CN117362032A - Temperature-stable low-loss low-temperature cofiring ceramic material and preparation method thereof - Google Patents
Temperature-stable low-loss low-temperature cofiring ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 64
- 239000013078 crystal Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 125
- 239000002002 slurry Substances 0.000 claims description 79
- 238000010438 heat treatment Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 36
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
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- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000002352 surface water Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 4
- 239000004332 silver Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 72
- 239000011777 magnesium Substances 0.000 description 52
- 239000000463 material Substances 0.000 description 37
- 238000001035 drying Methods 0.000 description 28
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- 238000003825 pressing Methods 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007873 sieving Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000010344 co-firing Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000010354 integration Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000003921 particle size analysis Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009766 low-temperature sintering Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910008572 Li2O—B2O3-SiO2 Inorganic materials 0.000 description 1
- 229910008585 Li2O—B2O3—SiO2 Inorganic materials 0.000 description 1
- RMORUKBSBQILPR-UHFFFAOYSA-N [Nb].[Mg].[Li] Chemical class [Nb].[Mg].[Li] RMORUKBSBQILPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a temperature-stable low-loss low-temperature co-fired ceramic material and a preparation method thereof, wherein the raw materials of the ceramic material comprise a main crystal phase, a secondary crystal phase and low-melting-point oxide; the main crystal phase is pure phase Li 3 Mg 2 NbO 6 TiO with rutile structure as secondary crystal phase 2 The low-melting point oxide is V 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The mass of the secondary crystal phase accounts for 0.5-4wt% of the mass of the main crystal phase; the mass of the low-melting point oxide accounts for 0.5-3 wt% of the mass of the main crystal phase. In the ceramic material provided by the invention, rutile type TiO 2 Can improve temperature stability, has pinning effect in the growth process of crystal grains, and has low melting point V 2 O 5 The ceramic material is well sintered at 800-950 ℃ and can be co-sintered with a silver electrode. Meanwhile, the sintering temperature is reduced, the density of the ceramic is improved, the microcosmic appearance is optimized, and the ceramic has excellent dielectric properties.
Description
Technical Field
The invention relates to the technical field of microwave dielectric ceramic materials, in particular to a temperature-stable low-loss low-temperature co-fired ceramic material and a preparation method thereof.
Background
With the rapid development of communication technology, microwave devices with low consumption and high integration level are becoming the market dominant. Currently, many integrated packaging methods are available, including thin film technology, semiconductor technology, low temperature co-fired ceramic technology, and the like. Among the integrated packaging technologies, LTCC technology has become a mainstream technology for realizing the integration of current electronic components due to advantages of strong integration capability, low cost, high compatibility, high transmission characteristics, and the like.
In recent years, li 3 Mg 2 NbO 6 The ceramic is a novel low-loss microwave dielectric ceramic newly developed in recent years, has good microwave dielectric property and is widely studied, but the application of the ceramic in the LTCC integration field is limited by the excessively high sintering temperature (more than or equal to 1250 ℃). Such as Tianjin university Zhang et al (Low temperature sintering and microwave dielectric properties of Li) 3 Mg 2 NbO 6 ceramics doped with Li 2 O-B 2 O 3 -SiO 2 glass, journal of Alloys and Compounds,2017, 690:688-691) can suitably reduce Li by low melting additives 3 Mg 2 NbO 6 The sintering temperature of the ceramic, but also the introduction of the second phase, worsens the temperature coefficient of the resonant frequency of the ceramic. Therefore, the former research results show that the sintering temperature can be reduced by adding the sintering aid into the ceramic, so that the ceramic is crystallized at a temperature point lower than the normal sintering temperature, and the sintering is realizedDensification. However, li 3 Mg 2 NbO 6 The microwave ceramic is sintered at low temperature under the condition of uneven crystallization, and after the sintering aid is added, densification can be realized at a lower temperature, but the addition of the sintering aid also causes uneven ceramic grain size, so that the dielectric property of the ceramic is limited.
