CN117383927A - Li for LTCC 3 Mg 2 TiO 5 F microwave dielectric ceramic material and preparation method thereof - Google Patents
Li for LTCC 3 Mg 2 TiO 5 F microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000011812 mixed powder Substances 0.000 claims description 26
- 239000011268 mixed slurry Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003979 granulating agent Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 10
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 229910052719 titanium Inorganic materials 0.000 abstract description 7
- 239000010936 titanium Substances 0.000 abstract description 7
- -1 titanium ions Chemical class 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 239000006104 solid solution Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000004891 communication Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000009766 low-temperature sintering Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000010354 integration Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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Abstract
The invention belongs to the field of electronic information functional materials and microelectronic devices, and particularly provides Li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material and the preparation method thereof are applied to the fields of wireless communication technology microwave dielectric substrates, integrated substrates, microwave antennas, microwave filters and the like. The invention uses LiF and Li 2 Mg 2 TiO 5 Formation of Li 3 Mg 2 TiO 5 F, the solid solution ceramic material effectively inhibits volatilization of lithium and reduction of tetravalent titanium ions, reduces the sintering temperature to below the melting point of the silver electrode, and realizes low-temperature sintering at 700-950 ℃, thereby meeting the application of LTCC; meanwhile, the microwave dielectric ceramic material provided by the invention also has excellent microwave dielectric properties: relative dielectric constant ε r 13.0-15.0, the quality factor Qxf is 110000 GHz-160000 GHz, and the temperature coefficient tau of resonance frequency f Provides a way for the development of microwave electronic components to high frequency, light weight and portability at-15 to-40 ppm/DEG CAn effective solution.
Description
Technical Field
The invention belongs to the field of electronic information functional materials and microelectronic devices, relates to a microwave dielectric ceramic material, and particularly provides Li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material and the preparation method thereof are applied to the fields of wireless communication technology microwave dielectric substrates, integrated substrates, microwave antennas, microwave filters and the like.
Background
The rapid development of technologies such as internet of things, mobile communication and radio frequency communication promotes the development of key electronic components towards the goals of miniaturization, light weight, high integration level, low loss and the like, and puts higher demands on electronic components such as various dielectric resonators, filters, diplexers, antennas and the like, so that researchers are required to take microwave dielectric ceramics with more excellent emission performance as substrate materials without breaking. Ideal microwave dielectric materials generally need to meet the following three conditions: (a) A material with a high relative permittivity may effectively reduce the size of the electronic device, while a material with a low relative permittivity may reduce the signal delay; (b) Low dielectric loss (tan δ), i.e., a high quality factor qxf, dielectric materials with a high quality factor can reduce insertion loss, thereby suppressing signal attenuation; (c) The good temperature coefficient of resonance frequency can ensure the use reliability of the electronic device in extreme environment. Meanwhile, the low temperature co-fired ceramic technology (LTCC technology) has become a mainstream process for preparing new generation electronic devices, and plays an important role in high integration, miniaturization and modularization of electronic devices, which requires that the sintering temperature of the microwave dielectric ceramic is lower than the melting point of the metal electrode (typically, silver electrode, the melting point is 961 ℃).
In recent years, researchers have been based on Li 2 O-MgO-TiO 2 Ternary systems developed a series of high quality products with different relative dielectric constantsA microwave dielectric ceramic material with good quality factor and resonant frequency temperature coefficient; wherein Li is 2 Mg 2 TiO 5 The microwave dielectric ceramic has relatively excellent dielectric property: epsilon r ＝13.4、Q×f＝95000GHz、τ f -32.5ppm/°c. However, li 2 Mg 2 TiO 5 The sintering temperature of the microwave dielectric ceramic is as high as 1320 ℃, and the high-temperature sintering can lead to the volatilization of lithium and the reduction of tetravalent titanium ions into trivalent titanium ions, thereby deteriorating the dielectric property; in addition, li 2 Mg 2 TiO 5 The relatively high sintering temperature of microwave dielectric ceramics also makes them unusable in LTCC technology. The present invention therefore envisages how to suppress lithium volatilization and the reduction of tetravalent titanium ions and to reduce the sintering temperature below the melting point of the silver electrode, in optimizing Li 2 Mg 2 TiO 5 The dielectric property of the microwave dielectric ceramic can meet the application of LTCC.
