CN116789448A - Medium-temperature sintering high-Q-value microwave dielectric material and preparation method and application thereof - Google Patents
Medium-temperature sintering high-Q-value microwave dielectric material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a medium-temperature sintering high-Q-value microwave dielectric material and a preparation method thereof. The chemical composition of the medium-temperature sintering high-Q-value microwave dielectric material comprises: mgNb 2 O 6 Major phase, mg-V low melting second phase and Sb 2 O 5 A phase in which Sb 2 O 5 The phase exists in the ceramic in the form of solid solution; the medium-temperature sintering high-Q-value microwave dielectric material contains Mg element: nb element: (V element + Sb element) =1:2-2 x: x is more than or equal to 0.010 and less than or equal to 0.075; the total amount of the V element and the Sb element is x.
Description
Technical Field
The invention relates to a microwave dielectric material with a medium-temperature sintering high Q value and a preparation method thereof, belonging to the field of ceramic materials.
Background
The microwave dielectric ceramic is a functional ceramic which is applied to a microwave frequency band (300 MHz-300 GHz) and is used as a core device of a dielectric filter, and with the continuous development of the communication industry, tiO is used as the material 2 The ceramic filters represented gradually replaced the filter systems with metal cavities as the main material. In recent years, the rapid development of the fifth generation mobile communication, the demand of microwave dielectric ceramics reaches millions.
The three main directions of the development of microwave dielectric ceramics in recent years are that the dielectric constants are serialized, the temperature coefficient of the resonant frequency is near 0 and the low-temperature co-firing is performed. The dielectric constants are serialized to be suitable for devices with different signal frequency bands, and the device requirements of different sizes are met by adjusting the dielectric constants; the temperature coefficient of the resonant frequency is near 0, which is an important guarantee of the working stability of the device, and the good temperature coefficient of the resonant frequency is a big precondition for realizing the application; the traditional microwave dielectric ceramic is usually sintered at a high temperature above 1200 ℃ to obtain excellent dielectric properties, however, the high-temperature electrode material is high in price on one hand, and on the other hand, is limited to a certain extent in terms of conductivity and other properties, and in order to expand the application range of the microwave dielectric ceramic, a certain amount of sintering auxiliary agent is added to reduce the sintering temperature of the ceramic to 1083 ℃ so that the ceramic can be co-sintered with metallic copper or reduced to 950 ℃ so that the LTCC process can be realized, and the process can be suitable for the preparation of various electronic components, and greatly expands the application range of the microwave dielectric ceramic.
In order to further meet the use requirement of 5G communication on microwave dielectric ceramics, the sintering temperature is reduced, and meanwhile, the material itself is guaranteed to have a higher Qf value so as to guarantee the use requirement of high-frequency and large-flux of microwave communication equipment. MgNb in the existing K20 ceramic system 2 O 6 Ceramics, as a representative of K20 ceramic systems, have a higher Qf value (qf=100,000 ghz) and at the same time a higher Qf value relative to tantalate systemsThe low cost, high stability relative to niobate systems, makes it one of the key candidates for the new generation of communication technology. Currently, mgNb is prepared 2 O 6 The ceramic may be prepared by various methods such as solid phase reaction, sol-gel method, and hydrothermal method. However, the sintering temperature of the system material reaches 1300 ℃, meanwhile, the reduction of the sintering temperature is difficult to realize by taking Mg as a high-temperature metal, and the application range of the system material is limited by the excessively high sintering temperature.
Disclosure of Invention
Aiming at the problems, the invention provides a medium-temperature sintering high-Q-value microwave dielectric material and a preparation method thereof.
In one aspect, the invention provides a medium temperature sintered high Q microwave dielectric material, the chemical composition of which mainly comprises: mgNb 2 O 6 Major phase, mg-V low melting second phase and Sb 2 O 5 A phase in which Sb 2 O 5 The phase exists in the ceramic in the form of solid solution; the medium-temperature sintering high-Q-value microwave dielectric material contains Mg element: nb element: (V element+sb element) =1 (2-2 x): x is more than or equal to 0.010 and less than or equal to 0.075; the total amount of the V element and the Sb element is x.
