature of 880 ℃;
Apparent density ρ: > 4.7g/cm 3;
Saturation magnetization 4 pi M s: 3900 Gs+ -3%;
ferromagnetic resonance linewidth Δh: <120Oe;
Spin wave linewidth Δh k: > 10Oe;
Dielectric loss tangent tan delta ε：＜3×10-4;
rectangle degree R: more than or equal to 0.85;
curie temperature T c: > 300 ℃;
Compared with the prior art, the invention has the beneficial effects that:
1. In the Li-based microwave ferrite, high valence Mn ions are introduced to change the size distribution of ferrite grains, and especially the small grain ratio is increased so that the spin wave line width delta H k is improved; on the basis of grain refinement, a proper amount of Co ions with rapid relaxation property are introduced, so that the spin wave linewidth delta H k of ferrite is further improved.
2. In the invention, an iron-deficiency formula is considered in the structural design of the material, and high-valence metal oxides Mn 3O4 and Co 3O4 are added in the raw materials, and meanwhile, comprehensive measures of oxygen atmosphere treatment are adopted in the presintering process, so that the microwave dielectric and magnetic loss of ferrite are greatly reduced.
3. The high-power low-loss Li-based microwave ferrite for LTCC prepared by the invention has low sintering temperature (880 ℃), and also has good electromagnetic performance: high spin-wave linewidth (Δh k > 10 Oe), low dielectric loss (tan δ ε＜3×10-4), low magnetic loss (Δh <120 Oe), high saturation magnetization (4pi M s =3900 gs±3%, high density (ρ >4.7g/cm 3), and high curie temperature (T c > 300 ℃). The prepared high-power low-loss Li-based microwave ferrite material not only meets the LTCC process requirement, but also has good electromagnetic performance of key substrate materials required by high-power microwave ferrite devices.
Drawings
FIG. 1 is XRD patterns of ferrites obtained in comparative example, example 1 and example 8;
Fig. 2 is an SEM image of the Li-based microwave ferrite sample obtained in comparative example (a) and example 1 (b).
Detailed Description
The technical scheme of the invention is described in detail below with reference to the accompanying drawings and examples.
Example 1
A preparation method of high-power low-loss Li-based microwave ferrite for LTCC comprises the following steps:
Step 1, weighing:
Analytically pure lithium carbonate (Li 2CO3), zinc oxide (ZnO), titanium oxide (TiO 2), manganous oxide (Mn 3O4), ferric oxide (Fe 2O3) and bismuth oxide (Bi 2O3) are taken as raw materials, and the raw materials are calculated and weighed according to the content Li2CO3 12.06mol％,ZnO 20.09mol％,TiO2 10.91mol％,Mn3O4 1.53mol％,Fe2O3 55.32mol％,Bi2O3 0.09mol％ of each standard substance;
Step 2, ball milling for the first time:
Adding the raw materials weighed in the step 1 into a planetary ball mill for ball milling for one time, wherein a dispersing agent is deionized water, and the mass ratio of the raw materials to the deionized water is 1:1.5, the rotating speed of the ball mill is 250r/min, and the ball milling time is 4h;
Step 3, presintering:
Drying and sieving the primary ball milling slurry obtained in the step 2, putting the slurry into a corundum crucible, presintering the slurry for 2 hours in an oxygen atmosphere (oxygen partial pressure is 0.3MPa, and oxygen flow rate is 300-400 mL/min) at 800 ℃, cooling the slurry to room temperature along with a furnace after the presintering of the slurry is completed, and taking out the slurry to obtain a Li system microwave ferrite presintering material;
Step 4, secondary ball milling:
Adding the Li-based microwave ferrite pre-sintering material and deionized water obtained in the step 3 into a planetary ball mill for secondary ball milling, wherein the mass ratio of the pre-sintering material to the deionized water is 1:1.3, the rotating speed of the ball mill is 250r/min, the ball milling time is 6h, and the slurry is dried after the ball milling is completed;
step 5, molding:
Sieving the secondary ball milling material obtained in the step 4, adding 10wt.% of polyvinyl alcohol (PVA) binder corresponding to the mass of powder for granulating, and pressing into an annular green body sample by using a hydraulic press;
step 6, sintering:
Placing the green body sample obtained in the step 5 into a sintering furnace, heating to 600 ℃ at a speed of 1 ℃/min, and preserving heat for 2 hours to perform glue discharging; then, heating to the sintering temperature of 880 ℃ at the speed of 1 ℃/min, and preserving heat for 2 hours; after sintering, cooling to 600 ℃ at a speed of 1 ℃/min; and finally, naturally cooling to room temperature along with the furnace to obtain the Li microwave ferrite.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 1 is as follows: the apparent density ρ was 4.76g/cm 3, the saturation magnetization 4. Pi.M s was 3882Gs, the ferromagnetic resonance line width ΔH (@ 9.3 GHz) was 88Oe, the spin wave line width ΔH k was 14.1Oe, the dielectric constant ε (@ 9.3 GHz) was 14.90, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 2.59X10 -4, the Curie temperature T c was 308℃and the squareness degree R was 0.90.