As another example, the university of western amp industry Wang Pinglu is in the literature (Low loss and low temperature sintering of Li 3 Mg 2 NbO 6 ceramics for LTCC applications, materials Research Express,2019, 6:086313) discloses a Li 3 Mg 2 NbO 6 -xV 2 O 5 (x=0.25-1.25 wt%) materials, although the q×f value of the materials is increased, the τf value is still lower and larger, and the low-temperature cofired ceramic materials realizing temperature stabilization type low loss are still not satisfied. For another example, in chinese patent application publication No. CN105693241a, a lithium magnesium niobium series microwave dielectric ceramic is prepared, after being presintered at 1000-1050 ℃, crushed, and then ground by using an organic system such as absolute ethyl alcohol, and sintered at 1175-1225 ℃, but the sintering temperature is high, and there is a problem of organic waste water treatment, and the characteristic matching with the metal cofiring is not achieved.
In order to obtain the low-temperature co-fired ceramic material with stable temperature and low loss, higher requirements are put on miniaturized, integrated, stable, low-cost and low-loss components.
Disclosure of Invention
The technical problem to be solved by the invention is how to improve Li under the premise of low-temperature sintering 3 Mg 2 NbO 6 Dielectric properties of ceramics.
The invention solves the technical problems by the following technical means:
a temperature stable low-loss low-temperature co-fired ceramic material comprises a main crystal phase, a secondary crystal phase and a low-melting-point oxide as raw materials; the main crystal phase is pure phase Li 3 Mg 2 NbO 6 The secondary crystal phase is rutile crystal structure TiO 2 The low-melting point oxide is V 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The mass of the secondary crystal phase accounts for 0.5-4wt% of the mass of the main crystal phase; the quality of the low-melting point oxideThe mass of the crystal phase is 0.5-3 wt% of the mass of the main crystal phase.
Preferably, the temperature stable low-loss low-temperature co-fired ceramic material has a relative dielectric constant epsilon r 13.5-15, the quality factor Qxf is 78,000-110,100 GHz, and the resonant frequency temperature coefficient tau f Is-10 to-1 ppm/DEG C.
The invention also provides a preparation method of the temperature-stable low-loss low-temperature co-fired ceramic material, which comprises the following steps: mgO, li 2 CO 3 、Nb 2 O 5 According to Li 3 Mg 2 NbO 6 Proportioning the stoichiometric ratio, ball milling the prepared raw materials for the first time, presintering, and mixing with V 2 O 5 And rutile crystal structure TiO 2 And mixing, performing secondary ball milling, granulating, forming and sintering to obtain the temperature-stable low-loss low-temperature cofired ceramic material.
Preferably, the method further comprises calcining MgO raw material at 1000 ℃ to ensure MgO crystal form and exclude surface water absorption; the presintering temperature is 850-1200 ℃ and the presintering time is 1-6 hours.
Preferably, the rutile crystal structure TiO 2 Selecting anatase type TiO 2 Is converted after high temperature treatment at 850-1200 ℃.
Preferably, the first ball milling and the second ball milling are wet ball milling; deionized water is used as a solvent, zirconium dioxide balls are used as ball milling media, and in the ball milling process, the mass ratio of raw materials, zirconium dioxide balls and deionized water is 1:3 to 6:1.5 to 3.5, the rotating speed is 200 to 350rad/min, and the ball milling time is 1 to 10 hours.
Preferably, the first ball milling is carried out to obtain a first slurry, the particle size D50 is 0.5-1.5 mu m, the second ball milling is carried out to obtain a second slurry, and the particle size D50 is 0.8-2.5 mu m.
Preferably, in the granulation process, the granulating agent is a polyvinyl alcohol aqueous solution with a mass concentration of 10-15%.
Preferably, the sintering temperature is 800-950 ℃ and the time is 1-6 hours.
Preferably, the sintering comprises heating from normal temperature to 400-500 ℃ at a heating rate of 1.0-2.5 ℃/min, maintaining at 400-500 ℃ for 1-6 hours, and heating to 800-950 ℃ at a heating rate of 1.0-2.5 ℃/min for 1-6 hours.