In the present invention, the raw materials are weighed by the solid phase reaction method, and the raw materials are subjected to the micro substitution of the Nb ions with the V ions and Sb ions (Mg (Nb 1-x G x/2 ) 2 O 6-2.5x G=v and Sb), to form a part of Mg-V second phase with low loss and low melting point, so that MgNb 2 O 6 The ceramic achieves high densification and maintains a high Qf value while reducing the sintering temperature.
Preferably, the Mg-V low melting second phase comprises Mg 3 (VO 4 ) 2 And Mg (magnesium) 2 V 2 O 7 At least one of them.
Preferably, the molar ratio of the V element to the Sb element is 1:0 to 0:1, preferably 9:1 to 7:3, and more preferably 8:2.
Preferably, the medium temperature sintered high Q value microwave dielectric material has a dielectric constant of 19.48-20.30 and a dielectric loss of 1.28X10 -4 ～9.35×10 -5 The Qf value is 78400 to 107000.
Preferably, the density of the medium-temperature sintering high-Q-value microwave dielectric material is 4.70-4.85 g/cm 3 The relative density is 95.75-98.00%.
On the other hand, the invention provides a preparation method of the medium-temperature sintered high-Q-value microwave dielectric material, which comprises the following steps:
(1) The Mg source, nb source, V source and Sb source are mixed according to Mg (Nb 1-x G x/2 ) 2 O 6-2.5x Weighing and mixing G=V or/and Sb, and presintering at 800-900 ℃ for at least 4 hours to obtain synthetic powder;
(2) Ball milling, granulating and forming the obtained synthetic powder to obtain a ceramic blank;
(3) And after the ceramic blank is subjected to glue discharging, heating to 950-1200 ℃ for heat preservation for 4-6 hours, and cooling to 700-800 ℃ for heat preservation for 4-6 hours to obtain the medium-temperature sintering high-Q-value microwave dielectric material.
In the invention, by using MgNb 2 O 6 Non-stoichiometric substitution of small amounts of G in the ceramic matrix (microwave dielectric material containing Mg, nb and O elements) 2 O 5 The components play a role in reducing the activation energy of the sintering reaction on the ceramic, successfully reduce the sintering temperature of the ceramic matrix and realize the medium-temperature sintering. Specifically, the invention firstly adopts stoichiometric ratio to synthesize Mg (Nb 1-x G x/2 ) 2 O 6-2.5x The powder ensures that the composition of G can successfully synthesize the low-melting-point second phase on the basis of ensuring the excessive content of Mg, thereby realizing the reduction of sintering temperature on the basis of ensuring the microwave dielectric property of the material; the substituted G component is V 2 O 5 And Sb (Sb) 2 O 5 A substance consisting of at least one of the two oxides (preferably, V 2 O 5 Or V 2 O 5 And Sb (Sb) 2 O 5 ) Both the two oxides have lower melting points, can generate a low-loss low-melting point second phase with excessive Mg in the reaction process, is beneficial to reducing the sintering temperature of the ceramic matrix on the basis of ensuring a high Qf value, and widens MgNb 2 O 6 The ceramic is at medium temperatureAnd the application in the cofiring field expands the application market. The material system adopted by the invention has higher Qf value and lower sintering temperature than those reported in literature. Research shows that the V 2 O 5 And Sb (Sb) 2 O 5 The micro substitution can obviously reduce MgO-Nb 2 O 5 The sintering temperature of the binary system is therefore employed in the present invention in V 2 O 5 And Sb (Sb) 2 O 5 The sintering temperature can be reduced better by replacing substances. The preparation process has low cost and convenient method.
Preferably, in the step (1), the Mg source is MgO powder or/and basic MgCO 3 Powder; the Nb source is Nb 2 O 5 Powder; the V source is V 2 O 5 Powder; the Sb source is Sb 2 O 5 Powder; preferably, the particle size D of the V source and the Sb source 90 ＜3μm。
Preferably, in the step (1), the molar ratio of the V source to the Sb source is 0:1 to 1:0, preferably 9:1 to 7:3, more preferably 8:2.
Preferably, in the step (2), a binder is added during granulation, and the binder is a polyvinyl alcohol aqueous solution; the concentration of the polyvinyl alcohol aqueous solution is 4-8wt%.
Preferably, in the step (3), the temperature of the adhesive discharging is 400-600 ℃ and the time is 1-2 hours; the heating rate is 4-10 ℃/min; the cooling rate is 1-5 ℃/min.