Example 2
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.17mol％,ZnO 20.33mol％,TiO2 11.04mol％,Mn3O4 0.39mol％,Co3O4 0.04mol％,Fe2O355.94mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 2 is as follows: the apparent density ρ was 4.74g/cm 3, the saturation magnetization 4. Pi. M s was 3970Gs, the ferromagnetic resonance line width ΔH (@ 9.3 GHz) was 95Oe, the spin wave line width ΔH k was 11.8Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.11, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 1.03X10 -4, the Curie temperature T c was 310℃and the squareness R was 0.88.
Example 3
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.14mol％,ZnO 20.34mol％,TiO2 11.04mol％,Mn3O4 0.39mol％,Co3O4 0.08mol％,Fe2O355.92mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 3 is as follows: the apparent density ρ was 4.74g/cm 3, the saturation magnetization 4. Pi. M s was 3977Gs, the ferromagnetic resonance linewidth ΔH (@ 9.3 GHz) was 99Oe, the spin-wave linewidth ΔH k was 14.3Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.03, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 1.07X 10 -4, the Curie temperature T c was 310℃and the squareness R was 0.85.
Example 4
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.12mol％,ZnO 20.34mol％,TiO2 11.04mol％,Mn3O4 0.39mol％,Co3O4 0.12mol％,Fe2O355.9mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 4 is as follows: the apparent density ρ was 4.74g/cm 3, the saturation magnetization 4. Pi.M s was 3990Gs, the ferromagnetic resonance linewidth ΔH (@ 9.3 GHz) was 105Oe, the spin-wave linewidth ΔH k was 19.5Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.07, the dielectric loss tangent tan δ ε (@ 9.3 GHz) was 1.24X10 -4, the Curie temperature T c was 311℃and the squareness R was 0.89.
Example 5
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.09mol％,ZnO 20.34mol％,TiO2 11.04mol％,Mn3O4 0.39mol％,Co3O4 0.16mol％,Fe2O355.89mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 5 is as follows: the apparent density ρ was 4.75g/cm 3, the saturation magnetization 4. Pi.M s was 3973Gs, the ferromagnetic resonance line width ΔH (@ 9.3 GHz) was 104Oe, the spin wave line width ΔH k was 23.7Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.13, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 1.14X10 -4, the Curie temperature T c was 311℃and the squareness R was 0.89.
Example 6
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.06mol％,ZnO 20.35mol％,TiO2 11.05mol％,Mn3O4 0.39mol％,Co3O4 0.19mol％,Fe2O355.87mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 6 is as follows: the apparent density ρ was 4.75g/cm 3, the saturation magnetization 4. Pi. M s was 3955Gs, the ferromagnetic resonance line width ΔH (@ 9.3 GHz) was 105Oe, the spin wave line width ΔH k was 25.4Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.08, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 1.17X10 -4, the Curie temperature T c was 310℃and the squareness R was 0.87.
Example 7
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.04mol％,ZnO 20.35mol％,TiO2 11.05mol％,Mn3O4 0.39mol％,Co3O4 0.23mol％,Fe2O355.85mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 7 is as follows: the apparent density ρ was 4.75g/cm 3, the saturation magnetization 4. Pi.M s was 3926Gs, the ferromagnetic resonance linewidth ΔH (@ 9.3 GHz) was 107Oe, the spin-wave linewidth ΔH k was 22.1Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.17, the dielectric loss tangent tan δ ε (@ 9.3 GHz) was 1.26X10 -4, the Curie temperature T c was 310℃and the squareness degree R was 0.89.
Example 8
This embodiment differs from embodiment 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.01mol％,ZnO 20.35mol％,TiO2 11.05mol％,Mn3O4 0.39mol％,Co3O4 0.27mol％,Fe2O355.84mol％,Bi2O30.09mol％, and the other steps were the same as in example 1.