Disclosure of Invention
The invention aims at Li 2 Mg 2 TiO 5 The existing defect of microwave dielectric ceramics proposes Li for LTCC 3 Mg 2 TiO 5 F microwave dielectric ceramic material and preparation method thereof. The invention uses LiF and Li 2 Mg 2 TiO 5 Formation of Li 3 Mg 2 TiO 5 F, the solid solution ceramic material effectively inhibits volatilization of lithium and reduction of tetravalent titanium ions, and reduces the sintering temperature to below the melting point of the silver electrode, thereby meeting the application of LTCC; meanwhile, the microwave dielectric ceramic material provided by the invention has the characteristics of medium and low relative dielectric constant, high quality factor, adjustable resonant frequency temperature coefficient and the like, and provides an effective solution for the development of microwave electronic components to high frequency, light weight and portability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material is characterized by having a chemical general formula: li (Li) 3 Mg 2 TiO 5 And F, the crystal phase of the F is a cubic rock salt structure.
Further, the relative dielectric constant epsilon of the microwave dielectric ceramic material r 13.0-15.0, the quality factor Qxf is 110000 GHz-160000 GHz, and the temperature coefficient tau of resonance frequency f The sintering temperature is 700-950 ℃ and is minus 15 to minus 40 ppm/DEG C.
Li for LTCC 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material comprises the following steps:
step 1, using Li 2 CO 3 、MgO、TiO 2 LiF is taken as raw material, according to the molecular formula Li 3 Mg 2 TiO 5 Weighing the stoichiometric ratio of F to obtain a mixed raw material;
step 2, performing wet ball milling on the mixed raw materials weighed in the step 1 to obtain first mixed slurry;
step 3, drying the first mixed slurry obtained in the step 2, and grinding and sieving the dried mixed material to obtain dried first mixed powder;
step 4, calcining the first mixed powder obtained in the step 3 at 700-900 ℃ for 2-6 hours to enable the first mixed powder to perform a presintering reaction to obtain presintering powder;
step 5, performing wet ball milling on the presintered powder obtained in the step 4 to obtain second mixed slurry;
step 6, drying, grinding, granulating and sieving the second mixed slurry obtained in the step 5, and then pressing the collected particles to form a green body;
step 7, placing the green compact obtained in the step 6 in a sintering furnace, and sintering for 2-8 hours at 700-950 ℃ to prepare Li 3 Mg 2 TiO 5 F, microwave dielectric ceramic material.
Further, in the step 2 and the step 5, deionized water and zirconium dioxide balls are adopted as ball milling media for wet ball milling, and powder is mixed: deionized water: the mass ratio of the zirconium dioxide balls is 1: (2-5): (4-8), the rotating speed of the ball mill is 200-350 rad/min, and the ball milling time is 3-12 hours.
Further, in the step 3 and the step 6, the drying temperature of the slurry is 60-150 ℃.
Further, in the step 4, the temperature change rate of calcination is 1-5 ℃/min.
In the step 6, the granulating agent is polyvinyl alcohol solution (PVA), and the mass fraction of the PVA solution is 8-15%; and (5) sieving and collecting powder particles with the particle size of 20-200 meshes.
Further, in the step 7, the sintering curve is: firstly heating to 350-600 ℃, preserving heat for 1-5 hours at the temperature for discharging glue, and then heating to the sintering temperature; the temperature change rate is 1-5 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides Li for LTCC 3 Mg 2 TiO 5 F microwave dielectric ceramic material, because LiF has lower sintering temperature (800 ℃) and is matched with Li 2 Mg 2 TiO 5 Has the same crystal structure (cubic rock salt structure), and therefore, is formed by LiF and Li 2 Mg 2 TiO 5 Formation of Li 3 Mg 2 TiO 5 F, the solid solution ceramic effectively inhibits volatilization of lithium and reduction of tetravalent titanium ions; and O is 2- Ion quilt F - Ion substitution to form solid solution, the substitution weakens the strength of oxygen bond, so that diffusion is easier, the sintering temperature is reduced, thereby realizing low-temperature sintering at 700-950 ℃, and the sintering temperature is reduced to below the melting point of silver electrode, thereby meeting the application of LTCC; at the same time Li 3 Mg 2 TiO 5 The F microwave dielectric ceramic material has excellent microwave dielectric property: relative dielectric constant ε r 13.0-15.0, the quality factor Qxf is 110000 GHz-160000 GHz, and the temperature coefficient tau of resonance frequency f Is-15 to-40 ppm/DEG C.
In addition, the present invention provides Li 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material has rich raw materials and low cost, and Li is prepared 3 Mg 2 TiO 5 The F microwave dielectric ceramic material has smaller density, is favorable for industrialized application, and can be used as electronic devices such as antennas, dielectric resonators, filters, microstrip lines and the likeThe substrate material has important application prospect in the fields of microwave communication, radar systems, satellite communication and the like.