Preferably, the preparation method of the temperature-stable low-loss low-temperature co-fired ceramic material comprises the following steps:
step 1: preparing materials for the first time; calcining MgO raw material at 1000 ℃ to ensure crystal form and eliminate the influence of water absorption, and then calcining MgO and Li as raw materials 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Is prepared according to the stoichiometric ratio of the raw materials;
step 2: mixing materials; ball milling the raw materials obtained in the step 1, and placing the raw materials, a solvent and a ball milling medium in a ball mill for wet ball milling in the ball milling process to obtain first slurry, wherein the particle size D50 of the first slurry is 0.5-1.5 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; presintering the dried powder obtained in the step 3 at 900-1100 ℃ for 1-6 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase type TiO 2 Calcining at 850-1200 deg.c to convert into rutile crystal structure;
step 6: performing secondary batching and ball milling; the presintered powder obtained in the step 4 and the rutile crystal structure TiO obtained in the step 5 are calcined 2 V (V) 2 O 5 Mixing and then carrying out mixed ball milling; in the ball milling process, placing the raw materials, a solvent and a ball milling medium into a ball mill for wet ball milling to obtain second slurry, wherein the particle size D50 of the second slurry is 0.8-2.5 mu m;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body;
step 8: sintering; sintering the green body obtained in the step 7 for 1-6 hours at 800-950 ℃ to prepare the temperature-stable low-loss low-temperature cofiring ceramic material.
Preferably, in step 3, the temperature of the drying is 70 to 150 ℃.
Compared with the prior art, the invention has the following beneficial effects:
due to Li 3 Mg 2 NbO 6 When the sintering aid is added into the ceramic, the ceramic is easy to crystallize, the grains of the ceramic material are easy to be uneven, and the crystallization of a plurality of small-size grains is caused, so that the dielectric property of the ceramic is limited. The invention selects V 2 O 5 TiO as a low-melting-point sintering aid 2 As the temperature coefficient compensator and the pinning material are secondary crystal phases, li can be realized 3 Mg 2 NbO 6 The sintering temperature of the ceramic is regulated to be within the range of 800-950 ℃, so that the forming sintering temperature of the crystal form can be remarkably reduced, and most importantly, the ceramic powder material can be matched with an Ag electrode for co-firing, and the Ag diffusion is basically avoided, thereby meeting the requirements of low-temperature co-firing temperature and co-firing matching property. Moreover, the formula and the preparation process of the invention also obviously improve the density of the ceramic matrix and the uniformity of the grain size, and realize the temperature coefficient of the near zero resonance frequency. The temperature-stable low-loss low-temperature cofiring ceramic material prepared by the invention has the relative dielectric constant epsilon r 13.5-15, the quality factor Qxf is 78,000-110,100 GHz, and the resonant frequency temperature coefficient tau f Is-10 to-1 ppm/DEG C.
Therefore, deionized water is adopted as a ball milling mixing medium, and the simple low-melting-point oxide V is adopted 2 O 5 Preparation of TiO of rutile Crystal form Structure as sintering aid 2 As a temperature coefficient regulator of a secondary crystal phase, plays a role in pinning and controlling abnormal growth of crystal grains, reduces sintering temperature conditions to realize matching cofiring with metallic silver, and improves micro-ceramicThe wave dielectric property realizes the effects of environmental protection, energy saving and safety, and has remarkable industrial application prospect.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of materials obtained in various examples and comparative examples of the present invention;
FIG. 2 is an SEM image of the materials prepared in comparative example 1 (FIG. a) and example 4 (FIG. b) of the present invention;
FIG. 3 is an XRD pattern (upper left), SEM pattern (upper right) and EDS pattern (lower left and lower right) of the material prepared in example 4 of the present invention after co-firing with a silver electrode;
FIG. 4 shows anatase TiO according to example 1 of the present invention 2 SEM image before sintering;
FIG. 5 shows anatase TiO according to example 1 of the present invention 2 XRD pattern before sintering;
FIG. 6 shows a rutile crystalline structure TiO prepared in example 1 of the present invention 2 SEM images of (a);
FIG. 7 shows a rutile crystalline structure TiO prepared by sintering in example 1 of the present invention 2 An XRD pattern of (b);
FIG. 8 is a PSA graph of a first slurry particle size obtained by a first ball milling in example 1 of the present invention;
fig. 9 is a PSA chart showing the particle size of the second slurry obtained by the second ball milling in example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
MgO in the following examples and comparative examples is MgO after calcination at 1000 ℃.