In the invention, the medium-temperature sintering high-Q microwave dielectric material can be used for preparing an LTCC substrate, particularly for preparing the LTCC substrate by co-firing with Cu metal in a reducing atmosphere, and the sintering is realized at 950-1200 ℃.
The beneficial effects are that:
the dielectric constant of the microwave dielectric ceramic material prepared by the invention is 19.52, the resonance temperature coefficient is-70 ppm/DEG C, the higher Qf value 101300GHz and the sintering system is 1050 ℃/4h, and the microwave dielectric ceramic material can be used as a key core material of electronic components such as an antenna, a substrate and the like for microwave mobile communication and is widely applied to the fifth generation mobile communication industry. Compared with the prior art, the invention can prepareMgNb for medium temperature sintering 2 O 6 The method of the ceramic has the characteristics of simple process, can obviously improve the yield of the material while ensuring the performance of the material, is suitable for mass industrial production, and has important application value.
Drawings
FIG. 1 shows XRD patterns of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3 and example 4;
FIG. 2 is an enlarged XRD pattern of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3 and example 4;
fig. 3 shows the dielectric constant values of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3, and example 4;
fig. 4 shows Qf values of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3, and example 4.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof.
In the present disclosure, the medium temperature sintered high Q microwave dielectric material is made of Mg (Nb 1-x G x/2 ) 2 O 6-2.5x The system comprises a main body of a microwave dielectric material containing Mg, nb and O elements, wherein the component G contains V or/and Sb. Of these, qf is preferably not lower than 78400.
Preferably, the ratio of V to Sb is 0.9:0.1 to 0.7:0.3, preferably 0.8:0.2. Wherein x is from 0.01 to 0.075, more preferably from 0.025 to 0.05. Too high substitution amount of G is easy to cause deterioration of material performance, and a small amount of G can be added to effectively reduce sintering temperature of the material on the basis of keeping high Qf value.
The following exemplarily illustrates a preparation method of the medium-temperature sintered high-Q-value microwave dielectric material.
And (3) preparing synthetic powder. According to Mg (Nb) 1-x G x/2 ) 2 O 6-2.5x Is composed of Mg source, nb source, G source (V source and Sb source)) Mixing, and presintering to obtain synthetic powder. The molar substitution amount of G is between 0.05 and 0.20. The Mg source can be MgO or basic MgCO 3 . The Nb source may be Nb 2 O 5 . The V source may be V 2 O 5 . The Sb source may be Sb 2 O 5 . As an example, the microwave dielectric material comprises Mg (Nb 1-x G x/2 ) 2 O 6-2.5x Weighing, adding water, grinding into slurry by using zirconium balls on a planetary ball mill, drying, calcining and synthesizing to obtain synthetic powder. Wherein, the granularity D of the ball milling slurry 50 < 3 μm. The presintering synthesis temperature is 800-900 ℃, and the heat preservation time is not less than 4 hours. Preferably, the burn-in temperature is 850 ℃.
Wherein the G source may be G 2 O 5 For example V 2 O 5 And Sb (Sb) 2 O 5 Etc. Preferably, two types of V are controlled 2 O 5 And Sb (Sb) 2 O 5 The molar ratio of (2) is 9:1 to 7:3, preferably 8:2.
And ball milling, granulating and forming the synthesized powder to obtain a ceramic blank.
And sintering the ceramic blank under a specific sintering system to obtain the microwave dielectric material with the ultrahigh Q value. The specific sintering schedule includes: heating to 950-1150 ℃ at 5-10 ℃/min, preserving heat for 4-6 hours, then cooling to 700-800 ℃ at 1 ℃/min, and preserving heat for 4-6 hours.