Drawings
FIG. 1 shows XRD patterns of the microwave dielectric ceramic materials prepared in examples 1 to 3 and comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantageous effects of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention provides Li for LTCC 3 Mg 2 TiO 5 F microwave dielectric ceramic material and preparation method thereof for solving Li 2 Mg 2 TiO 5 The problems with microwave dielectric ceramics at present, and other functions and advantages of the present invention can be more clearly illustrated by examples 1 to 3 and comparative example 1.
Example 1
This example provides a Li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material is prepared by the following steps:
step 1, according to Li 3 Mg 2 TiO 5 Stoichiometric ratio of F, weighing raw material Li 2 CO 3 、MgO、TiO 2 25g of LiF, wherein the purity of the raw materials is more than 99 percent;
step 2, carrying out wet ball milling on the mixed raw materials weighed in the step 1, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, rotating the planetary ball mill at 250rad/min for 10 hours to obtain first mixed slurry;
step 3, drying the first mixed slurry obtained in the step 2 at 120 ℃, grinding the dried mixed material, and sieving the ground mixed material through a 120-mesh standard sieve to obtain dried first mixed powder;
step 4, calcining the first mixed powder obtained in the step 3 at 850 ℃ for 4 hours, wherein the temperature change rate is 5 ℃/min, so that the first mixed powder performs a presintering reaction to obtain presintering powder;
and 5, carrying out wet ball milling on the presintered powder obtained in the step 4, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, the rotating speed of the planetary ball mill is 250rad/min, and the ball milling time is 10 hours, so as to obtain second mixed slurry;
step 6, drying the second mixed slurry obtained in the step 5 at 120 ℃, grinding, adding 10wt.% of PVA solution with the mass fraction of 12% for granulating, sieving by using a standard sieve, collecting powder particles between 40 meshes and 120 meshes, and pressing the collected particles into a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7, placing the green body obtained in the step 6 into a sintering furnace, wherein the temperature change rate is 3 ℃/min; the specific sintering curve is as follows: heating to 500 ℃, preserving heat for 2 hours at the temperature for discharging glue, heating to 800 ℃ for sintering for 4 hours, cooling to 500 ℃, and naturally cooling to obtain Li 3 Mg 2 TiO 5 F, microwave dielectric ceramic material.
Example 2
This example provides a Li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material is prepared by the following steps:
step 1, according to Li 3 Mg 2 TiO 5 Stoichiometric ratio of F, weighing raw material Li 2 CO 3 、MgO、TiO 2 25g of LiF, wherein the purity of the raw materials is more than 99 percent;
step 2, carrying out wet ball milling on the mixed raw materials weighed in the step 1, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, rotating the planetary ball mill at 250rad/min for 10 hours to obtain first mixed slurry;
step 3, drying the first mixed slurry obtained in the step 2 at 120 ℃, grinding the dried mixed material, and sieving the ground mixed material through a 120-mesh standard sieve to obtain dried first mixed powder;
step 4, calcining the first mixed powder obtained in the step 3 at 850 ℃ for 4 hours, wherein the temperature change rate is 5 ℃/min, so that the first mixed powder performs a presintering reaction to obtain presintering powder;
and 5, carrying out wet ball milling on the presintered powder obtained in the step 4, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, the rotating speed of the planetary ball mill is 250rad/min, and the ball milling time is 10 hours, so as to obtain second mixed slurry;
step 6, drying the second mixed slurry obtained in the step 5 at 120 ℃, grinding, adding 10wt.% of PVA solution with the mass fraction of 12% for granulating, sieving by using a standard sieve, collecting powder particles between 40 meshes and 120 meshes, and pressing the collected particles into a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7, placing the green body obtained in the step 6 into a sintering furnace, wherein the temperature change rate is 3 ℃/min; the specific sintering curve is as follows: heating to 500 ℃, preserving heat for 2 hours at the temperature for discharging glue, heating to 825 ℃ for sintering for 4 hours, cooling to 500 ℃, and naturally cooling to obtain Li 3 Mg 2 TiO 5 F, microwave dielectric ceramic material.