Example 1
A preparation method of a temperature-stable low-loss low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:6:1.5, the rotating speed is 320rad/min, the ball milling time is 1 hour, and the first slurry is obtained, and the particle size of the slurry D50 is 0.69 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1050 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase type TiO 2 The powder is calcined after being kept at 1060 ℃ for 3 hours and then is converted into TiO with rutile crystal structure 2 。
Step 6: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And the rutile crystal structure TiO in the step 5 2 V (V) 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1.5wt% of TiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 0.5wt% of the mass. During the ball milling processPutting the raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as ball milling media into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:6:1.5, the rotating speed is 320rad/min, the ball milling time is 1 hour, and a second sizing agent is obtained, and the size D50 of the sizing agent is 1.88 mu m;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 10%;
step 8: sintering; and (3) heating the green body obtained in the step (7) to 400 ℃ from normal temperature at a heating rate of 2 ℃/min, keeping the temperature for 6 hours, and heating to 900 ℃ at a heating rate of 1 ℃/min to sinter for 4 hours to prepare the temperature-stable low-loss low-temperature co-fired ceramic material.
Example 2
A preparation method of a temperature-stable low-loss low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:3:3.5, the rotating speed is 220rad/min, the ball milling time is 6 hours, and the first slurry is obtained, and the particle size of the slurry D50 is 0.70 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase type TiO 2 The powder is calcined after heat preservation for 3h at 980 ℃ and is converted into TiO with rutile crystal structure 2 。
Step 6: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And the rutile crystal structure TiO in the step 5 2 V (V) 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1wt% of TiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1wt% of the mass. In the ball milling process, placing raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as a ball milling medium into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:3:3.5, the rotating speed is 220rad/min, the ball milling time is 6 hours, and a second slurry is obtained, and the particle size of the slurry D50 is 2.0 mu m;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 15%;
step 8: sintering; and (3) heating the green body obtained in the step (7) to 500 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 1 hour, and heating to 900 ℃ at a heating rate of 2 ℃/min to sinter for 4 hours to prepare the temperature-stable low-loss low-temperature co-fired ceramic material.
Example 3
A preparation method of a temperature-stable low-loss low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:6:2, the rotating speed is 300rad/min, the ball milling time is 3 hours, and the first slurry is obtained, and the particle size of the slurry D50 is 0.85 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 for 2 hours at 950 ℃ to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase TiO 2 Calcining at 1000 ℃ for 4 hours and then converting the mixture into TiO with rutile crystal structure 2 。
Step 6: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And the rutile crystal structure TiO in the step 5 2 V (V) 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1wt% of TiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 2wt% of the mass. In the ball milling process, placing raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as a ball milling medium into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:6:2, the rotating speed is 300rad/min, the ball milling time is 3 hours, and a second slurry is obtained, and the particle size of the slurry D50 is 1.95 mu m;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 12%;
step 8: sintering; and (3) heating the green body obtained in the step (7) to 420 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 4 hours, and heating to 900 ℃ at a heating rate of 1 ℃/min to sinter for 4 hours to prepare the temperature-stable low-loss low-temperature co-fired ceramic material.
Example 4
A preparation method of a temperature-stable low-loss low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:3:3, the rotating speed is 250rad/min, the ball milling time is 4 hours, and the first slurry is obtained, and the particle size of the slurry D50 is 0.76 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase TiO 2 Calcining at 950 ℃ for 4 hours and then converting the mixture into TiO with rutile crystal structure 2 。
Step 6: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And the rutile crystal structure TiO in the step 5 2 V (V) 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1wt% of TiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 4wt% of the mass. In the ball milling process, the raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as ball milling media are placed in a ball mill for wet ball milling, and the raw materials and the zirconium dioxide balls are subjected to wet ball millingThe mass ratio of deionized water is 1:3:3, the rotating speed is 250rad/min, the ball milling time is 4 hours, and a second slurry with the particle size of 2.13 mu m is obtained;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 13%;
step 8: sintering; and (3) heating the green body obtained in the step (7) to 480 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 5 hours, and heating to 900 ℃ at a heating rate of 1 ℃/min to sinter for 4 hours to prepare the temperature-stable low-loss low-temperature co-fired ceramic material.