The performance of the high-power low-loss Li-based microwave ferrite for LTCC prepared in the embodiment 8 is as follows: the apparent density ρ was 4.74g/cm 3, the saturation magnetization 4. Pi. M s was 3901Gs, the ferromagnetic resonance line width ΔH (@ 9.3 GHz) was 110Oe, the spin wave line width ΔH k was 33.2Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.18, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 1.37X10 -4, the Curie temperature T c was 310℃and the squareness R was 0.88.
Comparative example
The comparative example is different from example 1 in that: in step 1, the raw materials were calculated and weighed according to Li2CO3 12.24mol％,ZnO 20.41mol％,TiO2 11.08mol％,Fe2O3 56.18mol％,Bi2O3 0.09mol％, and the other steps were the same as in example 1.
The properties of the Li-based microwave ferrite prepared in the comparative example are as follows: the apparent density ρ was 4.77g/cm 3, the saturation magnetization 4. Pi. M s was 4022Gs, the ferromagnetic resonance linewidth ΔH (@ 9.3 GHz) was 127Oe, the spin-wave linewidth ΔH k was 8.3Oe, the dielectric constant ε' (@ 9.3 GHz) was 15.29, the dielectric loss tangent tan. Delta. ε (@ 9.3 GHz) was 1.53X10 -4, the Curie temperature T c was 317℃and the squareness R was 0.87.
FIG. 1 is XRD patterns of ferrites obtained in comparative example, example 1 and example 8; FIG. 2 is a SEM image of a cross section of a Li-based microwave ferrite sample obtained in comparative example (a) and example 1 (b). Table 1 shows the performance parameters of the examples and comparative examples. In the Li ferrite with the Fe-deficient formula, the grain size distribution is changed by substitution of a trace amount of Mn, the proportion of fine grains (less than or equal to 1.0 mu m) is increased, the spin wave line width delta H k is obviously improved, and on the basis, co ions with rapid relaxation property are introduced, so that the spin wave line width delta H k of the microwave ferrite is further improved. Meanwhile, the addition of the micro-high valence Mn and the high valence Co is beneficial to reducing the Fe 2+ ion content in ferrite and reducing the microwave dielectric loss. In addition, mn is added to weaken the super-exchange effect of the A-B bit of the spinel ferrite, so that the magnetocrystalline anisotropy induced line width delta H a is reduced, and the total ferroresonance line width delta H is narrowed.
TABLE 1
Claims (2)
1. A high-power low-loss Li-based microwave ferrite for LTCC, characterized in that the Li-based microwave ferrite has the following contents according to respective standards ：Li2CO3 11.80～12.24mol％,ZnO19.87～20.41mol％,TiO2 10.78～11.08mol％,Mn3O4 0.39～2.65mol％,Co3O40.04～0.58mol％,Fe2O3 54.70～56.18mol％,Bi2O3 0.09mol％.
2. The preparation method of the high-power low-loss Li-based microwave ferrite for the LTCC is characterized by comprising the following steps of:
Step 1, weighing:
Taking Li2CO3、ZnO、TiO2、Mn3O4、Co3O4、Fe2O3、Bi2O3 as a raw material, and weighing the raw material according to the content Li2CO311.80～12.24mol％,ZnO 19.87～20.41mol％,TiO210.78～11.08mol％,Mn3O4 0.39～2.65mol％,Co3O4 0.04～0.58mol％,Fe2O354.70～56.18mol％,Bi2O3 0.09mol％ of each standard substance;
Step 2, ball milling for the first time:
Performing primary ball milling on the raw materials weighed in the step 1, wherein the rotating speed of the ball mill is 250r/min, and the ball milling time is 4h;
Step 3, presintering:
Drying and sieving the primary ball milling slurry obtained in the step2, presintering for 2-3 hours in an oxygen atmosphere at 750-850 ℃, cooling to room temperature along with a furnace after the presintering is completed, and taking out to obtain a Li microwave ferrite presintering material;
Step 4, secondary ball milling:
Performing secondary ball milling on the Li-based microwave ferrite pre-sintered material obtained in the step 3, wherein the rotating speed of the ball mill is 250r/min, the ball milling time is 6h, and drying the slurry after the ball milling is completed;
step 5, molding:
sieving the secondary ball milling material obtained in the step 4, adding a polyvinyl alcohol adhesive for granulating, and pressing into a green body sample by using a hydraulic press;
step 6, sintering:
Placing the green body sample obtained in the step 5 into a sintering furnace, heating to 600 ℃, and preserving heat for 1-2 h to perform glue discharging; then heating to the sintering temperature of 880-890 ℃, and preserving heat for 2-3 h; cooling to 600 ℃ after sintering is completed; and finally, naturally cooling to room temperature along with the furnace to obtain the Li microwave ferrite.
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