Example 3
This example provides a Li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material is prepared by the following steps:
step 1, according to Li 3 Mg 2 TiO 5 Stoichiometric ratio of F, weighing raw material Li 2 CO 3 、MgO、TiO 2 25g of LiF, wherein the purity of the raw materials is more than 99 percent;
step 2, carrying out wet ball milling on the mixed raw materials weighed in the step 1, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, rotating the planetary ball mill at 250rad/min for 10 hours to obtain first mixed slurry;
step 3, drying the first mixed slurry obtained in the step 2 at 120 ℃, grinding the dried mixed material, and sieving the ground mixed material through a 120-mesh standard sieve to obtain dried first mixed powder;
step 4, calcining the first mixed powder obtained in the step 3 at 850 ℃ for 4 hours, wherein the temperature change rate is 5 ℃/min, so that the first mixed powder performs a presintering reaction to obtain presintering powder;
and 5, carrying out wet ball milling on the presintered powder obtained in the step 4, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, the rotating speed of the planetary ball mill is 250rad/min, and the ball milling time is 10 hours, so as to obtain second mixed slurry;
step 6, drying the second mixed slurry obtained in the step 5 at 120 ℃, grinding, adding 10wt.% of PVA solution with the mass fraction of 12% for granulating, sieving by using a standard sieve, collecting powder particles between 40 meshes and 120 meshes, and pressing the collected particles into a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7, placing the green body obtained in the step 6 into a sintering furnace, wherein the temperature change rate is 3 ℃/min; the specific sintering curve is as follows: heating to 500 ℃, preserving heat for 2 hours at the temperature for discharging glue, heating to 850 ℃ for sintering for 4 hours, cooling to 500 ℃, and naturally cooling to obtain Li 3 Mg 2 TiO 5 F, microwave dielectric ceramic material.
Comparative example 1
This comparative example provides a Li 2 Mg 2 TiO 5 The microwave dielectric ceramic is prepared by the following steps:
step 1, according to Li 2 Mg 2 TiO 5 Is prepared by weighing raw material Li 2 CO 3 、MgO、TiO 2， A total of 25g, the purity of the raw materials is more than 99%;
step 2, carrying out wet ball milling on the mixed raw materials weighed in the step 1, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, rotating the planetary ball mill at 250rad/min for 10 hours to obtain first mixed slurry;
step 3, drying the first mixed slurry obtained in the step 2 at 120 ℃, grinding the dried mixed material, and sieving the ground mixed material through a 120-mesh standard sieve to obtain dried first mixed powder;
step 4, calcining the first mixed powder obtained in the step 3 at 1100 ℃ for 4 hours, wherein the temperature change rate is 5 ℃/min, so that the first mixed powder performs a presintering reaction to obtain presintering powder;
and 5, carrying out wet ball milling on the presintered powder obtained in the step 4, wherein the specific process is as follows: deionized water and zirconium dioxide balls are used as ball milling media; wherein, the mixed powder material: deionized water: the mass ratio of the zirconium dioxide balls is 1:3:5, the rotating speed of the planetary ball mill is 250rad/min, and the ball milling time is 10 hours, so as to obtain second mixed slurry;
step 6, drying the second mixed slurry obtained in the step 5 at 120 ℃, grinding, adding 10wt.% of PVA solution with the mass fraction of 12% for granulating, sieving by using a standard sieve, collecting powder particles between 40 meshes and 120 meshes, and pressing the collected particles into a cylindrical green body with the diameter of 12mm and the thickness of 6 mm;
step 7, placing the green body obtained in the step 6 into a sintering furnace, wherein the temperature change rate is 3 ℃/min; the specific sintering curve is as follows: heating to 500 ℃, preserving heat for 2 hours at the temperature for discharging glue, heating to 1325 ℃ for sintering for 4 hours, cooling to 500 ℃, and naturally cooling to obtain Li 2 Mg 2 TiO 5 Microwave dielectric ceramic material.
XRD patterns of the microwave dielectric ceramic materials prepared in the above examples 1 to 3 and comparative example 1 are shown in FIG. 1, and microwave dielectric properties are shown in Table 1;
TABLE 1
| Project | Chemical composition | Sintering temperature (. Degree. C.) | ε r | Q×f(GHz) | τ f (ppm/℃) |
| Example 1 | Li 3 Mg 2 TiO 5 F | 800 | 14.56 | 122464 | -29.4 |
| Example 2 | Li 3 Mg 2 TiO 5 F | 825 | 14.60 | 135119 | -28.6 |
| Example 3 | Li 3 Mg 2 TiO 5 F | 850 | 14.77 | 148105 | -25.9 |
| Comparative example 1 | Li 2 Mg 2 TiO 5 | 1325 | 14.91 | 97292 | -30.7 |
The dielectric properties of the examples of the present invention are analyzed in detail below in conjunction with the drawings and table 1:
in comparative example 1, li 2 Mg 2 TiO 5 The relative dielectric constant of the microwave dielectric ceramic is 14.91, the quality factor is 97292GHz resonant frequency temperature coefficient is-30.7 ppm/DEG C, and the sintering temperature is 1325 ℃; in examples 1 to 3, li in example 3 3 Mg 2 TiO 5 The maximum quality factor of the F microwave dielectric ceramic is 148105GHz, and the sintering temperature is 850 ℃, which shows that LiF and Li 2 Mg 2 TiO 5 The solid solution ceramic is formed, so that the dielectric loss of the microwave dielectric ceramic can be effectively reduced, the sintering temperature of the microwave dielectric ceramic can be obviously reduced, the microwave dielectric ceramic can meet the LTCC application, the relative dielectric constant is 14.77, the temperature coefficient of the resonant frequency is-25.9 ppm/DEG C, and the comprehensive performance is optimal.