Example 5
A preparation method of a temperature-stable low-loss low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:5:2, the rotating speed is 280rad/min, and the ball milling time is 5 hours, so as to obtain first slurry; slurry D50 particle size of 0.92 μm;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase TiO 2 Calcining at 1200 ℃ for 4 hours and then turningTiO changed into rutile crystal structure 2 。
Step 6: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And the rutile crystal structure TiO in the step 5 2 V (V) 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 2wt% of mass, tiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 4wt% of the mass. In the ball milling process, placing raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as a ball milling medium into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:5:2, the rotating speed is 280rad/min, the ball milling time is 5 hours, and a second slurry is obtained, and the particle size of the slurry D50 is 2.38 mu m;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 14%;
step 8: sintering; and (3) heating the green body obtained in the step (7) to 400 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 3 hours, and heating to 875 ℃ at a heating rate of 1 ℃/min to sinter for 4 hours to prepare the temperature-stable low-loss low-temperature cofired ceramic material.
Comparative example 1
A preparation method of a low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:3:3.5, the rotating speed is 220rad/min, the ball milling time is 6 hours, and the first slurry is obtained, and the particle size of the slurry D50 is 1.09 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And V is equal to 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1wt% of the mass, in the ball milling process, putting the raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as a ball milling medium into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:3:3.5, the rotating speed is 220rad/min, the ball milling time is 6 hours, and a second slurry is obtained, and the particle size of the slurry D50 is 3.55 mu m;
step 6: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 5, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 15%;
step 7: sintering; and (3) heating the green body obtained in the step (6) to 500 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 1 hour, and heating to 950 ℃ at a heating rate of 2 ℃/min to sinter for 4 hours to prepare the low-temperature co-fired ceramic material.
Comparative example 2
A preparation method of a low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:3:3.5, the rotating speed is 220rad/min, the ball milling time is 6 hours, and the first slurry is obtained, and the particle size of the slurry D50 is 0.95 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: tiO with rutile crystal structure 2 Preparing; anatase TiO 2 Calcining at 1200 ℃ for 4 hours and then converting the mixture into TiO with rutile crystal structure 2 。
Step 6: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 And the rutile crystal structure TiO in the step 5 2 V (V) 2 O 5 Ball milling after mixing, wherein V 2 O 5 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 1wt% of TiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 0.1wt% of the mass. In the ball milling process, placing raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as a ball milling medium into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:3:3.5, the rotating speed is 220rad/min, the ball milling time is 6 hours, and a second slurry is obtained, and the particle size of the slurry D50 is 8.58 mu m;
step 7: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 6, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 15%;
step 8: sintering; and (3) heating the green body obtained in the step (7) to 500 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 1 hour, and heating to 925 ℃ at a heating rate of 2 ℃/min to sinter for 4 hours to prepare the low-temperature co-fired ceramic material.
Comparative example 3
A preparation method of a low-temperature co-fired ceramic material comprises the following steps:
step 1: batching; mgO, li as raw material 2 CO 3 、Nb 2 O 5 According to the chemical formula Li 3 Mg 2 NbO 6 Proportioning the materials according to the stoichiometric ratio;
step 2: mixing materials; ball milling is carried out on the raw materials obtained in the step 1, in the ball milling process, the raw materials, solvent deionized water and ball milling medium zirconium dioxide balls are placed in a ball mill for wet ball milling, and the mass ratio of the raw materials, the zirconium dioxide balls and the deionized water is 1:5:2.5, rotating at 200rad/min, ball milling for 5 hours to obtain a first slurry, wherein the particle size of the slurry D50 is 2.35 mu m;
step 3: drying the slurry; drying the first slurry obtained in the step 2 to obtain a dried mixture, and sieving the dried mixture to obtain dry powder;
step 4: presintering; calcining the dried powder obtained in the step 3 at 1000 ℃ for 2 hours to enable the dried powder to perform presintering reaction to obtain presintering powder Li 3 Mg 2 NbO 6 ；
Step 5: ball milling; the presintered powder Li obtained in the step 4 is subjected to 3 Mg 2 NbO 6 TiO with rutile crystal structure 2 Ball milling is carried out after mixing, wherein TiO 2 The mass of (a) is that the presintered powder Li 3 Mg 2 NbO 6 4wt% of the mass, in the ball milling process, putting the raw materials, deionized water serving as a solvent and zirconium dioxide balls serving as a ball milling medium into a ball mill for wet ball milling, wherein the mass ratio of the raw materials to the zirconium dioxide balls to the deionized water is 1:5:2.5, the rotating speed is 200rad/min, the ball milling time is 6 hours, and a second slurry is obtained, and the particle size of the slurry D50 is 4.85 mu m;
step 6: granulating and pressing a green body; drying and crushing the second slurry obtained in the step 5, adding a granulating agent into the second slurry for granulating, and pressing the granulated powder to form a green body; wherein the granulating agent is a polyvinyl alcohol aqueous solution with the mass concentration of 15%;
step 7: sintering; and (3) heating the green body obtained in the step (6) to 400 ℃ from normal temperature at a heating rate of 1 ℃/min, keeping the temperature for 1 hour, and heating to 950 ℃ at a heating rate of 2 ℃/min to sinter for 4 hours to prepare the low-temperature co-fired ceramic material.