In the invention, a vector network analyzer is adopted to test the dielectric constant of the obtained medium-temperature sintering high-Q-value microwave dielectric material. And testing the dielectric loss of the obtained medium-temperature sintered high-Q-value microwave dielectric material by adopting a vector network analyzer. And testing the density of the medium-temperature sintered high-Q-value microwave dielectric material by adopting an Archimedes drainage method. And testing the relative density of the medium-temperature sintered high-Q-value microwave dielectric material by adopting an Archimedes drainage method. And testing the Qf of the obtained medium-temperature sintered high-Q-value microwave dielectric material by adopting a vector network analyzer.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
(1) Accurately weighing Nb with purity more than 99.9 percent 2 O 5 0.975 mols, basic MgCO 3 1.0moL and G 2 O 5 0.0125moL (x=0.025, G is V and Sb, the ratio of the two elements is 0.8:0.2), adding into a nylon ball milling tank, pouring into deionized water, and the weight ratio of the zirconia balls with the diameter of 10mm is as follows: ball: water = 1:2:1.5; ball milling time is 4 hours, the granularity D50 of ball milling slurry is 3, and after ball milling, the slurry is dried and dried in an oven at 120 ℃ for one night. Placing the dried powder into a sagger, calcining for 4 hours at 850 ℃, and cooling along with a furnace to obtain synthetic powder;
(2) 100g of the synthetic powder was weighed, added to a nylon ball mill tank, and deionized water and zirconia balls with a diameter of 10mm were poured. The weight ratio of the materials is as follows: ball: water = 1:2:1.5; ball milling time is 4h until ball milling slurry granularity D 50 Is 3 μm. After ball milling, the slurry is poured into a enamel tray, put into an oven and dried at 130 ℃. Granulating with PVA water solution to obtain granulated powder. Placing the granulated powder into a die with the diameter of 6mm for molding under the pressure of 100MPa, and setting the height of a molded sample to be 4mm to obtain a ceramic blank;
(3) And (3) placing the ceramic blank into a muffle furnace, heating to 600 ℃ at a speed of 4 ℃/min, preserving heat for 2 hours, and performing glue discharging treatment. Then heating to 1150 ℃ at the speed of 4 ℃/min, preserving heat for 4 hours, then cooling to 800 ℃ at the speed of 1 ℃/min, and preserving heat for 5 hours to obtain the microwave dielectric material, wherein the performance is shown in table 1.
Example 2
The preparation process of the microwave dielectric material in this embodiment 2 is described with reference to embodiment 1, and the difference is that: x=0.050; then the five samples are respectively heated to 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and heat-preserving for 4 hours according to the speed of 4 ℃/min, then 1 ℃/min is reduced to 800 ℃ and heat-preserving for 5 hours, and the microwave medium material is prepared.
Example 3
The preparation process of the microwave dielectric material in this embodiment 3 is described with reference to embodiment 2, and the difference is that: x=0.075.
Example 4
The preparation process of the microwave dielectric material in this example 4 is described with reference to example 2, except that: x=0.010.
Example 5
The preparation process of the microwave dielectric material in this example 5 is described with reference to example 2, except that: x=0.040.
Example 6
The preparation process of the microwave dielectric material in this example 6 is described with reference to example 2, except that: x=0.060.
Example 7
The preparation process of the microwave dielectric material in this example 7 is described with reference to example 2, except that: v: sb=9:1.
Example 8
The preparation process of the microwave dielectric material in this example 8 is described with reference to example 2, except that: v: sb=7:3, its samples were raised to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ respectively.
Example 9
The preparation process of the microwave dielectric material in this example 9 is described with reference to example 2, except that: v: sb=6:1, the samples of which were raised to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ respectively.
Example 10
The preparation process of the microwave dielectric material in this embodiment 10 is described with reference to embodiment 2, except that: v: sb=5:5, and the samples were heated to 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃ respectively.
Example 11
The preparation process of the microwave dielectric material in this example 11 is described with reference to example 2, except that: v: sb=1:0.
Example 12
The preparation process of the microwave dielectric material in this embodiment 12 is described with reference to embodiment 2, except that: v: sb=0:1, and the samples thereof were heated to 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, respectively.
Comparative example 1
The procedure for the preparation of the microwave dielectric material of this comparative example 1 is described with reference to example 2, with the difference that: the preparation of the synthetic powder comprises the following steps: 1.0moL of MgNb 2 O 6 V of powder, 0.025moL 2 O 5 Powder and Sb 2 O 5 Mixed powder of the powders (V: sb=8:2) was mixed as a synthetic powder.
Comparative example 2
The procedure for preparing the microwave dielectric material in this comparative example 2 is described with reference to example 2, except that: according to Mg (Nb) 1-x G x ) 2 O 6 The raw materials are weighed without shortage.