In summary, the invention provides a Li for LTCC 3 Mg 2 TiO 5 F microwave dielectric ceramic material and preparation method thereof, and LiF and Li are used for preparing the same 2 Mg 2 TiO 5 Formation of Li 3 Mg 2 TiO 5 F solid solution ceramic effectively inhibits volatilization of lithium and reduction of tetravalent titanium ions, reduces sintering temperature to below melting point of silver electrode, obtains a microwave dielectric ceramic material with high Q value, satisfies application of LTCC, and provides a new solution for development of microwave electronic components to high frequency, light weight and integration.
While the invention has been described in terms of specific embodiments, any feature disclosed in this specification may be replaced by alternative features serving the equivalent or similar purpose, unless expressly stated otherwise; all of the features disclosed, or all of the steps in a method or process, except for mutually exclusive features and/or steps, may be combined in any manner.
Claims (8)
1. Li for LTCC 3 Mg 2 TiO 5 The F microwave dielectric ceramic material is characterized by having a chemical general formula: li (Li) 3 Mg 2 TiO 5 And F, the crystal phase of the F is a cubic rock salt structure.
2. Li for LTCC according to claim 1 3 Mg 2 TiO 5 F microwave dielectric ceramic material characterized in that the relative dielectric constant epsilon of the microwave dielectric ceramic material r 13.0-15.0, the quality factor Qxf is 110000 GHz-160000 GHz, and the temperature coefficient tau of resonance frequency f The sintering temperature is 700-950 ℃ and is minus 15 to minus 40 ppm/DEG C.
3. Li for LTCC according to claim 1 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material is characterized by comprising the following steps:
step 1, using Li 2 CO 3 、MgO、TiO 2 LiF is taken as raw material, according to the molecular formula Li 3 Mg 2 TiO 5 Weighing the stoichiometric ratio of F to obtain a mixed raw material;
step 2, performing wet ball milling on the mixed raw materials weighed in the step 1 to obtain first mixed slurry;
step 3, drying the first mixed slurry obtained in the step 2, and grinding and sieving the dried mixed material to obtain dried first mixed powder;
step 4, calcining the first mixed powder obtained in the step 3 at 700-900 ℃ for 2-6 hours to enable the first mixed powder to perform a presintering reaction to obtain presintering powder;
step 5, performing wet ball milling on the presintered powder obtained in the step 4 to obtain second mixed slurry;
step 6, drying, grinding, granulating and sieving the second mixed slurry obtained in the step 5, and then pressing the collected particles to form a green body;
step 7, placing the green compact obtained in the step 6 in a sintering furnace, and sintering for 2-8 hours at 700-950 ℃ to prepare Li 3 Mg 2 TiO 5 F, microwave dielectric ceramic material.
4. Li for LTCC according to claim 3 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material is characterized in that in the step 2 and the step 5, deionized water and zirconium dioxide balls are adopted as ball milling media for wet ball milling, and powder is mixed: deionized water: the mass ratio of the zirconium dioxide balls is 1: (2-5): (4-8), the rotating speed of the ball mill is 200-350 rad/min, and the ball milling time is 3-12 hours.
5. Li for LTCC according to claim 3 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material is characterized in that in the step 3 and the step 6, the drying temperature of the slurry is 60-150 ℃.
6. Li for LTCC according to claim 3 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material is characterized in that in the step 4, the temperature change rate of calcination is 1-5 ℃/min.
7. Li for LTCC according to claim 3 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material is characterized in that in the step 6, the granulating agent is polyvinyl alcohol solution (PVA), and the mass fraction of the PVA solution is 8-15%; and (5) sieving and collecting powder particles with the particle size of 20-200 meshes.
8. Li for LTCC according to claim 3 3 Mg 2 TiO 5 The preparation method of the F microwave dielectric ceramic material is characterized in that in the step 7, the sintering curve is as follows: firstly heating to 350-600 ℃, preserving heat for 1-5 hours at the temperature for discharging glue, and then heating to the sintering temperature; the temperature change rate is 1-5 ℃/min.
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