FIG. 1 is an X-ray diffraction (XRD) pattern of materials obtained in various examples and comparative examples of the present invention; wherein the patterns expressed by 0wt%, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 4wt% are XRD of comparative example 1, comparative example 2, example 1, example 2, example 3, example 4, respectively; as can be seen from the graph in FIG. 1, in TiO 2 At levels less than 2wt%, the XRD diffractometer did not find the presence of the second phase, indicating that the second phase was not sufficiently detectable, whereas at levels up to 4wt%, the second phase appeared, with a pinned base structure.
FIG. 2 is an SEM image of the material prepared in comparative example 1 (FIG. a) and example 4 (FIG. b), from which it can be seen that TiO is added 2 Indeed, the pinning effect can be achieved, the microcosmic appearance is optimized, and the uniformity of grains is ensured.
Fig. 3 shows XRD, SEM and EDS results of the material prepared in example 4 of the present invention after co-firing with silver electrodes, from which it can be seen that the ceramic matrix did not chemically react with Ag during co-firing. And there is a clear boundary between ceramic and Ag electrode. These results show that the ceramic material provided by the invention has good chemical compatibility with Ag electrode, and is beneficial to practical application in LTCC devices.
Fig. 4 is an SEM image of the nano-scale anatase titania material used in example 1 of the present invention, and it can be seen from the image that the nano-scale titania particles are fine and uniform, have extremely high specific surface energy, and exhibit the appearance of agglomeration properties of the nanomaterial, which illustrates the nanomaterial properties of the material.
Fig. 5 is an XRD pattern of the nano-sized anatase titania material used in example 1 according to the present invention, from which it can be seen that the nano-sized titania particles were anatase upon X-ray diffraction analysis.
Fig. 6 is an SEM image of titanium dioxide formed by calcining the nano-sized anatase titanium dioxide material according to example 1 of the present invention, and it can be seen from the figure that the titanium dioxide particles have been significantly grown after the conversion by high temperature firing, and are in a primary agglomerate shape, which provides a scheme basis for the ball milling conditions of the present invention.
Fig. 7 is an X-ray diffraction analysis of titanium dioxide formed by calcining the nano-sized anatase titanium dioxide material of example 1 according to the present invention, showing that a rutile titanium dioxide crystal phase diagram is formed, from which it can be seen that the titanium dioxide particles have all been converted to the rutile form after being subjected to high temperature firing transformation, providing a titanium dioxide raw material having a pure rutile phase structure according to the present invention.
Fig. 8 is a graph of laser particle size analysis and particle size analysis of the slurry after the first ball milling in example 1 of the present invention, and it can be seen from the graph that the particle size of the slurry formed by the first ball milling is effectively controlled to be submicron, and good support is provided for sieving in the subsequent stage of the present invention.
Fig. 9 is a graph of laser particle size analysis and particle size analysis of the slurry after the second ball milling in the embodiment 1 of the present invention, and it can be seen from the graph that the particle size of the slurry formed by the second mixed ball milling is effectively controlled, and is all submicron, so that good support is provided for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to the present invention.
Table 1 shows the sintering temperatures and microwave dielectric properties of samples of the present invention and comparative examples, and the microwave dielectric properties were measured by the resonant cavity method.