Table 1 shows the composition and properties of the microwave dielectric material prepared by the invention
FIGS. 1 and 2 show XRD patterns of the microwave dielectric materials before and after doping the G component prepared in example 1, example 2, example 3, and example 4, in which it can be seen that MgNb as a main crystal phase can be obtained after substituting the sintering aid of the present invention 2 O 6 Accompanied by a small amount of Mg-V low melting second phase. Fig. 3 and 4 are graphs showing the effect of the substitution of the sintering aid oxide of the present invention on the dielectric constant and the quality factor of the ceramic according to example 1, wherein the substitution amount of G is 0.010, 0.025, 0.050, and 0.075, respectively, corresponding to examples 1, 2, 3, and 4 of the present invention, it can be seen that the sintering temperature of the ceramic can be reduced while maintaining a high quality factor, but the sintering temperature of the material is not significantly reduced when the substitution amount is too high, and the quality factor is reduced.
Claims (11)
1. The medium-temperature sintering high-Q-value microwave dielectric material is characterized by comprising the following chemical components in percentage by weight: mgNb 2 O 6 Major phase, mg-V low melting second phase and Sb 2 O 5 A phase in which Sb 2 O 5 The phase exists in the ceramic in the form of solid solution; the medium-temperature sintering high-Q-value microwave dielectric material contains Mg element: nb element: (V element + Sb element) =1:2-2 x: x is more than or equal to 0.010 and less than or equal to 0.075; the total amount of the V element and the Sb element is x.
2. The medium temperature sintered high Q microwave dielectric material of claim 1, wherein the Mg-V low melting second phase comprises Mg 3 (VO 4 ) 2 And Mg (magnesium) 2 V 2 O 7 At least one of them.
3. The medium temperature sintered high Q microwave dielectric material according to claim 1, wherein the molar ratio of V element to Sb element is 1:0 to 0:1, preferably 9:1 to 7:3, more preferably 8:2.
4. The medium temperature sintered high Q microwave dielectric material according to claim 1, characterized in that the medium temperature sintered high Q microwave dielectric material has a dielectric constant of 19.48-20.30 and a dielectric loss of 1.28 x 10 -4 ～9.35×10 -5 The Qf value is 78400 to 107000.
5. The medium temperature sintered high Q microwave dielectric material according to any one of claims 1-4, wherein the medium temperature sintered high Q microwave dielectric material has a density of 4.70-4.85 g/cm 3 The relative density is 95.75-98.00%.
6. A method for preparing a medium temperature sintered high Q microwave dielectric material according to any one of claims 1 to 5, comprising:
(1) The Mg source, nb source, V source and Sb source are mixed according to Mg (Nb 1-x G x/2 ) 2 O 6-2.5x Weighing and mixing G=V or/and Sb, and presintering at 800-900 ℃ for at least 4 hours to obtain synthetic powder;
(2) Ball milling, granulating and forming the obtained synthetic powder to obtain a ceramic blank;
(3) And after the ceramic blank is subjected to glue discharging, heating to 950-1200 ℃ for heat preservation for 4-6 hours, and cooling to 700-800 ℃ for heat preservation for 4-6 hours to obtain the medium-temperature sintering high-Q-value microwave dielectric material.
7. The method according to claim 6, wherein in the step (1), the Mg source is MgO powder or/and basic MgCO 3 Powder; the Nb source is Nb 2 O 5 Powder; the V source is V 2 O 5 Powder; the Sb source is Sb 2 O 5 Powder; preferably, the particle size D of the V source and the Sb source 90 ＜3μm。
8. The method according to claim 6 or 7, wherein in step (1), the molar ratio of V source to Sb source is 0:1 to 1:0, preferably 9:1 to 7:3, more preferably 8:2.
9. The method according to any one of claims 6 to 8, wherein in step (2), a binder is added during granulation, and the binder is an aqueous solution of polyvinyl alcohol; the concentration of the polyvinyl alcohol aqueous solution is 4-8wt%.
10. The method according to any one of claims 6 to 9, wherein in step (3), the temperature of the discharged glue is 400 to 600 ℃ for 1 to 2 hours; the heating rate is 4-10 ℃/min; the cooling rate is 1-5 ℃/min.
11. Use of a medium temperature sintered high Q microwave dielectric material according to any one of claims 1-5 for the preparation of an LTCC substrate.
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