TABLE 1
The invention selects V 2 O 5 TiO as a burn aid 2 Li is used as a temperature coefficient compensator and a pinning material 3 Mg 2 NbO 6 The sintering temperature of the ceramic is regulated to be within the range of 800-950 ℃, and the sintering temperature is obviously reduced, so that the powder material can be matched with an Ag electrode for co-firing, and the Ag diffusion is basically avoided, and the requirement of low-temperature co-firing temperature is met. Meanwhile, the compactness of the ceramic matrix is improved, the uniformity of the grain size is improved, and the near-zero resonance frequency temperature coefficient is realized. Meanwhile, the temperature-stable low-loss low-temperature cofiring ceramic material prepared by the invention has the relative dielectric constant epsilon r 13.5-15, the quality factor Qxf is 78,000-110,100 GHz, and the resonant frequency temperature coefficient tau f Is-10 to-1 ppm/DEG C.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A temperature stable low-loss low-temperature co-fired ceramic material is characterized in that: the raw materials comprise a main crystal phase, a secondary crystal phase and low-melting-point oxide; the main crystal phase is pure phase Li 3 Mg 2 NbO 6 The secondary crystal phase is rutile crystal structure TiO 2 The low-melting point oxide is V 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The mass of the secondary crystal phase accounts for 0.5-4wt% of the mass of the main crystal phase; the mass of the low-melting point oxide accounts for 0.5-3 wt% of the mass of the main crystal phase.
2. The temperature stable low loss low temperature cofired ceramic material of claim 1, wherein: its relative dielectric constant epsilon r 13.5-15, the quality factor Qxf is 78,000-110,100 GHz, the temperature coefficient of resonance frequencyτ f Is-10 to-1 ppm/DEG C.
3. A method for preparing the temperature-stable low-loss low-temperature cofired ceramic material according to claim 1 or 2, characterized in that: the method comprises the following steps: mgO, li 2 CO 3 、Nb 2 O 5 According to Li 3 Mg 2 NbO 6 Proportioning the stoichiometric ratio, ball milling the prepared raw materials for the first time, presintering, and mixing with V 2 O 5 And rutile crystal structure TiO 2 And mixing, performing secondary ball milling, granulating, forming and sintering to obtain the temperature-stable low-loss low-temperature cofired ceramic material.
4. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to claim 3, wherein the method comprises the following steps of: the method also comprises the steps of calcining MgO raw material at 1000 ℃ to ensure MgO crystal form and exclude surface water absorption; the presintering temperature is 850-1200 ℃ and the presintering time is 1-6 hours.
5. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to claim 3, wherein the method comprises the following steps of: tiO with rutile crystal structure 2 Selecting anatase type TiO 2 Is converted after high temperature treatment at 850-1200 ℃.
6. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to claim 3, wherein the method comprises the following steps of: the first ball milling and the second ball milling are wet ball milling; deionized water is used as a solvent, zirconium dioxide balls are used as ball milling media, and in the ball milling process, the mass ratio of raw materials, zirconium dioxide balls and deionized water is 1:3 to 6:1.5 to 3.5, the rotating speed is 200 to 350rad/min, and the ball milling time is 1 to 10 hours.
7. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to claim 3, wherein the method comprises the following steps of: the first ball milling is carried out to obtain a first slurry, the particle size D50 is 0.5-1.5 mu m, the second ball milling is carried out to obtain a second slurry, and the particle size D50 is 0.8-2.5 mu m.
8. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to claim 3, wherein the method comprises the following steps of: in the granulating process, the granulating agent is 10-15% polyvinyl alcohol aqueous solution by mass concentration.
9. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to claim 3, wherein the method comprises the following steps of: the sintering temperature is 800-950 ℃ and the sintering time is 1-6 hours.
10. The method for preparing the temperature-stable low-loss low-temperature co-fired ceramic material according to any one of claims 3 to 9, characterized in that: the sintering comprises heating to 400-500 ℃ from normal temperature at a heating rate of 1.0-2.5 ℃/min, maintaining at 400-500 ℃ for 1-6 hours, heating to 800-950 ℃ at a heating rate of 1.0-2.5 ℃/min, and sintering for 1-6 hours.
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